JP5732787B2 - Polyester elastomer resin composition - Google Patents
Polyester elastomer resin composition Download PDFInfo
- Publication number
- JP5732787B2 JP5732787B2 JP2010204219A JP2010204219A JP5732787B2 JP 5732787 B2 JP5732787 B2 JP 5732787B2 JP 2010204219 A JP2010204219 A JP 2010204219A JP 2010204219 A JP2010204219 A JP 2010204219A JP 5732787 B2 JP5732787 B2 JP 5732787B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester elastomer
- elastomer resin
- resin composition
- thermoplastic polyester
- plasticizer
- 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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- 229920000728 polyester Polymers 0.000 title claims description 49
- 229920001971 elastomer Polymers 0.000 title claims description 43
- 239000000806 elastomer Substances 0.000 title claims description 42
- 239000011342 resin composition Substances 0.000 title claims description 29
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 claims description 59
- -1 oxytetramethylene Chemical group 0.000 claims description 38
- 239000004014 plasticizer Substances 0.000 claims description 37
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 34
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 7
- 238000010102 injection blow moulding Methods 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 17
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 14
- 238000005259 measurement Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 13
- 238000004898 kneading Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000000071 blow moulding Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 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 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 2
- 239000004114 Ammonium polyphosphate Substances 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-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
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 2
- 235000010261 calcium sulphite Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-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
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012948 isocyanate Substances 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 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
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- JZWFDVDETGFGFC-UHFFFAOYSA-N salacetamide Chemical group CC(=O)NC(=O)C1=CC=CC=C1O JZWFDVDETGFGFC-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
- 239000007790 solid phase Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 2
- POLSVAXEEHDBMJ-UHFFFAOYSA-N (2-hydroxy-4-octadecoxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 POLSVAXEEHDBMJ-UHFFFAOYSA-N 0.000 description 1
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- AHBGXHAWSHTPOM-UHFFFAOYSA-N 1,3,2$l^{4},4$l^{4}-dioxadistibetane 2,4-dioxide Chemical compound O=[Sb]O[Sb](=O)=O AHBGXHAWSHTPOM-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AGHHRSWORINRIV-UHFFFAOYSA-N 1-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(NC(=O)NC2=O)=O)=C1 AGHHRSWORINRIV-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- ZJNLYGOUHDJHMG-UHFFFAOYSA-N 1-n,4-n-bis(5-methylhexan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CCC(C)NC1=CC=C(NC(C)CCC(C)C)C=C1 ZJNLYGOUHDJHMG-UHFFFAOYSA-N 0.000 description 1
- IHWDIGHWDQPQMQ-UHFFFAOYSA-N 1-octadecylsulfanyloctadecane Chemical compound CCCCCCCCCCCCCCCCCCSCCCCCCCCCCCCCCCCCC IHWDIGHWDQPQMQ-UHFFFAOYSA-N 0.000 description 1
- LLSKXGRDUPMXLC-UHFFFAOYSA-N 1-phenylpiperidine Chemical compound C1CCCCN1C1=CC=CC=C1 LLSKXGRDUPMXLC-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical class CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 1
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
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- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- AJCDFVKYMIUXCR-UHFFFAOYSA-N oxobarium;oxo(oxoferriooxy)iron Chemical compound [Ba]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O.O=[Fe]O[Fe]=O AJCDFVKYMIUXCR-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- NECLQTPQJZSWOE-UHFFFAOYSA-N spiro[5.5]undecane Chemical compound C1CCCCC21CCCCC2 NECLQTPQJZSWOE-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- CIWAOCMKRKRDME-UHFFFAOYSA-N tetrasodium dioxido-oxo-stibonatooxy-lambda5-stibane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Sb]([O-])(=O)O[Sb]([O-])([O-])=O CIWAOCMKRKRDME-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- IVIIAEVMQHEPAY-UHFFFAOYSA-N tridodecyl phosphite Chemical compound CCCCCCCCCCCCOP(OCCCCCCCCCCCC)OCCCCCCCCCCCC IVIIAEVMQHEPAY-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical class COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 description 1
- QOQNJVLFFRMJTQ-UHFFFAOYSA-N trioctyl phosphite Chemical compound CCCCCCCCOP(OCCCCCCCC)OCCCCCCCC QOQNJVLFFRMJTQ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- PYFJQRSJTZCTPX-UHFFFAOYSA-N tris(2,3-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(OP(OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)OC=2C(=C(C=CC=2)C(C)(C)C)C(C)(C)C)=C1C(C)(C)C PYFJQRSJTZCTPX-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- JZNDMMGBXUYFNQ-UHFFFAOYSA-N tris(dodecylsulfanyl)phosphane Chemical compound CCCCCCCCCCCCSP(SCCCCCCCCCCCC)SCCCCCCCCCCCC JZNDMMGBXUYFNQ-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 229960000281 trometamol Drugs 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は、射出成形などの成形に用いられるポリエステルエラストマー樹脂組成物に関する。特に、電気部品や家電製品、自動車部品や工業部材に用いられ、耐屈曲疲労性に優れるポリエステルエラストマー樹脂組成物に関する。 The present invention relates to a polyester elastomer resin composition used for molding such as injection molding. In particular, the present invention relates to a polyester elastomer resin composition that is used in electrical parts, home appliances, automobile parts, and industrial members and has excellent bending fatigue resistance.
リサイクル性の環境面、耐屈曲疲労性の性能面、そして生産性のコスト面における優位性から従来のゴムの代替として熱可塑性エラストマーが活用されている。その用途は幅広く、それに伴い樹脂に求められる性能も柔軟性、高耐熱性、高耐屈曲疲労性などの組合せが多岐に渡る。 Thermoplastic elastomers are used as an alternative to conventional rubber because of their superiority in environmental aspects of recyclability, performance of bending fatigue resistance, and cost of productivity. The application is wide, and the performance required for the resin is variously combined with flexibility, high heat resistance, and high bending fatigue resistance.
熱可塑性ポリエステルエラストマー樹脂の成形方法としてはインジェクション、押出し成形、ブロー成形があげられる。さらにブロー成形にはダイレクトブロー成形、インジェクションブロー成形、延伸ブロー成形、多層ブロー成形と様々な手法がある。 Examples of the method for molding the thermoplastic polyester elastomer resin include injection, extrusion molding, and blow molding. Further, blow molding includes various methods such as direct blow molding, injection blow molding, stretch blow molding, and multilayer blow molding.
熱可塑性ポリエステルエラストマー樹脂は、その成形方法に応じて要求される粘度特性が異なる。例えばインジェクションでは高せん断速度での十分な流動性を示す低粘度特性が要求され、押出し成形では固化までの間に十分な形状保持性を示す高粘度特性が要求される。 The thermoplastic polyester elastomer resin has different viscosity characteristics depending on the molding method. For example, injection requires low viscosity characteristics that exhibit sufficient fluidity at a high shear rate, and extrusion molding requires high viscosity characteristics that exhibit sufficient shape retention before solidification.
しかしながら様々な手法があるブロー成形では、一つの成形の中で工程に応じた粘度特性が必要となる。例えばインジェクションブロー成形の場合はインジェクションでパリソンを成形し、後にパリソンを熱してブロー成形を施す。つまりインジェクションによるパリソン成形時には、十分な流動性を示す低粘度特性が要求され、ブロー時にはパリソン形状保持のための高粘度特性が要求される。従来の熱可塑性ポリエステルエラストマー樹脂の固有粘度によって調節された粘度特性では、高粘度特性と低粘度特性の両立は困難であった。 However, blow molding with various methods requires viscosity characteristics according to the process in one molding. For example, in the case of injection blow molding, a parison is formed by injection, and then the parison is heated to perform blow molding. That is, a low viscosity characteristic exhibiting sufficient fluidity is required at the time of parison molding by injection, and a high viscosity characteristic for maintaining the parison shape is required at the time of blow. With the viscosity characteristics adjusted by the intrinsic viscosity of the conventional thermoplastic polyester elastomer resin, it is difficult to achieve both high viscosity characteristics and low viscosity characteristics.
