JP2006104341A - Polyester elastomer composition, its preparation method and polyester elastomer molded product and polyester elastic fiber made of the same - Google Patents
Polyester elastomer composition, its preparation method and polyester elastomer molded product and polyester elastic fiber made of the same Download PDFInfo
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- JP2006104341A JP2006104341A JP2004293414A JP2004293414A JP2006104341A JP 2006104341 A JP2006104341 A JP 2006104341A JP 2004293414 A JP2004293414 A JP 2004293414A JP 2004293414 A JP2004293414 A JP 2004293414A JP 2006104341 A JP2006104341 A JP 2006104341A
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- Prior art keywords
- polyester
- elastomer composition
- color
- polyester elastomer
- color adjusting
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 108
- 229920001971 elastomer Polymers 0.000 title claims abstract description 57
- 239000000806 elastomer Substances 0.000 title claims abstract description 57
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 210000004177 elastic tissue Anatomy 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 74
- 125000003118 aryl group Chemical group 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 19
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002835 absorbance Methods 0.000 claims abstract description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002148 esters Chemical class 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000000975 dye Substances 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 238000000862 absorption spectrum Methods 0.000 claims description 19
- 230000031700 light absorption Effects 0.000 claims description 19
- -1 polyethylene terephthalate Polymers 0.000 claims description 16
- 150000003609 titanium compounds Chemical class 0.000 claims description 15
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000002074 melt spinning Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229920000874 polytetramethylene terephthalate Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract description 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000003963 antioxidant agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- 229910052719 titanium Inorganic materials 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 10
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus 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
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 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 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- ZKIVUFFTMWIBCO-UHFFFAOYSA-N 1,5-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC1=CC=CC2=C1C(=O)C1=CC=CC(NC=3C=CC(C)=CC=3)=C1C2=O ZKIVUFFTMWIBCO-UHFFFAOYSA-N 0.000 description 1
- BWQIGAJDKXZJTG-UHFFFAOYSA-N 1-(cyclohexylamino)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1CCCCC1 BWQIGAJDKXZJTG-UHFFFAOYSA-N 0.000 description 1
- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 1
- ITYXXSSJBOAGAR-UHFFFAOYSA-N 1-(methylamino)-4-(4-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=C(C)C=C1 ITYXXSSJBOAGAR-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- ZPSZXWVBMOMXED-UHFFFAOYSA-N 2-(2-bromo-5-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC(Cl)=CC=C1Br ZPSZXWVBMOMXED-UHFFFAOYSA-N 0.000 description 1
- VFBJXXJYHWLXRM-UHFFFAOYSA-N 2-[2-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]ethylsulfanyl]ethyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCSCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 VFBJXXJYHWLXRM-UHFFFAOYSA-N 0.000 description 1
- UBZVRROHBDDCQY-UHFFFAOYSA-N 20749-68-2 Chemical compound C1=CC(N2C(=O)C3=C(C(=C(Cl)C(Cl)=C3C2=N2)Cl)Cl)=C3C2=CC=CC3=C1 UBZVRROHBDDCQY-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AMPCGOAFZFKBGH-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]-n,n-dimethylaniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 AMPCGOAFZFKBGH-UHFFFAOYSA-N 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- NMZURKQNORVXSV-UHFFFAOYSA-N 6-methyl-2-phenylquinoline Chemical compound C1=CC2=CC(C)=CC=C2N=C1C1=CC=CC=C1 NMZURKQNORVXSV-UHFFFAOYSA-N 0.000 description 1
- VJUKWPOWHJITTP-UHFFFAOYSA-N 81-39-0 Chemical compound C1=CC(C)=CC=C1NC1=CC=C2C3=C1C(=O)C1=CC=CC=C1C3=CC(=O)N2C VJUKWPOWHJITTP-UHFFFAOYSA-N 0.000 description 1
- HLNMYBZPLZNJPZ-UHFFFAOYSA-N N-cyclohexylcyclohexanamine 7-hydroxy-8-[(4-phenyldiazenylphenyl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1CCC(CC1)NC1CCCCC1.Oc1ccc2cc(cc(c2c1N=Nc1ccc(cc1)N=Nc1ccccc1)S(O)(=O)=O)S(O)(=O)=O HLNMYBZPLZNJPZ-UHFFFAOYSA-N 0.000 description 1
- NPGIHFRTRXVWOY-UHFFFAOYSA-N Oil red O Chemical compound Cc1ccc(C)c(c1)N=Nc1cc(C)c(cc1C)N=Nc1c(O)ccc2ccccc12 NPGIHFRTRXVWOY-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- SGOVXXIDIHIZRH-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;2-tert-butyl-4,6-dimethylphenol Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1.CC1=CC(C)=C(O)C(C(C)(C)C)=C1 SGOVXXIDIHIZRH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NHXXLZBKTKNTEF-UHFFFAOYSA-N chembl1997306 Chemical compound CC1=CC=CC(N=NC=2C(=CC(=CC=2)N=NC=2C3=CC=CC=C3C=CC=2O)C)=C1 NHXXLZBKTKNTEF-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- RCTGMCJBQGBLKT-PAMTUDGESA-N scarlet red Chemical compound CC1=CC=CC=C1\N=N\C(C=C1C)=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 RCTGMCJBQGBLKT-PAMTUDGESA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229940033816 solvent red 27 Drugs 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明はポリエステルエラストマー組成物、その製造方法及びそれよりなるポリエステルエラストマー成形品に関する。さらに詳しくは、鮮明性の改善されたポリエステルエラストマー組成物、優れた色相を持ったポリエステルエラストマー成形品、及び優れた弾性回復率性能を有するポリエステル弾性繊維に関する。 The present invention relates to a polyester elastomer composition, a method for producing the same, and a polyester elastomer molded article comprising the same. More specifically, the present invention relates to a polyester elastomer composition having improved sharpness, a polyester elastomer molded article having an excellent hue, and a polyester elastic fiber having an excellent elastic recovery rate performance.
ポリエーテルエステルエラストマーは優れた弾性性能を有し、機械的、物理的、化学的性能が優れているため、繊維、及びその他の成形物に広く利用されている。
その中で例えば主たるグリコール成分がエチレングリコール又はテトラメチレングリコールである芳香族ポリエステルをハードセグメントとし、ポリアルキレンオキシドグリコールをソフトセグメントとするポリエーテルエステルエラストマーは、次のような２段階の工程で製造されている。通常まずテレフタル酸とエチレングリコール若しくはテトラメチレングリコールを直接エステル化反応させるか、又はテレフタル酸ジメチルのようなテレフタル酸の低級アルキルエステルとエチレングリコール若しくはテトラメチレングリコール及びポリアルキレンオキシドグリコールとをエステル交換反応させて、テレフタル酸のエチレングリコールエステル若しくはテトラメチレングリコールエステル及びポリアルキレンオキシドグリコールエステル又はその低重合体を生成させる。次いでこの反応生成物を重合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって製造されている。
Polyether ester elastomers have excellent elastic performance and excellent mechanical, physical, and chemical performance, and are therefore widely used in fibers and other molded articles.