粘度特性を調節する手法としては固有粘度の高い高重合度熱可塑性ポリエステルエラストマー樹脂を用いる方法、分岐を有する熱可塑性ポリエステルエラストマー樹組を用いる方法、更に熱可塑性ポリエステルエラストマー樹脂に対してイソシアネート化合物、エポキシ化合物の如き分岐剤を配合することなどが公知であるが、どれも高粘度特性と低粘度特性の両立を達成するものではない。 As a method for adjusting the viscosity characteristics, a method using a thermoplastic polyester elastomer resin having a high intrinsic viscosity and a high polymerization degree, a method using a thermoplastic polyester elastomer resin having a branch, and an isocyanate compound or an epoxy for the thermoplastic polyester elastomer resin are used. It is known to blend a branching agent such as a compound, but none achieves both high viscosity characteristics and low viscosity characteristics.
熱可塑性ポリエステルエラストマーへの粘度特性付与の方法として、そのほかに可塑剤の使用がある。例えば特許文献１では流動性付与のために可塑剤が用いられているが、ブロー成形時の高粘度特性については触れられていない。 Another method for imparting viscosity characteristics to a thermoplastic polyester elastomer is the use of a plasticizer. For example, Patent Document 1 uses a plasticizer for imparting fluidity, but does not mention the high viscosity characteristics at the time of blow molding.
従来の手法では解決できなかった、各種成形方法や工程に対応した粘度特性を示す熱可塑性ポリエステルエラストマー樹脂組成を達成することを課題とする。特に成形品加熱字時には高粘度特性を示し、高せん断速度では十分な流動性を示すことを目的とする。 It is an object to achieve a thermoplastic polyester elastomer resin composition exhibiting viscosity characteristics corresponding to various molding methods and processes that could not be solved by conventional techniques. In particular, it is intended to exhibit high viscosity characteristics when the molded product is heated and to exhibit sufficient fluidity at high shear rates.
前記課題を解決するため、本発明者らは鋭意、研究、検討した結果、遂に本発明を完成するに到った。つまり、本発明は、溶液粘度２．３〜２．８を示す熱可塑性ポリエステルエラストマー［Ａ］と可塑剤［Ｂ］の割合が、下記式１を満たすポリエステルエラストマー樹脂組成物であり、１８０℃、６ｒｐｍで１秒後の伸長粘度が１０００００Ｐａ・ｓ〜１００００００Ｐａ・ｓであることを特徴とするポリエステルエラストマー樹脂組成物である。
（式１） ０．０１≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．１
（式１において、Ｗ（Ｂ）／Ｗ（Ａ）は、ポリエステルエラストマー樹脂組成物中の、可塑剤［Ｂ］／熱可塑性ポリエステルエラストマー［Ａ］の質量割合である。）
In order to solve the above-mentioned problems, the present inventors have intensively studied and studied, and finally completed the present invention. That is, the present invention is a polyester elastomer resin composition in which the ratio of the thermoplastic polyester elastomer [A] and the plasticizer [B] having a solution viscosity of 2.3 to 2.8 satisfies the following formula 1, The polyester elastomer resin composition is characterized in that the extensional viscosity after 1 second at 6 rpm is 100,000 Pa · s to 1,000,000 Pa · s.
(Formula 1) 0.01 ≦ W (B) / W (A) ≦ 0.1
(In Formula 1, W (B) / W (A) is a mass ratio of plasticizer [B] / thermoplastic polyester elastomer [A] in the polyester elastomer resin composition.)
この場合において、２３０℃、２１６０ｇにおけるメルトフローインデックスの値が２〜１０ｇ／１０ｍｉｎであることが好ましい。
この場合において、前記Ｗ（Ｂ）／Ｗ（Ａ）が、下記式２を満たすことが好ましい。
（式２） ０．０２≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．０８
In this case, the melt flow index value at 230 ° C. and 2160 g is preferably 2 to 10 g / 10 min.
In this case, it is preferable that W (B) / W (A) satisfies the following formula 2.
(Formula 2) 0.02 ≦ W (B) / W (A) ≦ 0.08
この場合において、熱可塑性ポリエステルエラストマー［Ａ］が芳香族ジカルボン酸と低分子量グリコールからなるハードセグメントと、芳香族ジカルボン酸とポリ（オキシテトラメチレン）グリコールからなるソフトセグメントとを構成成分とすることが好ましい。 In this case, the thermoplastic polyester elastomer [A] may be composed of a hard segment made of an aromatic dicarboxylic acid and a low molecular weight glycol, and a soft segment made of an aromatic dicarboxylic acid and poly (oxytetramethylene) glycol. preferable.
［Ａ］及び［Ｂ］を（式１）の割合で混合されることで、高せん断速度時には可塑剤［Ｂ］による十分な流動性を示し、成形品加熱時は熱可塑性ポリエステルエラストマー［Ａ］の持つ固有粘度による形状保持性を示す利点を持つ。 By mixing [A] and [B] at a ratio of (Formula 1), the plasticizer [B] exhibits sufficient fluidity at a high shear rate, and the thermoplastic polyester elastomer [A] when the molded product is heated. It has the advantage of showing shape retention due to the inherent viscosity of
以下、本発明について詳細に説明する。
（熱可塑性ポリエステルエラストマー［Ａ］）
本発明にかかる熱可塑性ポリエステルエラストマー［Ａ］は、ハードセグメントとソフトセグメントから構成される。ハードセグメントは、芳香族ジカルボン酸と低分子量グリコールからなるポリエステルが好ましい。ソフトセグメントは、芳香族ジカルボン酸とポリ（オキシテトラメチレン）グリコールからなることが好ましい。
Hereinafter, the present invention will be described in detail.
(Thermoplastic polyester elastomer [A])
The thermoplastic polyester elastomer [A] according to the present invention is composed of a hard segment and a soft segment. The hard segment is preferably a polyester composed of an aromatic dicarboxylic acid and a low molecular weight glycol. The soft segment is preferably composed of an aromatic dicarboxylic acid and poly (oxytetramethylene) glycol.
本発明にかかる熱可塑性ポリエステルエラストマー［Ａ］において、ハードセグメントのポリエステルを構成する芳香族ジカルボン酸は、通常の芳香族ジカルボン酸が広く用いられ、特に限定されないが、主たる芳香族ジカルボン酸としてはテレフタル酸又はナフタレンジカルボン酸であることが望ましい。その他の酸成分としては、ジフェニルジカルボン酸、イソフタル酸、５−ナトリウムスルホイソフタル酸などの芳香族ジカルボン酸、シクロヘキサンジカルボン酸、テトラヒドロ無水フタル酸などの脂環族ジカルボン酸、コハク酸、グルタル酸、アジピン酸、アゼライン酸、セバシン酸、ドデカン二酸、ダイマー酸、水添ダイマー酸などの脂肪族ジカルボン酸などが挙げられる。これらは樹脂の融点を大きく低下させない範囲で用いられ、その量は全酸成分の３０モル％未満、好ましくは２０モル％未満である。 In the thermoplastic polyester elastomer [A] according to the present invention, the aromatic dicarboxylic acid constituting the hard segment polyester is not particularly limited, and the main aromatic dicarboxylic acid is terephthalate. An acid or naphthalenedicarboxylic acid is desirable. Other acid components include diphenyl dicarboxylic acid, isophthalic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, cycloaliphatic dicarboxylic acid, alicyclic dicarboxylic acid such as tetrahydrophthalic anhydride, succinic acid, glutaric acid, adipine Examples thereof include aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid, and hydrogenated dimer acid. These are used within a range that does not significantly lower the melting point of the resin, and the amount thereof is less than 30 mol%, preferably less than 20 mol% of the total acid component.