Among them, for example, a polyether ester elastomer having an aromatic polyester whose main glycol component is ethylene glycol or tetramethylene glycol as a hard segment and a polyalkylene oxide glycol as a soft segment is produced by the following two-stage process. ing. Usually, terephthalic acid is first directly esterified with ethylene glycol or tetramethylene glycol, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate is transesterified with ethylene glycol or tetramethylene glycol and polyalkylene oxide glycol. Thus, ethylene glycol ester or tetramethylene glycol ester and polyalkylene oxide glycol ester of terephthalic acid or a low polymer thereof is produced. Next, the reaction product is produced by heating under reduced pressure in the presence of a polymerization catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached.
これらのポリエーテルエステルにおいては、重縮合反応段階で使用する触媒の種類によって、反応速度及び得られるポリエステルの品質が大きく左右されることはよく知られている。この点について従来から検討の結果、重縮合触媒としては、低温にて、優れた重縮合触媒性能を有するなどの理由からチタン化合物が最も広く使用されている（例えば特許文献１参照。）。 In these polyether esters, it is well known that the reaction rate and the quality of the resulting polyester are greatly influenced by the type of catalyst used in the polycondensation reaction stage. As a result of conventional studies on this point, titanium compounds are most widely used as polycondensation catalysts because of their excellent polycondensation catalyst performance at low temperatures (see, for example, Patent Document 1).
しかしながら、得られたポリエステル自身が黄色く着色するという問題が発生する。この着色問題を解決するために、コバルト化合物をポリエステルに添加して黄味を抑えることが一般的に行われている。確かにコバルト化合物を添加することによってポリエステルの色相（ｂ値）は改善することができるが、コバルト化合物を添加することによってポリエステルの溶融熱安定性がさらに低下し、ポリマーの分解も起こりやすくなるという問題がある。 However, there arises a problem that the obtained polyester itself is colored yellow. In order to solve this coloring problem, it is a common practice to suppress yellowishness by adding a cobalt compound to polyester. Certainly, the hue (b value) of the polyester can be improved by adding a cobalt compound. However, the addition of a cobalt compound further lowers the thermal stability of the polyester and facilitates polymer degradation. There's a problem.
また、他のチタン化合物として、水酸化チタン、又はα−チタン酸をポリエステル製造用触媒として使用することが開示されている（それぞれ例えば特許文献２、特許文献３参照。）。しかしながら、前者の方法では水酸化チタンの粉末化が容易でなく、一方後者の方法ではα−チタン酸が変質し易いため、その保存、取扱いが容易でない。したがっていずれも工業的に採用するには適当ではなく、さらに、良好な色相（ｂ値）のポリマーを得ることも困難である。 Further, it is disclosed that titanium hydroxide or α-titanic acid is used as a catalyst for producing a polyester as another titanium compound (see, for example, Patent Document 2 and Patent Document 3 respectively). However, in the former method, powdering of titanium hydroxide is not easy, whereas in the latter method, α-titanic acid is likely to be altered, so that storage and handling are not easy. Accordingly, none of them are suitable for industrial use, and it is also difficult to obtain a polymer having a good hue (b value).
このような問題を解決する為に、チタン化合物と特定のリン化合物とを反応させて得られた生成物を（例えば特許文献４及び特許文献５参照。）、またチタン化合物と特定のリン化合物の未反応混合物あるいは反応生成物を（例えば特許文献６参照。）、それぞれポリエステル製造用触媒として使用することが開示されている。確かにこの方法によればポリエステルの溶融熱安定性は向上し、得られるポリマーの色相も大きく改善されるが、これらの方法ではポリエステル製造時の重合反応速度が遅い為、ポリエステルの生産性がやや劣ってしまう問題を有している。
したがってチタン触媒を使用し、かつ色相に優れたポリエーテルエステルが求められていた。
In order to solve such a problem, a product obtained by reacting a titanium compound with a specific phosphorus compound (see, for example, Patent Document 4 and Patent Document 5), or a titanium compound and a specific phosphorus compound are used. It is disclosed that an unreacted mixture or a reaction product (see, for example, Patent Document 6) is used as a catalyst for polyester production. Certainly, this method improves the melt heat stability of the polyester and greatly improves the hue of the resulting polymer. However, in these methods, the polymerization reaction rate during the production of the polyester is slow, so that the productivity of the polyester is slightly higher. Has the problem of being inferior.
Accordingly, there has been a demand for a polyether ester that uses a titanium catalyst and is excellent in hue.
本発明の目的は色相に優れたポリエステルエラストマー組成物、それよりなる弾性繊維及び成形品を提供することにある。 An object of the present invention is to provide a polyester elastomer composition excellent in hue, an elastic fiber comprising the same, and a molded article.
本発明者らは上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。
すなわち主たるグリコール成分がエチレングリコール又はテトラメチレングリコールである芳香族ポリエステルをハードセグメントとし、ポリアルキレンオキシドグリコールをソフトセグメントとして共重合された芳香族ポリエステル共重合体を主たる構成成分とし、整色剤をポリエステル組成物の全質量を基準として０．１〜１０質量ｐｐｍ含有するポリエーテルエステルエラストマー組成物であって、
１３０℃、２時間熱処理後のＬ＊ａ＊ｂ＊表色系におけるカラーａ＊値が−５〜０、カラーｂ＊値が−５〜４の範囲にあり、
該整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ該最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記式（１）〜（４）のすべてを満たすポリエステルエラストマー組成物
及びこれを溶融成形して得られるポリエステルエラストマー成形品及び弾性回復率が６０％〜９０％のポリエステル弾性繊維であり、これによって上記の課題が解決できる。
As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
That is, an aromatic polyester copolymer in which the main glycol component is ethylene glycol or tetramethylene glycol is used as a hard segment, and an aromatic polyester copolymer copolymerized using polyalkylene oxide glycol as a soft segment is used as a main component, and the color adjuster is polyester. A polyether ester elastomer composition containing 0.1 to 10 mass ppm based on the total mass of the composition,
The color a * value in the L * a * b * color system after heat treatment at 130 ° C. for 2 hours is in the range of −5 to 0, and the color b * value is in the range of −5 to 4;
When a visible light absorption spectrum of a wavelength of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L in the color adjusting agent at an optical path length of 1 cm, the maximum absorption wavelength was in the range of 540 to 600 nm, and the maximum absorption wavelength was Polyester elastomer composition in which the ratio of absorbance at each wavelength below to the absorbance satisfies all of the following formulas (1) to (4)
And a polyester elastomer molded article obtained by melt-molding the polyester elastomer and a polyester elastic fiber having an elastic recovery rate of 60% to 90%, whereby the above-described problems can be solved.
本発明によればポリエステルエラストマーの優れた特性を保持しながら、ＳｂやＧｅ触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。その結果、色相に優れたポリエステル弾性繊維及び成形品を提供することができる。 According to the present invention, it is possible to eliminate the deterioration of hue, which is a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent characteristics of the polyester elastomer. As a result, it is possible to provide a polyester elastic fiber and a molded product excellent in hue.