また、本発明にかかる熱可塑性ポリエステルエラストマー［Ａ］において、ハードセグメントのポリエステルを構成する低分子量グリコールは、一般の脂肪族又は脂環族ジオールが広く用いられ、特に限定されないが、主として炭素数２〜８のアルキレングリコール類であることが望ましい。具体的にはエチレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、１，６−ヘキサンジオール、１，４−シクロヘキサンジメタノール、ダイマーグリコールなどが挙げられる。エチレングリコール、１，４−ブタンジオール、１，４−シクロヘキサンジメタノール、ダイマーグリコーが好ましく、特に１，４−ブタンジオールが好ましい。 In the thermoplastic polyester elastomer [A] according to the present invention, the low molecular weight glycol constituting the hard segment polyester is not limited to a general aliphatic or alicyclic diol. It is desirable that the alkylene glycol is ˜8. Specific examples include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dimer glycol and the like. Ethylene glycol, 1,4-butanediol, 1,4-cyclohexanedimethanol and dimer glyco are preferred, and 1,4-butanediol is particularly preferred.
上記のハードセグメントのポリエステルを構成する成分としては、ブチレンテレフタレート単位あるいはブチレンナフタレート単位よりなるものが物性、成形性、コストパフォーマンスの点より好ましい。 The component constituting the hard segment polyester is preferably a butylene terephthalate unit or a butylene naphthalate unit from the viewpoint of physical properties, moldability, and cost performance.
また、本発明に用いられる熱可塑性ポリエステルエラストマー［Ａ］におけるハードセグメントを構成するポリエステルとして好適な芳香族ポリエステルは、通常のポリエステルの製造法に従って容易に得ることができる。また、かかるポリエステルは、数平均分子量５００００〜１０００００を有しているものが望ましい。 Moreover, the aromatic polyester suitable as polyester which comprises the hard segment in the thermoplastic polyester elastomer [A] used for this invention can be easily obtained according to the manufacturing method of a normal polyester. Moreover, what has the number average molecular weight 50000-100000 is desirable for this polyester.
また、本発明に用いられる熱可塑性ポリエステルエラストマー［Ａ］におけるソフトセグメントを構成する成分として好ましいポリ（オキシテトラメチレン）グリコールの数平均分子量は、下記する理由により、５００〜１５００のものが望ましい。好ましい下限は６００、より好ましくは８００である。本発明の特性を損なわない範囲で、ソフトセグメントの一部として、他のポリ（オキシアルキレン）グリコールや脂肪族ポリエステルグリコール等を用いても良い。 In addition, the number average molecular weight of poly (oxytetramethylene) glycol that is preferable as a component constituting the soft segment in the thermoplastic polyester elastomer [A] used in the present invention is preferably 500 to 1500 for the following reasons. A preferred lower limit is 600, more preferably 800. Other poly (oxyalkylene) glycols, aliphatic polyester glycols, and the like may be used as part of the soft segment as long as the characteristics of the present invention are not impaired.
本発明にかかる熱可塑性ポリエステルエラストマー［Ａ］は、ハードセグメントとソフトセグメントを反応させて得られるものである。ソフトセグメントの重量比率は、エラストマー性能を発現できる５〜８０重量％が好ましく、また４０〜６０重量％がより好ましい。上記反応は、反応温度、触媒濃度、反応時間の組み合わせを任意に決定して行なうことができる。すなわち、反応条件は、用いるハードセグメント及びソフトセグメントの種類及び量比、用いる装置の形状、攪拌状況などの種々の要因によってその適正値が変化する。 The thermoplastic polyester elastomer [A] according to the present invention is obtained by reacting a hard segment and a soft segment. The weight ratio of the soft segment is preferably 5 to 80% by weight, and more preferably 40 to 60% by weight, which can exhibit the elastomer performance. The above reaction can be carried out by arbitrarily determining a combination of reaction temperature, catalyst concentration, and reaction time. That is, the appropriate values of the reaction conditions vary depending on various factors such as the types and amount ratios of the hard segments and soft segments to be used, the shape of the apparatus to be used, and the stirring conditions.
本発明に用いられる熱可塑性ポリエステルエラストマー［Ａ］は、少量に限り三官能以上のポリカルボン酸、ポリオールを含んでもよい。例えば無水トリメリット酸、ベンゾフェノンテトラカルボン酸、トリメチロールプロパン、グリセリンなどを使用できる。 The thermoplastic polyester elastomer [A] used in the present invention may contain a tri- or higher functional polycarboxylic acid or polyol only in a small amount. For example, trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylolpropane, glycerin and the like can be used.
熱可塑性ポリエステルエラストマー［Ａ］の溶液粘度は、２．３〜２．８ｄｌ／ｇである必要がある。［Ａ］の溶液粘度は、２．４〜２．８ｄｌ／ｇが好ましく、２．５〜２．７ｄｌ／ｇがより好ましい。溶液粘度は、後記する実施例の項目で説明する方法により測定されるものである。溶液粘度が２．３未満では加熱時に形状を保持することが難しく、２．８超では可塑剤［Ｂ］による流動性付与の効果が著しく低下する。 The solution viscosity of the thermoplastic polyester elastomer [A] needs to be 2.3 to 2.8 dl / g. The solution viscosity of [A] is preferably 2.4 to 2.8 dl / g, more preferably 2.5 to 2.7 dl / g. The solution viscosity is measured by the method described in the item of Examples described later. If the solution viscosity is less than 2.3, it is difficult to maintain the shape during heating, and if it exceeds 2.8, the effect of imparting fluidity by the plasticizer [B] is significantly reduced.
次に本発明にかかる熱可塑性ポリエステルエラストマー［Ａ］を得る方法としては、公知の任意の方法を採用することができる。例えば、溶融重合法、溶液重合法、固相重合法などいずれも適宜用いられる。溶融重合法の場合、エステル交換法でも直接重合法であってもよい。樹脂の粘度を向上させるため、溶融重合後に固相重合を行うことはもちろん望ましいことである。
反応に用いる触媒としては、アンチモン触媒、ゲルマニウム触媒、チタン触媒が良好である。特にチタン触媒が好ましく、詳しくはテトラブチルチタネート、テトラメチルチタネートなどのテトラアルキルチタネート、シュウ酸チタンカリなどのシュウ酸金属塩などが好ましい。またその他の触媒としては公知の触媒であれば特に限定はしないが、ジブチルスズオキサイド、ジブチルスズジラウリレートなどのスズ化合物、酢酸鉛などの鉛化合物が挙げられる。
Next, as a method for obtaining the thermoplastic polyester elastomer [A] according to the present invention, any known method can be employed. For example, any of a melt polymerization method, a solution polymerization method, a solid phase polymerization method and the like can be used as appropriate. In the case of a melt polymerization method, a transesterification method or a direct polymerization method may be used. In order to improve the viscosity of the resin, it is of course desirable to perform solid phase polymerization after melt polymerization.
As the catalyst used for the reaction, an antimony catalyst, a germanium catalyst, and a titanium catalyst are preferable. In particular, a titanium catalyst is preferable. Specifically, tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal oxalates such as titanium potassium oxalate are preferable. The other catalyst is not particularly limited as long as it is a known catalyst, and examples thereof include tin compounds such as dibutyltin oxide and dibutyltin dilaurate, and lead compounds such as lead acetate.