以下本発明を詳しく説明する。
本発明における芳香族ポリエステルとは、その主たるグリコール成分がエチレングリコール又はテトラメチレングリコールであるポリエステルである。より好ましくは、テレフタル酸、あるいはこれらのエステル形成性誘導体に代表される芳香族ジカルボン酸成分と、グリコール成分を重縮合反応せしめて得られるポリエステルのことであり、共重合成分として、芳香族ジカルボン酸成分と上記のグリコール成分以外の成分、例えば脂肪族ジカルボン酸成分、芳香族ジヒドロキシ化合物、オキシカルボン酸成分が共重合されていても良い。ここで「主たる」とは８０モル％以上であることを表す。該芳香族ポリエステルとしては、ポリエチレンテレフタレート及びポリテトラメチレンテレフタレートよりなる群から少なくとも１種選ばれるポリエステルであることが好ましく、これらの中でもポリテトラメチレンテレフタレートを主たる構成成分とするポリエステルであることが好ましい。そしてこの芳香族ポリエステルをハードセグメントとして共重合されている。
The present invention will be described in detail below.
The aromatic polyester in the present invention is a polyester whose main glycol component is ethylene glycol or tetramethylene glycol. More preferably, it is a polyester obtained by polycondensation reaction of an aromatic dicarboxylic acid component typified by terephthalic acid or an ester-forming derivative thereof and a glycol component, and an aromatic dicarboxylic acid is used as a copolymerization component. Components other than the above-mentioned glycol components, for example, aliphatic dicarboxylic acid components, aromatic dihydroxy compounds, and oxycarboxylic acid components may be copolymerized. Here, “main” means 80 mol% or more. The aromatic polyester is preferably a polyester selected from at least one selected from the group consisting of polyethylene terephthalate and polytetramethylene terephthalate, and among these, a polyester having polytetramethylene terephthalate as a main constituent is preferable. This aromatic polyester is copolymerized as a hard segment.
さらに本発明においてはポリアルキレンオキシドグリコールがソフトセグメントとして共重合されている必要がある。共重合物としてのポリアルキレンオキシドグリコールとしては、平均分子量が４００〜１００００のものが好ましく用いることができ、平均分子量が１０００〜８０００のものがより好ましく、平均分子量が２０００〜６０００のものがさらにより好ましい。より具体的には一般式（ＩＩＩ）で表されるポリエチレングリコール（ＰＥＧ）、一般式(ＩＶ)で表されるポリテトラメチレングリコール（ＰＴＭＧ）又はポリプロピレングリコールが好ましくあげられ、これらの中でも平均分子量が２０００のＰＴＭＧ（ＰＴＭＧ２０００）がより好ましい。 Furthermore, in the present invention, polyalkylene oxide glycol needs to be copolymerized as a soft segment. As the polyalkylene oxide glycol as the copolymer, those having an average molecular weight of 400 to 10000 can be preferably used, those having an average molecular weight of 1000 to 8000 are more preferable, and those having an average molecular weight of 2000 to 6000 are even more preferable. preferable. More specifically, polyethylene glycol (PEG) represented by the general formula (III), polytetramethylene glycol (PTMG) or polypropylene glycol represented by the general formula (IV) are preferably exemplified, and among these, the average molecular weight is preferably 2000 PTMG (PTMG2000) is more preferred.
本発明のポリエステルエラストマー組成物は整色剤を０．１〜１０質量ｐｐｍ含有する必要がある。なおその整色剤とは、有機の多芳香族環系染料又は顔料を表す。具体的には後述のように青色系整色用色素、紫系整色用色素、赤色系整色用色素、橙色系整色用色素等が挙げられる。これらは単一種で用いても複数種を併用して用いても良い。後述のような可視光吸収スペクトルに関する要件を満たしやすい点において、複数種を用いることが好ましい。更にその整色剤においては、整色剤の２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記式（１）〜（４）のすべてを満たす必要がある。 The polyester elastomer composition of the present invention needs to contain 0.1-10 mass ppm of the color adjusting agent. The color adjusting agent represents an organic polyaromatic ring dye or pigment. Specific examples thereof include a blue color adjusting dye, a purple color adjusting dye, a red color adjusting dye, and an orange color adjusting dye as described later. These may be used alone or in combination of two or more. It is preferable to use a plurality of types in terms of easily satisfying the requirements regarding the visible light absorption spectrum as described later. Furthermore, in the color adjusting agent, when the visible light absorption spectrum in the wavelength range of 380 to 780 nm was measured at an optical path length of 1 cm for a 20 mg / L chloroform solution of the color adjusting agent, the maximum absorption wavelength was in the range of 540 to 600 nm. And the ratio of the light absorbency in the following each wavelength with respect to the light absorbency in the maximum absorption wavelength needs to satisfy | fill all of following formula (1)-(4).
ここで可視光吸収スペクトルとは、通常分光光度計によって測定されるスペクトルであるが、本発明のポリエステルエラストマー組成物に含有される整色剤溶液の可視光吸収スペクトルの最大吸収波長が５４０ｎｍ未満の場合は得られるポリエステルエラストマー組成物の赤味が強くなり、また６００ｎｍを超える場合は得られるポリエステルエラストマー組成物の青味が強くなる為好ましくない。最大吸収波長の範囲は５４５〜５９５ｎｍの範囲が好ましく、５５０〜５９０ｎｍの範囲が更に好ましい。 Here, the visible light absorption spectrum is a spectrum usually measured by a spectrophotometer, but the maximum absorption wavelength of the visible light absorption spectrum of the color-fixing agent solution contained in the polyester elastomer composition of the present invention is less than 540 nm. In this case, the redness of the resulting polyester elastomer composition becomes strong, and when it exceeds 600 nm, the blueness of the resulting polyester elastomer composition becomes strong, which is not preferable. The range of the maximum absorption wavelength is preferably 545 to 595 nm, and more preferably 550 to 590 nm.
また本発明のポリエステルエラストマー組成物に含有される整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて、波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長における吸光度に対する上記の４００ｎｍ、５００ｎｍ、６００ｎｍ、７００ｎｍでの吸光度の割合が上記式（１）〜（４）のいずれか一つでも外れる場合、得られるポリエステルエラストマー組成物の着色が大きくなり好ましくない。上記式（１）〜（４）はそれぞれ下記式（５）〜（８）のいずれか１つ以上の範囲にあることが好ましく、更に下記式（５）〜（８）すべてを満たしていることが好ましい。 In addition, when a visible light absorption spectrum in a wavelength range of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L in a color adjusting agent contained in the polyester elastomer composition of the present invention at an optical path length of 1 cm, the absorbance at the maximum absorption wavelength was measured. If the absorbance ratio at 400 nm, 500 nm, 600 nm, and 700 nm is out of any one of the above formulas (1) to (4), the resulting polyester elastomer composition is unfavorably colored. It is preferable that said formula (1)-(4) exists in the range of any one or more of following formula (5)-(8), respectively, and also satisfy | fills all following formula (5)-(8). Is preferred.
更に本発明のポリエステルエラストマー組成物に含有される上述の整色剤の含有量が、０．１質量ｐｐｍ未満の場合、ポリエステルエラストマー組成物の黄色味が強くなる。一方、１０質量ｐｐｍを超える場合、明度が弱くなり見た目に黒味が強くなる為好ましくない。該整色剤の含有量は０．３質量ｐｐｍ〜９質量ｐｐｍの範囲が好ましく、０．５〜８質量ｐｐｍの範囲にあることが更に好ましい。 Furthermore, when content of the above-mentioned color adjusting agent contained in the polyester elastomer composition of the present invention is less than 0.1 mass ppm, the yellowness of the polyester elastomer composition becomes strong. On the other hand, if it exceeds 10 ppm by mass, the brightness becomes weak and the blackness becomes strong visually, which is not preferable. The content of the color adjusting agent is preferably in the range of 0.3 mass ppm to 9 mass ppm, and more preferably in the range of 0.5 to 8 mass ppm.
本発明のポリエステルエラストマー組成物は、１３０℃、２時間熱処理後のＬ＊ａ＊ｂ＊表色系におけるカラーａ＊値が−５〜０、カラーｂ＊値が−５〜４の範囲にある必要がある。該カラー値は含有される整色剤の量によって変化してくるが、カラーａ＊値が−５より小さい場合、ポリエステルエラストマー組成物は緑色味が強くなり、０より大きい場合は赤味が強くなり好ましくない。またカラーｂ＊値が−５より小さい場合、ポリエステルエラストマー組成物は青味が強くなり、４より大きい場合は黄色味が強くなる為好ましくない。カラーａ＊値は−４〜０の範囲が好ましく、−３〜−１の範囲が更に好ましい。またカラーｂ＊値は−４〜４範囲が好ましく、−３〜３の範囲が更に好ましい。 The polyester elastomer composition of the present invention has a color a * value of −5 to 0 and a color b * value of −5 to 4 in the L * a * b * color system after heat treatment at 130 ° C. for 2 hours. There is a need. The color value varies depending on the amount of the color adjusting agent contained, but when the color a * value is less than −5, the polyester elastomer composition has a strong green taste, and when it is greater than 0, the redness is strong. It is not preferable. Further, when the color b * value is smaller than −5, the polyester elastomer composition has a strong bluish color, and when it is larger than 4, the yellow color becomes strong, which is not preferable. The color a * value is preferably in the range of -4 to 0, and more preferably in the range of -3 to -1. The color b * value is preferably in the range of -4 to 4, more preferably in the range of -3 to 3.
本発明に使用する整色剤は窒素雰囲気下中、昇温速度１０℃／分の条件で熱天秤にて測定した質量減少開始温度が２５０℃以上である整色用色素から選ばれることが好ましい。ここで、熱天秤で測定した質量減少開始温度とは、ＪＩＳ Ｋ−７１２０に記載の質量減少開始温度（Ｔ１）のことであり、整色剤が有している耐熱性の指標となる。該質量減少開始温度が２５０℃未満である場合、整色剤の耐熱性が不十分であることから最終的に得られるポリエステルエラストマー組成物の着色の原因となり好ましくない。該質量減少開始温度は３００℃以上であることが更に好ましい。また芳香族ポリエステル共重合体が溶融状態にある温度条件下で分解しないことが更に好ましい。 The color adjusting agent used in the present invention is preferably selected from color adjusting dyes having a mass decrease starting temperature of 250 ° C. or higher measured with a thermobalance in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. . Here, the mass reduction start temperature measured with a thermobalance is the mass reduction start temperature (T 1 ) described in JIS K-7120, and serves as a heat resistance index possessed by the color adjusting agent. When the mass decrease starting temperature is less than 250 ° C., the heat resistance of the color adjusting agent is insufficient, which is not preferable because it causes coloring of the finally obtained polyester elastomer composition. The mass decrease starting temperature is more preferably 300 ° C. or higher. It is further preferable that the aromatic polyester copolymer does not decompose under temperature conditions where it is in a molten state.
さらに本発明におけるポリエステルエラストマー組成物においては、ポリエステルエラストマー組成物中に含有されるポリエステルに可溶性のチタン金属元素が芳香族ポリエステル共重合体を構成する全ジカルボン酸成分に対し、５０〜１５０ミリモル％の範囲にあることが好ましい。該チタン金属元素量が５０ミリモル％未満の場合、重縮合反応が十分に進行せず、１５０ミリモル％を超える場合、得られるポリエステルエラストマー組成物の色相が黄色味を帯び、更に耐熱性が低下し好ましくない。該チタン金属元素は９０〜１３０ミリモル％の範囲が更に好ましい。 Furthermore, in the polyester elastomer composition in the present invention, the titanium metal element soluble in the polyester contained in the polyester elastomer composition is 50 to 150 mmol% based on the total dicarboxylic acid component constituting the aromatic polyester copolymer. It is preferable to be in the range. When the amount of the titanium metal element is less than 50 mmol%, the polycondensation reaction does not proceed sufficiently, and when it exceeds 150 mmol%, the hue of the resulting polyester elastomer composition is yellowish and the heat resistance is further reduced. It is not preferable. The titanium metal element is more preferably in the range of 90 to 130 mmol%.
本発明のポリエステルエラストマー組成物の固有粘度（溶媒：オルトクロロフェノール、測定温度：３５℃）は特に制限は無いが、通常、繊維、樹脂成形品において通常使用することが出来る範囲であることが好ましく、具体的には０．８０〜１．５０ｄＬ／ｇの範囲にあることが好ましい。 The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester elastomer composition of the present invention is not particularly limited, but is usually preferably in a range that can be normally used in fibers and resin molded products. Specifically, it is preferably in the range of 0.80 to 1.50 dL / g.