（可塑剤［Ｂ］）
本発明において可塑剤［Ｂ］は熱可塑性ポリエステルエラストマーとの相溶性を損なわない限り以下の物を使用できる。フタル酸ジメチル、フタル酸ジエチル、フタル酸ジイソブチル、フタル酸ジ−２−エチルヘキシル等のフタル酸エステル、フタル酸ブチルベンジルエステル等のフタル酸混基エステル、コハク酸ジイソデシル、アジピン酸ジオクチル、セバシン酸ジオクチル等の脂肪族２塩基酸エステル、ジエチレングリコールジベンゾエート等のグリコールエステル、オレイン酸ブチル、アセチルリシノール酸メチル等の脂肪酸エステル、エポキシ化大豆油、エポキシ化アマニ油等のエポキシ可塑剤であり、その他、トリメリット酸トリオクチル、トリメリット酸トリ２−エチルヘキシル、エチルフタリルエチルグリコレート、ブチルフタリルブチルグリコレート、アセチルクエン酸トリブチル、塩素化パラフィン、ポリプロピレンアジペート、ポリエチレンセバケート、トリアセチン、トリブチリン、トルエンスルホンアミド、アルキルベンゼン、ビフェニル、部分水添ターフェニル、ショウノウ等を挙げることができる。
(Plasticizer [B])
In the present invention, the following can be used as the plasticizer [B] as long as the compatibility with the thermoplastic polyester elastomer is not impaired. Phthalic acid esters such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, di-2-ethylhexyl phthalate, phthalic acid mixed esters such as butyl benzyl phthalate, diisodecyl succinate, dioctyl adipate, dioctyl sebacate, etc. Aliphatic dibasic acid esters, glycol esters such as diethylene glycol dibenzoate, fatty acid esters such as butyl oleate and methyl acetylricinoleate, epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil, etc. Trioctyl acid, trimellitic acid tri-2-ethylhexyl, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, tributyl acetyl citrate, chlorinated paraffin, polypropylene adipate, polyethylene Sebacate, triacetin, can be cited tributyrin, toluenesulfonamide, alkylbenzenes, biphenyl, partially hydrogenated terphenyl, camphor and the like.
（ポリエステルエラストマー樹脂組成物）
本発明において、ポリエステルエラストマー樹脂組成物とは、前記熱可塑性ポリエステルエラストマー［Ａ］と前記可塑剤［Ｂ］を混合したものである。
本発明では、可塑剤［Ｂ］／熱可塑性ポリエステルエラストマー［Ａ］の質量割合・Ｗ（Ｂ）／Ｗ（Ａ）が、以下の（式１）を満たす必要がある。
（式１） ０．０１≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．１
この範囲であれば成形品加熱時には十分な高粘度特性を示し、高せん断速度時では十分な流動性を示す。
なお、Ｗ（Ｂ）／Ｗ（Ａ）が、以下の（式２）を満たすことが好ましい。この範囲を満たすことで、高せん断速度時には可塑剤［Ｂ］による十分な流動性、成形品加熱時は熱可塑性ポリエステルエラストマー［Ａ］の持つ固有粘度による形状保持性の両方を高度に満足させることができる。
（式２） ０．０２≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．０８
(Polyester elastomer resin composition)
In the present invention, the polyester elastomer resin composition is a mixture of the thermoplastic polyester elastomer [A] and the plasticizer [B].
In the present invention, the mass ratio of plasticizer [B] / thermoplastic polyester elastomer [A] · W (B) / W (A) needs to satisfy the following (formula 1).
(Formula 1) 0.01 ≦ W (B) / W (A) ≦ 0.1
If it is this range, sufficient high-viscosity characteristics will be exhibited when the molded product is heated, and sufficient fluidity will be exhibited at high shear rates.
In addition, it is preferable that W (B) / W (A) satisfy | fills the following (Formula 2). By satisfying this range, both the sufficient fluidity by the plasticizer [B] at high shear rate and the shape retention by the intrinsic viscosity of the thermoplastic polyester elastomer [A] when heating the molded product are highly satisfied. Can do.
(Formula 2) 0.02 ≦ W (B) / W (A) ≦ 0.08
本発明のポリエステルエラストマー樹脂組成物の１８０℃、６ｒｐｍで１秒後の伸長粘度が、１０００００Ｐａ・ｓ〜１００００００Ｐａ・ｓである必要がある。伸長粘度は、後記する実施例の項目で説明する方法により測定されるものである。伸張粘度が１０００００Ｐａ・ｓ未満の場合、ブロー時の賦型性が著しく低下し、１００００００Ｐａ・ｓ超の場合は形状を保持することが難しい。 The elongational viscosity after 1 second at 180 ° C. and 6 rpm of the polyester elastomer resin composition of the present invention needs to be 100,000 Pa · s to 1,000,000 Pa · s. The elongational viscosity is measured by the method described in the item of Examples described later. When the extensional viscosity is less than 100,000 Pa · s, the formability at the time of blowing is remarkably lowered, and when it exceeds 1,000,000 Pa · s, it is difficult to maintain the shape.
本発明のポリエステルエラストマー樹脂組成物の２３０℃、２１６０ｇにおけるメルトフローインデックスの値が２〜１０ｇ／１０ｍｉｎであることが好ましい。メルトフローインデックスの値が２ｇ／１０ｍｉｎ未満である場合、高せん断速度時に十分な流動性を得ることが出来ず、１０ｇ／１０ｍｉｎ超である場合、成形品加熱時に十分な形状保持性を得ることが出来ない。 The polyester elastomer resin composition of the present invention preferably has a melt flow index value of 2 to 10 g / 10 min at 230 ° C. and 2160 g. If the value of the melt flow index is less than 2 g / 10 min, sufficient fluidity cannot be obtained at a high shear rate, and if it exceeds 10 g / 10 min, sufficient shape retention can be obtained when the molded product is heated. I can't.
さらに、本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物には、目的に応じて種々の添加剤を配合して組成物を得ることができる。添加剤としては、公知のヒンダードフェノール系、硫黄系、燐系、アミン系の酸化防止剤、ヒンダードアミン系、トリアゾール系、ベンゾフェノン系、ベンゾエート系、ニッケル系、サリチル系などの光安定剤、帯電防止剤、滑剤、過酸化物などの分子調整剤、エポキシ系化合物、イソシアネート系化合物、カルボジイミド系化合物などの反応基を有する化合物、金属不活性剤、有機及び無機系の核剤、中和剤、制酸剤、防菌剤、蛍光増白剤、充填剤、難燃剤、難燃助剤、有機及び無機系の顔料などを添加することができる。 Furthermore, the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention can be blended with various additives depending on the purpose to obtain a composition. Additives include known hindered phenol-based, sulfur-based, phosphorus-based, amine-based antioxidants, hindered amine-based, triazole-based, benzophenone-based, benzoate-based, nickel-based, salicyl-based light stabilizers, antistatic agents, etc. Agents, lubricants, molecular modifiers such as peroxides, epoxy compounds, isocyanate compounds, compounds having reactive groups such as carbodiimide compounds, metal deactivators, organic and inorganic nucleating agents, neutralizing agents, control agents Acid agents, antibacterial agents, fluorescent brighteners, fillers, flame retardants, flame retardant aids, organic and inorganic pigments, and the like can be added.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができるヒンダードフェノール系酸化防止剤としては、３，５−ジ−ｔ−ブチル−４−ヒドロキシ−トルエン、ｎ−オクタデシル−β−（４’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）プロピオネート、テトラキス〔メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート〕メタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、カルシウム（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ベンジル−モノエチル−ホスフェート）、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート〕、ペンタエリスリチル−テトラキス〔３−（３，５−ジ−ｔ−ブチルアニリノ）−１，３，５−トリアジン、３，９−ビス〔１，１−ジメチル−２−｛β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝エチル〕２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、ビス〔３，３−ビス（４’−ヒドロキシ−３’−ｔ−ブチルフェニル）酪酸〕グリコールエステル、トリフェノール、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェノール）、Ｎ，Ｎ’−ビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニル〕ヒドラジン、２，２’−オキサミドビス〔エチル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，１，３−トリス（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシベンジル）−Ｓ−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）−トリオン、１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌレート、３，５−ジ−ｔ−ブチル−４−ヒドロキシヒドロシンナミックアヒドトリエステルウイズ−１，３，５−トリス（２−ヒドロキシエチル）−Ｓ−トリアジン−２，４，６（１Ｈ，３Ｈ，５Ｈ）、Ｎ，Ｎ−ヘキサメチレンビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−ヒドロシンナアミド）、３，９−ビス〔２−｛３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝−１，１−ジメチルエチル〕−２，４，８，１０−テトラオキサスピロ〔５．５〕ウンデカンなどを挙げることができる。 Examples of hindered phenolic antioxidants that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention include 3,5-di-t-butyl-4-hydroxy-toluene, n- Octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, calcium (3,5-di-tert-butyl-4) -Hydroxy-benzyl-monoethyl-phosphate), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4- Droxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butylanilino) -1,3,5-triazine, 3,9-bis [1,1-dimethyl-2- { β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis [3,3-bis (4 '-Hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, triphenol, 2,2'-ethylidenebis (4,6-di-t-butylphenol), N, N'-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2′-oxamidobis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Lopionate], 1,1,3-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6 (1H, 3H, 5H) -trione, , 3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-4-hydroxyhydrocinnamic atide triester with-1 , 3,5-tris (2-hydroxyethyl) -S-triazine-2,4,6 (1H, 3H, 5H), N, N-hexamethylenebis (3,5-di-t-butyl-4- Hydroxy-hydrocinnamide), 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 8,10-Tetraoki Or the like can be mentioned spiro [5.5] undecane.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができる硫黄系酸化防止剤としては、ジラウリル−３，３’−チオジプロピオン酸エステル、ジミリスチル−３，３’−チオジウロピオン酸エステル、ジステアリル−３，３’−チオジプロピオン酸エステル、ラウリルステアリル−３，３’−チオジプロピオン酸エステル、ジラウリルチオジプロピオネート、ジオクタデシルサルファイド、ペンタエリストリール−テトラ（β−ラウリル−チオプロピオネート）エステルなどを挙げることができる。 Examples of the sulfur-based antioxidant that can be added to the thermoplastic polyester elastomer or the polyester elastomer resin composition used in the present invention include dilauryl-3,3′-thiodipropionic acid ester, dimyristyl-3,3′-. Thiodiuropionate, distearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, dilauryl thiodipropionate, dioctadecyl sulfide, pentaerythritol tetra (β-lauryl-thiopropionate) ester and the like.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができる燐系酸化防止剤としては、トリス（ミックスド、モノ及びジノリルフェニル）フォスファイト、トリス（２，３−ジ−ｔ−ブチルフェニル）フォスファイト、４，４’−ブチリデン−ビス（３−メチル−６−ｔ−ブチルフェニル−ジ−トリデシル）フォスファイト、１，１，３−トリス（２−メチル−４−ジ−トリデシルホスファイト−５−ｔ−ブチルフェニル）ブタン、トリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトール−ジ−フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４’−ビフェニレンフォスファナイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリストール−ジ−フォスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）４，４’−ビフェニレンジホスフォナイト、トリフェニルホスファイト、ジフェニルデシルホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリドデシルホスファイト、トリオクタデシルフォスファイト、トリノニルフェニルホスファイト、トリドデシルトリチオホスファイトなどを挙げることができる。 Examples of the phosphorus-based antioxidant that can be blended in the thermoplastic polyester elastomer or the polyester elastomer resin composition used in the present invention include tris (mixed, mono and dinolylphenyl) phosphite, tris (2,3- Di-t-butylphenyl) phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4) -Di-tridecyl phosphite-5-t-butylphenyl) butane, tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di -Phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenephosphanai Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4'-biphenylenediphosphonite , Triphenyl phosphite, diphenyl decyl phosphite, tridecyl phosphite, trioctyl phosphite, tridodecyl phosphite, trioctadecyl phosphite, trinonylphenyl phosphite, tridodecyl trithiophosphite and the like.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができるアミン系酸化防止剤としては、Ｎ，Ｎ−ジフェニルエチレンジアミン、Ｎ，Ｎ−ジフェニルアセトアミジン、Ｎ，Ｎ−ジフェニルフルムアミジン、Ｎ−フェニルピペリジン、ジベンジルエチレンジアミン、トリエタノールアミン、フェノチアジン、Ｎ，Ｎ’−ジ−ｓｅＣ−ブチル−ｐ−フェニレンジアミン、４，４’−テトラメチル−ジアミノジフェニルメタン、Ｐ，Ｐ’−ジオクチル−ジフェニルアミン、Ｎ，Ｎ’−ビス（１，４−ジメチル−ペンチル）−ｐ−フェニレンジアミン、フェニル−α−ナフチルアミン、フェニル−β−ナフチルアミン、４，４’−ビス（４−α，α−ジメチル−ベンジル）ジフェニルアミンなどのアミン類及びその誘導体やアミンとアルデヒドの反応生成物、アミンとケトンの反応生成物から挙げることができる。 Examples of amine-based antioxidants that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention include N, N-diphenylethylenediamine, N, N-diphenylacetamidine, and N, N-diphenyl. Flumamidine, N-phenylpiperidine, dibenzylethylenediamine, triethanolamine, phenothiazine, N, N'-di-seC-butyl-p-phenylenediamine, 4,4'-tetramethyl-diaminodiphenylmethane, P, P'- Dioctyl-diphenylamine, N, N′-bis (1,4-dimethyl-pentyl) -p-phenylenediamine, phenyl-α-naphthylamine, phenyl-β-naphthylamine, 4,4′-bis (4-α, α- Dimethyl-benzyl) diphenyl Amines such as tromethamine and the reaction product of a derivative thereof or an amine and an aldehyde, can be mentioned a reaction product of amine and ketone.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができるベンゾフェノン系、ベンゾトリアゾール系、トリアゾール系、ニッケル系、サリチル系光安定剤としては、２，２’−ジヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノン、ｐ−ｔ−ブチルフェニルサリシレート、２，４−ジ−ｔ−ブチルフェニル−３，５−ジ−ｔ−ブチル−４−ヒドロキシベンゾエート、２−（２’−ヒドロキシ−５’−メチルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−アミル−フェニル）ベンゾトリアゾール、２−〔２’−ヒドロキシ−３’、５’−ビス（α，α−ジメチルベンジルフェニル）ベンゾトリアゾール、２−（２’−ヒドロキシ−３’−ｔ−ブチル−５’−メチルフェニル）−５−クロロベンアゾトリアゾール、２−（２’−ヒドロキシ−３’，５’−ジ−ｔ−ブチルフェニル）−５−クロロベンゾチリアゾール、２，５−ビス−〔５’−ｔ−ブチルベンゾキサゾリル−（２）〕−チオフェン、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル燐酸モノエチルエステル）ニッケル塩、２−エトキシ−５−ｔ−ブチル−２’−エチルオキサリックアシッド−ビス−アニリド８５〜９０％と２−エトキシ−５−ｔ−ブチル−２’−エチル−４’−ｔ−ブチルオキサリックアシッド−ビス−アニリド１０〜１５％の混合物、２−〔２−ヒドロキシ−３，５−ビス（α，α−ジメチルベンジル）フェニル〕−２Ｈ−ベンゾトリアゾール、２−エトキシ−２’−エチルオキサザリックアシッドビスアニリド、２−〔２’−ヒドロオキシ−５’−メチル−３’−（３’’，４’’，５’’，６’’−テトラヒドロフタルイミド−メチル）フェニル〕ベンゾトリアゾール、ビス（５−ベンゾイル−４−ヒドロキシ−２−メトキシフェニル）メタン、２−（２’−ヒドロキシ−５’−ｔ−オクチルフェニル）ベンゾトリアゾール、２−ヒドロキシ−４−ｉ−オクトキシベンゾフェノン、２−ヒドロキシ−４−ドデシルオキシベンゾフェノン、２−ヒドロキシ−４−オクタデシルオキシベンゾフェノン、サリチル酸フェニルなどの光安定剤を挙げることができる。 The benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers that can be blended in the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention include 2,2′-dihydroxy- 4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, pt-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-amyl-phenyl) benzotriazole, 2- [2′-hydroxy -3 ′, 5′-bis (α, α-dimethylbenzylphenyl) benzotria Sol, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzazotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butyl) Phenyl) -5-chlorobenzothiazole, 2,5-bis- [5'-t-butylbenzoxazolyl- (2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxy Benzyl phosphate monoethyl ester) nickel salt, 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid-bis-anilide 85-90% and 2-ethoxy-5-t-butyl-2'-ethyl- 4′-tert-butyl oxalic acid-bis-anilide 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-Ethoxy-2′-ethyloxazalic acid bisanilide, 2- [2′-hydroxy-5′-methyl-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimide) -Methyl) phenyl] benzotriazole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2-hydroxy-4- Examples thereof include light stabilizers such as i-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and phenyl salicylate.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができる充填剤としては、酸化マグネシウム、酸化アルミニウム、酸化珪素、酸化カルシウム、酸化チタン（ルチル型、アナターゼ型）、酸化クロム（三価）、酸化鉄、酸化亜鉛、シリカ、珪藻土、アルミナ繊維、酸化アンチモン、バリウムフェライト、ストロンチウムフェライト、酸化ベリリウム、軽石、軽石バルーンなどの酸化物や水酸化マウネシウム、水酸化アルミニウム、塩基性炭酸マグネシウムなどの塩基性物又は水酸化物又は、炭酸マグネシウム、炭酸カルシウウム、炭酸バリウム、炭酸アンモニウム、亜硫酸カルシウム、ドロマイト、ドーソナイトなどの炭酸塩又は、硫酸カルシウム、硫酸バリウム、硫酸アンモニウム、亜硫酸カルシウム、塩基性硫酸マグネシウムなどの（亜）硫酸塩又は、珪酸ナトリウム、珪酸マグネシウム、珪酸アルミニウム、珪酸カリウム、珪酸カルシウム、タルク、クレー、マイカ、アスベスト、ガラス繊維、モンモリナイト、ガラスバルーン、ガラスビーズ、ペントナイトなどの珪酸塩又は、カオリン（陶土）、パーライト、鉄粉、銅粉、鉛粉、アルミニウム粉、タングステン粉、硫化モリブデン、カーボンブラック、ボロン繊維、炭化珪素繊維、黄銅繊維、チタン酸カリウム、チタン酸ジルコン酸鉛、硼酸亜鉛、硼酸アルミニウム、メタ硼酸バリウム、硼酸カルシウム、硼酸ナトリウムなどを挙げることができる。 Fillers that can be blended in the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention include magnesium oxide, aluminum oxide, silicon oxide, calcium oxide, titanium oxide (rutile type, anatase type), and oxidation. Oxides such as chromium (trivalent), iron oxide, zinc oxide, silica, diatomaceous earth, alumina fiber, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, pumice, pumice balloon, etc., manesium hydroxide, aluminum hydroxide, basic Basic substances or hydroxides such as magnesium carbonate, or carbonates such as magnesium carbonate, calcium carbonate, barium carbonate, ammonium carbonate, calcium sulfite, dolomite, and dawsonite, or calcium sulfate, barium sulfate, and ammonium sulfate (Sulphite) sulfate such as monium, calcium sulfite, basic magnesium sulfate or sodium silicate, magnesium silicate, aluminum silicate, potassium silicate, calcium silicate, talc, clay, mica, asbestos, glass fiber, montmorillonite, glass balloon, glass Silicates such as beads and pentonite or kaolin (ceramic clay), perlite, iron powder, copper powder, lead powder, aluminum powder, tungsten powder, molybdenum sulfide, carbon black, boron fiber, silicon carbide fiber, brass fiber, titanic acid Examples include potassium, lead zirconate titanate, zinc borate, aluminum borate, barium metaborate, calcium borate, and sodium borate.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができる難燃助剤としては、三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、ピロアンチモン酸ソーダ、二酸化錫、メタ硼酸亜鉛、水酸化アルミニウム、水酸化マグネシウム、酸化ジルコニウム、酸化モリブデン、赤燐系化合物、ポリリン酸アンモニウム塩、メラミンシアヌレート、四フッ化エチレンなどが挙げられる。 Flame retardant aids that can be incorporated into the thermoplastic polyester elastomer or polyester elastomer resin composition used in the present invention include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, meta Examples thereof include zinc borate, aluminum hydroxide, magnesium hydroxide, zirconium oxide, molybdenum oxide, red phosphorus compound, ammonium polyphosphate, melamine cyanurate, and tetrafluoroethylene.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができるトリアジン基を有する化合物及び／又はその誘導体としては、メラミン、メラミンシアヌレート、燐酸メラメン、スルファミン酸グアニジンなどが挙げられる。 Examples of the thermoplastic polyester elastomer or the compound having a triazine group and / or a derivative thereof that can be blended in the polyester elastomer resin composition include melamine, melamine cyanurate, melamate phosphate, guanidine sulfamate, and the like. It is done.
本発明に用いられる熱可塑性ポリエステルエラストマーまたは、ポリエステルエラストマー樹脂組成物に配合することができる燐化合物の無機系燐化合物としては、赤燐系化合物、ポリリン酸アンモニウム塩などが挙げられる。赤燐系化合物としては、赤燐に樹脂をコートしたもの、アルミニウムとの複合化合物などが挙げられる。有機系燐化合物としては、燐酸エステル、燐酸メラミンなどが挙げられる。燐酸エステルとしては、ホスフェート類、ホスホネート類、ホスフィネート類のトリメチルホスフェート、トリエチルフォスフェート、トリブチルフォスフェート、トリオクチルホスフェート、トリオクチルフォスフィート、トリブトキシエチルフォスフェート、オクチルジフェニルフォスフェート、トリクレジルホスフェート、クレジルジフェニルフォスフェート、トリフェニルフォスフェート、トリキシレニルフォスフェート、トリス・イソプロピルフェニルフォスフェート、ジエチル−Ｎ，Ｎ−ビス（２−ヒドロキシエチル）アミノメチルホスホネート、ビス（１，３−フェニレンジフェニル）ホスフェート、芳香族縮合燐酸エステルの１，３−〔ビス（２，６−ジメチルフェノキシ）ホスフェニルオキシ〕ベンゼン、１，４−〔ビス（２，６−ジメチルフェノキシ）ホスフェニルオキシ〕ベンゼンなどが耐加水分解や熱安定性、難燃性から好ましい。 Examples of the inorganic phosphorus compound of the phosphorus compound that can be blended in the thermoplastic polyester elastomer or the polyester elastomer resin composition used in the present invention include red phosphorus compounds and ammonium polyphosphate. Examples of red phosphorus compounds include red phosphorus coated with a resin, and composite compounds with aluminum. Examples of organic phosphorus compounds include phosphate esters and melamine phosphate. Phosphate esters include phosphates, phosphonates, trimethyl phosphates of phosphinates, triethyl phosphate, tributyl phosphate, trioctyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, octyl diphenyl phosphate, tricresyl phosphate, Cresyl diphenyl phosphate, triphenyl phosphate, trixylenyl phosphate, tris-isopropylphenyl phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, bis (1,3-phenylenediphenyl) Phosphate, aromatic condensed phosphate ester 1,3- [bis (2,6-dimethylphenoxy) phosphenyloxy] benzene, 1,4- [bis 2,6-dimethyl-phenoxy) such as phosphorylase phenyloxy] benzene hydrolysis and heat stability, preferably a flame retardant.
これらの添加物の配合方法としては、加熱ロール、押出機、バンバリミキサーなどの混練機を用いて配合することができる。また、熱可塑性ポリエステルエラストマーを製造する際のエステル交換反応の前又は重縮合反応前のオリゴマー中に、添加及び混合することができる。 As a method for blending these additives, they can be blended using a kneader such as a heating roll, an extruder, or a Banbury mixer. Moreover, it can add and mix in the oligomer before the transesterification reaction or polycondensation reaction at the time of manufacturing a thermoplastic polyester elastomer.