また本発明におけるポリエステルエラストマー組成物は、必要に応じて少量の添加剤、例えば滑剤、酸化防止剤、固相重合促進剤、蛍光増白剤、帯電防止剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、遮光剤又は艶消剤等を含んでいてもよく、特に艶消剤として酸化チタン、酸化防止剤としてはヒンダートフェノール系の酸化防止剤が好ましく添加される。該酸化防止剤としてはヒンダードフェノール系の酸化防止剤が好ましい。具体的にはペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、３，９−ビス｛２−［３−（３−ｔｅｒｔ−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、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔｅｒｔ−ブチルフェニル）ブタン、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、１，３，５−トリス（４−ｔｅｒｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンゼン）イソフタル酸、トリエチルグリコール−ビス［３−（３−ｔｅｒｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２−チオ−ジエチレン−ビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］等が挙げられる。これらヒンダードフェノール系酸化防止剤の添加量はポリエステル組成物に対して１質量％以下であることが好ましい。１質量％を超えると成形時の異物発生の原因となり得る問題があり、また１質量％を超えて添加しても溶融安定性向上の効果が飽和してしまう為好ましくない。ヒンダードフェノール系酸化防止剤の添加量は０．００５〜０．５質量％の範囲が更に好ましい。またこれらヒンダードフェノール系酸化防止とチオエーテル系二次酸化防止剤を併用して用いることも好ましく実施される。該酸化防止剤のポリエステルエラストマー組成物への添加方法は特に制限はなく、後述の芳香族ポリエステル共重合体の製造段階若しくはポリエステルエラストマー組成物の製造段階のいずれにおいても実施できる。好ましくは芳香族ポリエステル共重合体の製造段階におけるエステル交換反応又はエステル化反応終了後、重合反応が完了するまでの間の任意の段階で添加する方法が挙げられる。 Further, the polyester elastomer composition of the present invention contains a small amount of additives as necessary, for example, a lubricant, an antioxidant, a solid phase polymerization accelerator, a fluorescent brightener, an antistatic agent, an antibacterial agent, an ultraviolet absorber, and a light stabilizer. An agent, a heat stabilizer, a light-shielding agent, a matting agent, and the like may be contained. In particular, titanium oxide is preferably added as a matting agent, and a hindered phenol antioxidant is preferably added as an antioxidant. The antioxidant is preferably a hindered phenol antioxidant. Specifically, pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,3,5 -Tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzene) isophthalic acid, triethylglycol-bis [3- (3-tert-butyl-5-methyl 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylene-bis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. The amount of these hindered phenol antioxidants added is preferably 1% by mass or less based on the polyester composition. If it exceeds 1% by mass, there is a problem that may cause generation of foreign matters during molding, and even if added in excess of 1% by mass, the effect of improving the melt stability is saturated, which is not preferable. The addition amount of the hindered phenol-based antioxidant is more preferably in the range of 0.005 to 0.5% by mass. It is also preferable to use these hindered phenol antioxidants and thioether secondary antioxidants in combination. The method for adding the antioxidant to the polyester elastomer composition is not particularly limited, and the antioxidant can be carried out at any of the stages for producing an aromatic polyester copolymer or the polyester elastomer composition described below. Preferably, a method of adding at an arbitrary stage after completion of the ester exchange reaction or esterification reaction in the production stage of the aromatic polyester copolymer and until the polymerization reaction is completed can be mentioned.
本発明における芳香族ポリエステル共重合体の製造方法は、通常知られているポリエステルの製造方法が用いられる。すなわち、まずテレフタル酸の如きジカルボン酸成分とエチレングリコールの如きグリコール成分とを直接エステル化反応させる、又はテレフタル酸ジメチルの如きジカルボン酸成分の低級アルキルエステルとエチレングリコールの如きグリコール成分とをエステル交換反応させ、ジカルボン酸のグリコールエステル及び／又はその低重合体を製造する。次いでこの反応生成物を重合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって目的とする芳香族ポリエステル共重合体が製造される。またポリエチレングリコール及び／又はその誘導外は重縮合反応が終了するまでの任意の段階で加えることができるが、好ましくはエステル化反応若しくはエステル交換反応させる段階の前からこれらの反応がほぼ終了し重縮合反応の段階の前までに加えることが好ましい。 As the method for producing the aromatic polyester copolymer in the present invention, a conventionally known polyester production method is used. That is, first, a dicarboxylic acid component such as terephthalic acid is directly esterified with a glycol component such as ethylene glycol, or a lower alkyl ester of a dicarboxylic acid component such as dimethyl terephthalate is transesterified with a glycol component such as ethylene glycol. To produce a glycol ester of dicarboxylic acid and / or a low polymer thereof. Then, the reaction product is heated under reduced pressure in the presence of a polymerization catalyst and subjected to a polycondensation reaction until a predetermined degree of polymerization is obtained, whereby a desired aromatic polyester copolymer is produced. Polyethylene glycol and / or its derivative can be added at any stage until the polycondensation reaction is completed, but preferably these reactions are almost completed before the stage of esterification reaction or transesterification reaction and It is preferably added before the stage of the condensation reaction.
更に詳説すると、芳香族ポリエステル共重合体が、チタン化合物を重合触媒として製造されたものであることが好ましい。ここで、チタン化合物としては特に限定されず、ポリエステルの重縮合触媒として一般的なチタン化合物、例えば、酢酸チタンやテトラ−ｎ−ブトキシチタンなどが挙げられる。チタン化合物としてより好ましいのは、下記一般式（Ｉ）で表わされる化合物、一般式（Ｉ）で表わされる化合物と下記一般式（ＩＩ）で表わされる芳香族多価カルボン酸若しくはその無水物とを反応させた生成物、又は下記一般式（Ｖ）で表される化合物を用いることである。 More specifically, the aromatic polyester copolymer is preferably produced using a titanium compound as a polymerization catalyst. Here, it does not specifically limit as a titanium compound, A titanium compound common as a polycondensation catalyst of polyester, for example, titanium acetate, tetra-n-butoxy titanium, etc. are mentioned. More preferable as the titanium compound is a compound represented by the following general formula (I), a compound represented by the general formula (I) and an aromatic polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof. The reaction product or the compound represented by the following general formula (V) is used.
また、これらチタン化合物は混合して用いても良いが、単独で用いるのが好ましい。なかでも最も好ましいのが上記一般式（Ｉ）で表わされる化合物、又は一般式（Ｉ）で表わされる化合物と上記一般式（ＩＩ）で表わされる芳香族多価カルボン酸若しくはその無水物とを反応させた生成物を単独で用いることである。 These titanium compounds may be used in combination, but are preferably used alone. Of these, the compound represented by the above general formula (I) or the compound represented by the general formula (I) is preferably reacted with the aromatic polycarboxylic acid represented by the above general formula (II) or its anhydride. The product obtained is used alone.
一般式（Ｉ）で表わされるテトラアルコキサイドチタン及び／又はテトラフェノキサイドチタンとしては、Ｒ１〜Ｒ４がアルキル基及び／又はフェニル基であれば特に限定されないが、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラエトキシチタン又はテトラフェノキシチタンなどが好ましく用いられる。また、かかるチタン化合物と反応させる一般式（ＩＩ）で表される芳香族多価カルボン酸又はその無水物としては、フタル酸、トリメリット酸、ヘミメリット酸若しくはピロメリット酸又はこれらの無水物が好ましく用いられる。上記チタン化合物と芳香族多価カルボン酸又はその無水物とを反応させる場合には、溶媒に芳香族多価カルボン酸又はその無水物の一部とを溶解し、これにチタン化合物を滴下し、０〜２００℃の温度で３０分以上反応させれば良い。又必要に応じてチタン化合物滴下後、残りの芳香族多価カルボン酸又はその無水物を加えればよい。 The tetraalkoxide titanium and / or tetraphenoxide titanium represented by the general formula (I) is not particularly limited as long as R 1 to R 4 are an alkyl group and / or a phenyl group, but tetraisopropoxy titanium, tetra -N-propoxy titanium, tetra-n-butoxy titanium, tetraethoxy titanium, tetraphenoxy titanium or the like is preferably used. In addition, the aromatic polyvalent carboxylic acid represented by the general formula (II) to be reacted with the titanium compound or the anhydride thereof includes phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, or an anhydride thereof. Preferably used. When the titanium compound and the aromatic polyvalent carboxylic acid or anhydride thereof are reacted, the aromatic polyvalent carboxylic acid or a part of the anhydride is dissolved in a solvent, and the titanium compound is dropped into this, What is necessary is just to make it react for 30 minutes or more at the temperature of 0-200 degreeC. Moreover, what is necessary is just to add the remaining aromatic polyhydric carboxylic acid or its anhydride after dripping a titanium compound as needed.