以下に実施例を示し、本発明をより具体的に説明するが、これに限定されるものではない。
（測定法）
伸長粘度測定：
ＡＲＥＳ−Ｇ２レオメーターのＥＶＦオプション（ＡＴテクノロジー社製）を用い、試験環境温度は試験温度１８０℃、回転数６ｒｐｍで試験を行なった。試験片はインジェクションで５ｍｍ×５５ｍｍ×１ｍｍｔを用意した。実際の成形を考慮し加熱後変形が終了するまでの最大時間である１秒後の伸張粘度を測定した。単位は、Ｐａ・ｓである。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto.
(Measurement method)
Elongation viscosity measurement:
Using the EVF option (manufactured by AT Technology) of ARES-G2 rheometer, the test environment temperature was tested at a test temperature of 180 ° C. and a rotation speed of 6 rpm. The test piece prepared 5 mm x 55 mm x 1 mmt by injection. Considering actual molding, the extensional viscosity after 1 second, which is the maximum time until the deformation after heating was completed, was measured. The unit is Pa · s.
メルトフローインデックス：
メルトインデックサＦ−Ｂ０１（東洋精機製）を用い、ＡＳＴＭ−Ｄ−１２３８法に準拠し、２１６０ｇ、２３０℃で測定した。単位は、ｇ／１０ｍｉｎである。
Melt flow index:
Using a melt indexer F-B01 (manufactured by Toyo Seiki Co., Ltd.), it was measured at 2160 g and 230 ° C. in accordance with ASTM-D-1238 method. The unit is g / 10 min.
溶液粘度：
熱可塑性ポリエステルエラストマー０．０５ｇを２５ｍＬの混合溶媒（フェノール／テトラクロロエタン＝６０／４０）に溶かし、オストワルド粘度計を用いて３０℃で測定した。
Solution viscosity:
0.05 g of thermoplastic polyester elastomer was dissolved in 25 mL of a mixed solvent (phenol / tetrachloroethane = 60/40) and measured at 30 ° C. using an Ostwald viscometer.
高せん断速度時流動性：
射出成形機ＥＣ−１００Ｎ（東芝機械製）を用いて１ｍｍｔのスパイラルフローの金型を用い流動性を測定した。シリンダ温度は２４０℃、金型温度は４０℃、射出圧力は１６０ＭＰａとした。評価は２００ｍｍ以上の流動性で◎、１５０ｍｍから２００ｍｍ未満で○、１００ｍｍから１５０ｍｍ未満で△、１００ｍｍ未満を×とした。
High shear rate fluidity:
The fluidity was measured using a 1 mmt spiral flow mold using an injection molding machine EC-100N (manufactured by Toshiba Machine). The cylinder temperature was 240 ° C., the mold temperature was 40 ° C., and the injection pressure was 160 MPa. The evaluation was ◎, with a fluidity of 200 mm or more, ◯, 150 mm to less than 200 mm, ◯, 100 mm to less than 150 mm, Δ, and less than 100 mm as x.
成形品加熱時形状保持性：
射出成形機ＥＣ−１００Ｎ（東芝機械製）を用いて２００ｍｍ×２００ｍｍ×２．５ｍｍｔの成形品を成形した後、１５０℃環境温度下で１８０ｍｍ離れたブロックの上に置いた成形品のたわみを測定した。評価は５ｍｍ以下で◎、５ｍｍ超から１０ｍｍで○、１０ｍｍ超から１５ｍｍで△、１５ｍｍ超を×とした。
Shape retention during heating of molded parts:
After molding a molded product of 200 mm x 200 mm x 2.5 mmt using an injection molding machine EC-100N (manufactured by Toshiba Machine), the deflection of the molded product placed on a block 180 mm away at 150 ° C ambient temperature is measured. did. The evaluation was 5 mm or less, ◎ over 5 mm to 10 mm, ◯ over 10 mm to 15 mm, and Δ over 15 mm.
（熱可塑性ポリエステルエラストマー［Ａ］の作製）
熱可塑性ポリエステルエラストマーＡ１：
ジメチルテレフタレート（ＤＭＴ）３２０ｇ、１，４−ブタンジオール（ＢＤ）２６０ｇ、ポリテトラメチレングリコール（ＰＴＭＧ，数平均分子量１０００）４２０ｇ、イルガノックス−１３３０（チバジャパン社製）１．８ｇ、テトラブチルチタネート（ＴＢＴ）１．０ｇを４Ｌのオートクレーブに仕込み、室温から２２０℃まで３時間かけて昇温しエステル交換反応を行った。次いで缶内を徐々に減圧すると共に更に昇温し、４５分かけて２５０℃、１ｔｏｒｒ以下にして初期縮合反応を行った。さらに２５０℃、１ｔｏｒｒ以下の状態で溶液粘度が２．７となるまで重合反応を行い、ポリマーをペレット状に取り出した。
(Production of thermoplastic polyester elastomer [A])
Thermoplastic polyester elastomer A1:
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, number average molecular weight 1000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate ( TBT) (1.0 g) was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed at 250 ° C. and 1 torr or less until the solution viscosity became 2.7, and the polymer was taken out into a pellet form.
熱可塑性ポリエステルエラストマーＡ２：
ジメチルテレフタレート（ＤＭＴ）３２０ｇ、１，４−ブタンジオール（ＢＤ）２６０ｇ、ポリテトラメチレングリコール（ＰＴＭＧ，数平均分子量１０００）４２０ｇ、イルガノックス−１３３０（チバジャパン社製）１．８ｇ、テトラブチルチタネート（ＴＢＴ）１．０ｇを４Ｌのオートクレーブに仕込み、室温から２２０℃まで３時間かけて昇温しエステル交換反応を行った。次いで缶内を徐々に減圧すると共に更に昇温し、４５分かけて２５０℃、１ｔｏｒｒ以下にして初期縮合反応を行った。さらに２５０℃、１ｔｏｒｒ以下の状態で溶液粘度が２．５となるまで重合反応を行い、ポリマーをペレット状に取り出した。
Thermoplastic polyester elastomer A2:
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, number average molecular weight 1000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate ( TBT) (1.0 g) was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Furthermore, a polymerization reaction was performed until the solution viscosity became 2.5 in a state of 250 ° C. and 1 torr or less, and the polymer was taken out into a pellet form.
熱可塑性ポリエステルエラストマーＡ３：
ジメチルテレフタレート（ＤＭＴ）３２０ｇ、１，４−ブタンジオール（ＢＤ）２６０ｇ、ポリテトラメチレングリコール（ＰＴＭＧ，数平均分子量１０００）４２０ｇ、イルガノックス−１３３０（チバジャパン社製）１．８ｇ、テトラブチルチタネート（ＴＢＴ）１．０ｇを４Ｌのオートクレーブに仕込み、室温から２２０℃まで３時間かけて昇温しエステル交換反応を行った。次いで缶内を徐々に減圧すると共に更に昇温し、４５分かけて２５０℃、１ｔｏｒｒ以下にして初期縮合反応を行った。さらに２５０℃、１ｔｏｒｒ以下の状態で溶液粘度が２．０となるまで重合反応を行い、ポリマーをペレット状に取り出した。
Thermoplastic polyester elastomer A3:
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, number average molecular weight 1000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate ( TBT) (1.0 g) was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed until the solution viscosity became 2.0 at 250 ° C. and 1 torr or less, and the polymer was taken out into a pellet form.
熱可塑性ポリエステルエラストマーＡ４：
ジメチルテレフタレート（ＤＭＴ）３２０ｇ、１，４−ブタンジオール（ＢＤ）２６０ｇ、ポリテトラメチレングリコール（ＰＴＭＧ，数平均分子量１０００）４２０ｇ、イルガノックス−１３３０（チバジャパン社製）１．８ｇ、テトラブチルチタネート（ＴＢＴ）１．０ｇを４Ｌのオートクレーブに仕込み、室温から２２０℃まで３時間かけて昇温しエステル交換反応を行った。次いで缶内を徐々に減圧すると共に更に昇温し、４５分かけて２５０℃、１ｔｏｒｒ以下にして初期縮合反応を行った。さらに２５０℃、１ｔｏｒｒ以下の状態で溶液粘度が３．０となるまで重合反応を行い、ポリマーをペレット状に取り出した。
Thermoplastic polyester elastomer A4:
320 g of dimethyl terephthalate (DMT), 260 g of 1,4-butanediol (BD), 420 g of polytetramethylene glycol (PTMG, number average molecular weight 1000), 1.8 g of Irganox-1330 (manufactured by Ciba Japan), tetrabutyl titanate ( TBT) (1.0 g) was charged into a 4 L autoclave, and the temperature was increased from room temperature to 220 ° C. over 3 hours to conduct a transesterification reaction. Next, the inside of the can was gradually depressurized and further heated, and an initial condensation reaction was performed at 250 ° C. and 1 torr or less over 45 minutes. Further, a polymerization reaction was performed until the solution viscosity became 3.0 in a state of 250 ° C. and 1 torr or less, and the polymer was taken out into a pellet form.
（可塑剤［Ｂ１］）
本実施例で用いた可塑剤Ｂ１は、フタル酸ジ−２−エチルヘキシルを使用した。
（可塑剤［Ｂ２］）
本実施例で用いた可塑剤Ｂ２は、アジピン酸ジオクチルを使用した。
（可塑剤［Ｂ３］）
本実施例で用いた可塑剤Ｂ３は、トリメリット酸トリ２−エチルヘキシルを使用した。
（可塑剤［Ｂ４］）
本実施例で用いた可塑剤Ｂ４は、アセチルクエン酸トリブチルを使用した。
（可塑剤［Ｂ５］）
本実施例で用いた可塑剤Ｂ５は、セバシン酸ジオクチルを使用した。
(Plasticizer [B1])
The plasticizer B1 used in this example was di-2-ethylhexyl phthalate.
(Plasticizer [B2])
The plasticizer B2 used in this example was dioctyl adipate.
(Plasticizer [B3])
As the plasticizer B3 used in this example, tri-2-ethylhexyl trimellitic acid was used.
(Plasticizer [B4])
As the plasticizer B4 used in this example, tributyl acetylcitrate was used.
(Plasticizer [B5])
As the plasticizer B5 used in this example, dioctyl sebacate was used.
（実施例１）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
Example 1
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B1 to W (B) / W (A) = 0.05, melting and kneading in the extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例２）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．０１とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 2)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B1 to W (B) / W (A) = 0.01, melting and kneading in an extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例３）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．１とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 3)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B1 to W (B) / W (A) = 0.1, melting and kneading in an extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例４）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ２をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
Example 4
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B2 to W (B) / W (A) = 0.05, melting and kneading in an extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例５）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ３をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 5)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B3 to W (B) / W (A) = 0.05, melting and kneading in an extruder, passing through cold water and forming a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例６）
上記により得た熱可塑性ポリエステルエラストマーＡ２と、可塑剤Ｂ４をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 6)
The polyester elastomer resin obtained by making the thermoplastic polyester elastomer A2 obtained above and the plasticizer B4 W (B) / W (A) = 0.05, melting and kneading in an extruder, passing through cold water, and forming a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例７）
上記により得た熱可塑性ポリエステルエラストマーＡ２と、可塑剤Ｂ５をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 7)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A2 obtained as described above and the plasticizer B5 to W (B) / W (A) = 0.05, melting and kneading in an extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例８）
上記により得た熱可塑性ポリエステルエラストマーＡ２と、可塑剤Ｂ５をＷ（Ｂ）／Ｗ（Ａ）＝０．０２とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Example 8)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A2 obtained above and the plasticizer B5 to W (B) / W (A) = 0.02, melting and kneading in the extruder, passing through cold water, and forming a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（実施例９）
上記により得た熱可塑性ポリエステルエラストマーＡ２と、可塑剤Ｂ５をＷ（Ｂ）／Ｗ（Ａ）＝０．０８とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
Example 9
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A2 obtained above and the plasticizer B5 to W (B) / W (A) = 0.08, melting and kneading in the extruder, passing through cold water and forming a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（比較例１）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．００５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Comparative Example 1)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained above and the plasticizer B1 to W (B) / W (A) = 0.005, melting and kneading in the extruder, passing through cold water and forming a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（比較例２）
上記により得た熱可塑性ポリエステルエラストマーＡ１と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．１５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Comparative Example 2)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A1 obtained as described above and the plasticizer B1 to W (B) / W (A) = 0.15, melting and kneading in the extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（比較例３）
上記により得た熱可塑性ポリエステルエラストマーＡ３と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Comparative Example 3)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A3 obtained as described above and the plasticizer B1 to W (B) / W (A) = 0.05, melting and kneading in an extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
（比較例４）
上記により得た熱可塑性ポリエステルエラストマーＡ４と、可塑剤Ｂ１をＷ（Ｂ）／Ｗ（Ａ）＝０．０５とし、押出機内で溶融・混練後、冷水に通して冷却ストランド化により、ポリエステルエラストマー樹脂組成物を得た。各種測定・評価を行った。結果を表１、表２に記す。
(Comparative Example 4)
The polyester elastomer resin is obtained by setting the thermoplastic polyester elastomer A4 obtained as described above and the plasticizer B1 to W (B) / W (A) = 0.05, melting and kneading in the extruder, and passing through cold water to form a cooling strand. A composition was obtained. Various measurements and evaluations were performed. The results are shown in Tables 1 and 2.
実施例で得られたポリエステルエラストマー樹脂組成物は、高せん断速度時流動性と成形品加熱時形状保持性を両立するものであった。 The polyester elastomer resin compositions obtained in the examples were compatible with both high shear rate fluidity and shape retention when the molded product was heated.
本発明のポリエステルエラストマー樹脂組成物は、高粘度特性と低粘度特性の両立を達成しており、例えばインジェクションブロー成形に最適である。 The polyester elastomer resin composition of the present invention achieves both high viscosity characteristics and low viscosity characteristics, and is optimal, for example, for injection blow molding.
Claims (3)
（式１） ０．０１≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．１
（式１において、Ｗ（Ｂ）／Ｗ（Ａ）は、ポリエステルエラストマー樹脂組成物中の、可塑剤［Ｂ］／熱可塑性ポリエステルエラストマー［Ａ］の質量割合である。） The ratio of the thermoplastic polyester elastomer [A] and the plasticizer [B] showing a solution viscosity of 2.3 to 2.8 is a polyester elastomer resin composition satisfying the following formula 1, and after 1 second at 180 ° C. and 6 rpm. A polyester elastomer resin composition having an extensional viscosity of 100,000 Pa · s to 1,000,000 Pa · s , wherein the thermoplastic polyester elastomer [A] comprises a hard segment comprising an aromatic dicarboxylic acid and a low molecular weight glycol, an aromatic dicarboxylic acid and a poly A polyester elastomer resin composition for injection blow molding comprising a soft segment comprising (oxytetramethylene) glycol as a constituent component .
(Formula 1) 0.01 ≦ W (B) / W (A) ≦ 0.1
(In Formula 1, W (B) / W (A) is a mass ratio of plasticizer [B] / thermoplastic polyester elastomer [A] in the polyester elastomer resin composition.)
（式２） ０．０２≦Ｗ（Ｂ）／Ｗ（Ａ）≦０．０８ The polyester elastomer resin composition for injection blow molding according to claim 1 or 2, wherein the W (B) / W (A) satisfies the following formula 2.
(Formula 2) 0.02 ≦ W (B) / W (A) ≦ 0.08
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