さらに本発明のポリエステルエラストマー組成物の製造方法は上述した芳香族ポリエステル共重合体の製造工程の任意の段階で整色剤を添加されることによって製造されることが好ましい。なかでも重縮合反応工程が終了するまでの任意の段階で添加されることが更に好ましい。特にエステル化反応若しくはエステル交換反応が終了した後に整色剤を添加することが最も好ましい。 Furthermore, it is preferable that the manufacturing method of the polyester elastomer composition of this invention is manufactured by adding a color adjusting agent in the arbitrary steps of the manufacturing process of the aromatic polyester copolymer mentioned above. Among these, it is more preferable to add at any stage until the polycondensation reaction step is completed. In particular, it is most preferable to add the color adjusting agent after completion of the esterification reaction or transesterification reaction.
本発明のポリエステルエラストマー組成物の製造方法においては、整色剤として青色系整色用色素と紫色系整色用色素を質量比９０：１０〜４０：６０の範囲で併用すること、又は青色系整色用色素と、赤色系若しくは橙色系整色用色素を質量比９８：２〜８０：２０の範囲で併用することが好ましい。ここで青色系整色用色素とは、一般に市販されている整色用色素の中で「Ｂｌｕｅ」と表記されているものであって、具体的には溶液中の可視光スペクトルにおける最大吸収波長が５８０〜６２０ｎｍ程度にあるものを示す。同様に紫色系整色用色素とは市販されている整色用色素の中で「Ｖｉｏｌｅｔ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が５６０〜５８０ｎｍ程度にあるものを示す。赤色系整色用色素とは市販されている整色用色素の中で「Ｒｅｄ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が４８０〜５２０ｎｍ程度にあるものである。橙色系整色用色素とは市販されている整色用色素の中で「Ｏｒａｎｇｅ」と表記されているものである。 In the method for producing a polyester elastomer composition of the present invention, a blue color adjusting dye and a purple color adjusting dye are used in combination in a mass ratio of 90:10 to 40:60 as a color adjusting agent, or blue It is preferable to use the color adjusting dye and the red or orange color adjusting dye in a mass ratio of 98: 2 to 80:20. Here, the blue color adjusting dye is generally indicated as “Blue” among commercially available color adjusting dyes, and specifically, the maximum absorption wavelength in the visible light spectrum in the solution. Is about 580 to 620 nm. Similarly, the purple color-modifying dye is the one described as “Violet” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is The thing in about 560-580 nm is shown. The red color-modifying dyes are those listed as “Red” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is 480 to 480. It is about 520 nm. The orange color-modifying dyes are those listed as “Orange” among commercially available color-adjusting dyes.
これらの整色剤としては油溶染料が特に好ましく、具体的な例としては、青色系整色剤には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ １１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３６、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ４５ （Ｔｅｌａｓｏｌ Ｂｌｕｅ ＲＬＳ）、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ５５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ６３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ７８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ９４等が挙げられる。紫色系整色剤には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ３６等が挙げられる。赤色系整色剤には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ３０、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ４９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ５２、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １００、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １０９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １１１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １６８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １７９等が例示される。橙色系整色剤には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｏｒａｎｇｅ ６０等が挙げられる。 As these color adjusters, oil-soluble dyes are particularly preferable. Specific examples of the color adjusters include C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45 (Telasol Blue RLS), C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94 and the like. Examples of purple color adjusters include C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Violet 28, C.I. I. Solvent Violet 36 etc. are mentioned. Examples of red color adjusters include C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 135, C.I. I. Solvent Red 168, C.I. I. Solvent Red 179 etc. are illustrated. Examples of orange color adjusters include C.I. I. Solvent Orange 60 etc. are mentioned.
ここで青色系整色用色素と紫色系整色用色素を併用する場合、質量比９０：１０より青色系整色用色素の質量比が大きい場合は、得られるポリエステルエラストマー組成物のカラーａ＊値が小さくなって緑色を呈し、４０：６０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。同様に青色系整色用色素と赤色系または橙色系整色用色素を併用する場合、質量比９８：２より青色系整色用色素の質量比が大きい場合は、得られるポリエステルエラストマー組成物のカラーａ＊値が小さくなって緑色を呈し、８０：２０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。該整色用色素は、青色系整色用色素と紫色系整色用色素を質量比８０：２０〜５０：５０の範囲で併用すること、あるいは青色系整色用色素と赤色系または橙色系整色用色素を質量比９５：５〜９０：１０の範囲で併用することが更に好ましい。 Here, when the blue color adjusting dye and the purple color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than 90:10, the color a * of the resulting polyester elastomer composition is obtained . If the value is small and green, and the mass ratio of the blue color-changing dye is smaller than 40:60, the color a * value becomes large and red is not preferable. Similarly, in the case where a blue color adjusting dye and a red or orange color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than 98: 2, the resulting polyester elastomer composition When the color a * value is small and green is exhibited, and the mass ratio of the blue color adjusting dye is smaller than 80:20, the color a * value is large and the red color is not preferable. The color adjusting dye is a combination of a blue color adjusting dye and a purple color adjusting dye in a mass ratio of 80:20 to 50:50, or a blue color adjusting dye and a red or orange color. It is more preferable to use the color adjusting dye in a mass ratio of 95: 5 to 90:10.
さらに本発明のポリエステル弾性繊維を製造する時の製造方法としては特に限定はなく、従来公知の溶融紡糸方法が用いられる。例えば乾燥したポリエステルエラストマー組成物を２５０℃〜２８０℃の範囲で溶融紡糸して製造することが好ましく、溶融紡糸の速度は４００〜５０００ｍ／分で紡糸することが好ましい。紡糸速度がこの範囲にあると、得られる繊維の強度も十分なものであると共に、安定して巻き取りを行うこともできる。また紡糸時に使用する口金の形状についても特に制限は無く、円形、異形、中実、中空などのいずれも採用することが出来る。更に本発明のポリエステル弾性繊維は風合いや染色性を高める為に、アルカリ減量処理も好ましく実施されるが、特に得られたポリエステル弾性繊維を用いて織編物の状態にした後にアルカリ減量処理を施すことが好ましい。本発明のポリエステルエラストマー成形品としては、具体的には射出成形による成形品が挙げられるが、これを製造する時の製造方法としては特に限定はなく、従来公知の溶融成形方法が用いられる。例えば乾燥したポリエステルエラストマー組成物を２５０℃〜２８０℃の範囲で溶融して、射出成形機を用いて、０〜８０℃程度の温度の金型中にポリエステル組成物を流し込んで成形する。 Furthermore, there is no limitation in particular as a manufacturing method when manufacturing the polyester elastic fiber of this invention, A conventionally well-known melt spinning method is used. For example, it is preferable to produce a dried polyester elastomer composition by melt spinning in the range of 250 ° C. to 280 ° C., and the melt spinning speed is preferably from 400 to 5000 m / min. When the spinning speed is in this range, the strength of the obtained fiber is sufficient, and the winding can be stably performed. Further, the shape of the die used at the time of spinning is not particularly limited, and any of circular, irregular, solid and hollow can be adopted. Further, the polyester elastic fiber of the present invention is preferably subjected to an alkali weight reduction treatment in order to enhance the texture and dyeability, but in particular, after the polyester elastic fiber obtained is made into a woven or knitted fabric, the alkali weight loss treatment is performed. Is preferred. Specific examples of the polyester elastomer molded article of the present invention include a molded article by injection molding, but the production method for producing this is not particularly limited, and a conventionally known melt molding method is used. For example, the dried polyester elastomer composition is melted in the range of 250 ° C. to 280 ° C., and is molded by pouring the polyester composition into a mold having a temperature of about 0 to 80 ° C. using an injection molding machine.
本発明をさらに下記実施例により具体的に説明するが、本発明の範囲はこれら実施例により限定されるものではない。尚、固有粘度、色相、チタン含有量及び弾性回復率等については、下記記載の方法により測定した。 The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. The intrinsic viscosity, hue, titanium content, elastic recovery rate and the like were measured by the methods described below.
（ア）固有粘度：
ポリエステルエラストマー組成物チップを１００℃、６０分間でオルトクロロフェノールに溶解し、得られた希薄溶液を、３５℃でウベローデ粘度計を用いて測定した値から求めた。
(A) Intrinsic viscosity:
The polyester elastomer composition chip was dissolved in orthochlorophenol at 100 ° C. for 60 minutes, and the resulting diluted solution was determined from the value measured at 35 ° C. using an Ubbelohde viscometer.
（イ）色相（Ｌ＊値、ａ＊値、ｂ＊値）：
ポリマーチップを２８５℃、真空下で１０分間溶融し、これをアルミニウム板上で厚さ３．０±１．０ｍｍのプレートに成形後ただちに氷水中で急冷し、該プレートを１３０℃、２時間乾燥結晶化処理を行った。その後、色差計調整用の白色標準プレート上に置き、プレート表面のハンターＬ＊及びｂ＊を、ミノルタ社製ハンター型色差計（ＣＲ−２００型）を用いて測定した。Ｌ＊は明度を示し、その数値が大きいほど明度が高いことを示し、ｂ＊はその値が大きいほど黄着色の度合いが大きいことを示す。また他の詳細な操作はＪＩＳ Ｚ−８７２９に準じて行った。
(A) Hue (L * value, a * value, b * value):
The polymer chip was melted at 285 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, immediately cooled in ice water, and the plate was dried at 130 ° C. for 2 hours. Crystallization was performed. Thereafter, the plate was placed on a white standard plate for color difference adjustment, and the hunters L * and b * on the plate surface were measured using a Hunter type color difference meter (CR-200 type) manufactured by Minolta. L * indicates lightness, and the larger the value, the higher the lightness, and b * the greater the value, the greater the degree of yellowing. Other detailed operations were performed according to JIS Z-8729.
（ウ）弾性回復率：
弾性回復率弾性糸試料１０ｃｍに、２００％伸長に対応する荷重をかけて、素早く２００％伸長させ、５秒後に荷重を取り除き、素早く試料の長さＬｃｍを読み取り、次式により算出した。
弾性回復率＝｛［２０−（Ｌ−１０）］／２０｝×１００（％）
(C) Elastic recovery rate:
Elasticity recovery rate A load corresponding to 200% elongation was applied to a 10 cm elastic yarn sample, quickly stretched by 200%, the load was removed after 5 seconds, the length Lcm of the sample was quickly read, and the following formula was calculated.
Elastic recovery factor = {[20− (L−10)] / 20} × 100 (%)
（エ）強度：
得られた弾性糸を島津製作所オリエンテック（株）製テンシロン引っ張り試験機を用いて、ＪＩＳ−Ｌ−１０１３に基づいて試料長２０ｃｍ、伸長速度 ２０ｃｍ／分の条件で測定し、得られた荷重・伸長曲線から求めた。
(D) Strength:
The obtained elastic yarn was measured under the conditions of a sample length of 20 cm and an elongation rate of 20 cm / min based on JIS-L-1013 using a Tensilon tensile tester manufactured by Shimadzu Corporation Orientec Co., Ltd. It was obtained from an elongation curve.
（オ）整色剤の質量減少開始温度：
リガク社製ＴＡＳ−２００熱天秤を用いてＪＩＳ Ｋ７１２０に従い、窒素雰囲気下中昇温速度１０℃／分で測定した。
(E) Mass reduction start temperature of color adjusting agent:
Using a TAS-200 thermobalance manufactured by Rigaku Corporation, the temperature was measured in a nitrogen atmosphere at a heating rate of 10 ° C./min according to JIS K7120.
［参考例１］チタン触媒Ａの合成
無水トリメリット酸のエチレングリコール溶液（０．２質量％）にテトラ−ｎ−ブトキシチタンを無水トリメリット酸に対して１／２モル添加し、空気中常圧下で８０℃に保持して６０分間反応せしめた。その後常温に冷却し、１０倍量のアセトンによって生成触媒を再結晶化させた。析出物をろ紙によって濾過し、１００℃で２時間乾燥せしめ、目的の化合物を得た。これをチタン触媒Ａとする。
[Reference Example 1] Synthesis of Titanium Catalyst A Tetra-n-butoxytitanium is added to an ethylene glycol solution (0.2% by mass) of trimellitic anhydride in an amount of ½ mol with respect to trimellitic anhydride, and under normal pressure in air. And kept at 80 ° C. for 60 minutes. Thereafter, it was cooled to room temperature, and the produced catalyst was recrystallized with 10 times the amount of acetone. The precipitate was filtered through filter paper and dried at 100 ° C. for 2 hours to obtain the target compound. This is designated as titanium catalyst A.
［参考例２］整色剤（整色用色素）の可視光吸収スペクトル測定、整色剤調製
表１に示す整色用色素を室温で濃度２０ｍｇ／Ｌのクロロホルム溶液とし、光路長１ｃｍの石英セルに充填し、対照セルにはクロロホルムのみを充填して、日立分光光度計Ｕ−３０１０型を用いて、３８０〜７８０ｎｍの可視光領域での可視光吸収スペクトルを測定した。整色用色素２種を混合する場合は合計で濃度２０ｍｇ／Ｌとなるようにした。最大吸収波長とその波長における吸光度に対する、４００、５００、６００及び７００ｎｍの各波長での吸光度の割合を測定した。更に粉末の整色用色素の熱質量減少開始温度を測定した。結果を表１に示す。尚、実施例、比較例でこれら整色用色素を芳香族ポリエステル共重合体製造工程で添加する場合は、１００℃の温度で、原料として用いるグリコール溶液に対し、濃度０．１質量％となるように溶解または分散させて調製した。
[Reference Example 2] Visible light absorption spectrum measurement of color-adjusting agent (color-adjusting dye), preparation of color-adjusting agent The color-adjusting dye shown in Table 1 was made into a chloroform solution at a concentration of 20 mg / L at room temperature, and quartz having an optical path length of 1 cm The cell was filled, and the control cell was filled with chloroform alone, and a visible light absorption spectrum in a visible light region of 380 to 780 nm was measured using a Hitachi spectrophotometer U-3010 type. In the case of mixing the two color adjusting dyes, the total concentration was 20 mg / L. The ratio of the absorbance at each wavelength of 400, 500, 600, and 700 nm to the maximum absorption wavelength and the absorbance at that wavelength was measured. Further, the thermal mass decrease start temperature of the powder color adjusting dye was measured. The results are shown in Table 1. In addition, when adding these color-adjusting dyes in the aromatic polyester copolymer production process in Examples and Comparative Examples, the concentration becomes 0.1% by mass with respect to the glycol solution used as a raw material at a temperature of 100 ° C. It was prepared by dissolving or dispersing as described above.
［実施例１］
・ポリエステルエラストマー組成物チップの製造
ジメチルテレフタレート、テトラメチレングリコール（モル比で、ジメチルテレフタレート／テトラメチレングリコール＝１／１．５）及び数平均分子量２０００のポリテトラメチレングリコール（ＰＴＭＧ２０００）を、ポリブチレンテレフタレート（ＰＢＴ）（ハードセグメント）／ポリテトラメチレングリコール（ＰＴＭＧ）（ソフトセセグメント）が質量比で３５／６５となるように反応器に仕込み、触媒として参考例１で調製したチタン触媒Ａ（ジメチルテレフタレートに対して１２０ミリモル％）を添加して、内温１８０℃でエステル交換反応を行った。
[Example 1]
-Manufacture of polyester elastomer composition chip Dimethyl terephthalate, tetramethylene glycol (in terms of molar ratio, dimethyl terephthalate / tetramethylene glycol = 1 / 1.5) and polytetramethylene glycol (PTMG2000) having a number average molecular weight of 2000 are converted into polybutylene terephthalate. (PBT) (hard segment) / polytetramethylene glycol (PTMG) (soft segment) was charged into a reactor so that the mass ratio was 35/65, and the titanium catalyst A (dimethyl terephthalate) prepared in Reference Example 1 was prepared as a catalyst. The transesterification was carried out at an internal temperature of 180 ° C.
理論量の約７０％のメタノールが留出した時点で、参考例３で調整した整色剤を５質量ｐｐｍ添加し、２５００℃まで昇温して重合反応を開始した。重合反応は３０分かけて４．０ｋＰａ（３０ｍｍＨｇ）とし、次の３０分で０．１３３ｋＰａ（１ｍｍＨｇ）以下とし、その後、１２０分間重合反応を継続した。 When about 70% of the theoretical amount of methanol was distilled, 5 mass ppm of the color adjusting agent prepared in Reference Example 3 was added, and the temperature was raised to 2500 ° C. to initiate the polymerization reaction. The polymerization reaction was set to 4.0 kPa (30 mmHg) over 30 minutes, and to 0.133 kPa (1 mmHg) or less in the next 30 minutes, and then the polymerization reaction was continued for 120 minutes.
・ポリエステル繊維の製造
チップを１３０℃、４時間乾燥後、紡糸温度２６０℃、巻き取り速度４００ｍ／分で８０ｄｔｅｘ／１２ｆｉｌの紡糸し、弾性糸を得た。
-Manufacture of polyester fiber The chip was dried at 130 ° C for 4 hours, and then spun at a spinning temperature of 260 ° C and a winding speed of 400 m / min at 80 dtex / 12 fil to obtain an elastic yarn.
［実施例２〜５］
実施例１において、整色剤を表２に示す種類及び量に変更したこと以外は実施例１と同様に実施した。
[Examples 2 to 5]
In Example 1, it implemented similarly to Example 1 except having changed the color adjusting agent into the kind and quantity which are shown in Table 2.
［比較例１］
整色剤をゼロしたこと以外は実施例１と同様に実施した。結果を表１に示す。
[Comparative Example 1]
The same procedure as in Example 1 was performed except that the color adjusting agent was zero. The results are shown in Table 1.
本発明によればポリエステルの優れた特性を保持しながら、アンチモンやゲルマニウム触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。その結果、色相に優れたポリエステル弾性繊維、及び成形品を提供することができる。 According to the present invention, it is possible to eliminate the deterioration of the hue, which is a defect of the polyester not using antimony or germanium catalyst, while maintaining the excellent characteristics of the polyester. As a result, a polyester elastic fiber excellent in hue and a molded product can be provided.
Claims (10)
１３０℃、２時間熱処理後のＬ＊ａ＊ｂ＊表色系におけるカラーａ＊値が−５〜０、カラーｂ＊値が−５〜４の範囲にあり、
該整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ該最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記式（１）〜（４）のすべてを満たすポリエステルエラストマー組成物。
The color a * value in the L * a * b * color system after heat treatment at 130 ° C. for 2 hours is in the range of −5 to 0, and the color b * value is in the range of −5 to 4;
When a visible light absorption spectrum of a wavelength of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L in the color adjusting agent at an optical path length of 1 cm, the maximum absorption wavelength was in the range of 540 to 600 nm, and the maximum absorption wavelength was A polyester elastomer composition in which the ratio of the absorbance at each wavelength below to the absorbance satisfies all of the following formulas (1) to (4).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5045895A (en) * | 1973-08-30 | 1975-04-24 | ||
| JPH08199428A (en) * | 1995-01-17 | 1996-08-06 | Teijin Ltd | Production of titanium dioxide-containing polyester fiber |
| JP2003012787A (en) * | 2001-06-27 | 2003-01-15 | Teijin Ltd | Thermoplastic polyester resin composition and film therefrom |
| JP2003147635A (en) * | 2001-08-29 | 2003-05-21 | Teijin Ltd | Polyester fiber and method for producing the same |
| JP2003238673A (en) * | 2002-02-19 | 2003-08-27 | Toray Ind Inc | Method for producing polyester |
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2004
- 2004-10-06 JP JP2004293414A patent/JP2006104341A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5045895A (en) * | 1973-08-30 | 1975-04-24 | ||
| JPH08199428A (en) * | 1995-01-17 | 1996-08-06 | Teijin Ltd | Production of titanium dioxide-containing polyester fiber |
| JP2003012787A (en) * | 2001-06-27 | 2003-01-15 | Teijin Ltd | Thermoplastic polyester resin composition and film therefrom |
| JP2003147635A (en) * | 2001-08-29 | 2003-05-21 | Teijin Ltd | Polyester fiber and method for producing the same |
| JP2003238673A (en) * | 2002-02-19 | 2003-08-27 | Toray Ind Inc | Method for producing polyester |
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