JP2004307553A - Method for producing polytrimethylene terephthalate and resin composition of the same - Google Patents
Method for producing polytrimethylene terephthalate and resin composition of the same Download PDFInfo
- Publication number
- JP2004307553A JP2004307553A JP2003099323A JP2003099323A JP2004307553A JP 2004307553 A JP2004307553 A JP 2004307553A JP 2003099323 A JP2003099323 A JP 2003099323A JP 2003099323 A JP2003099323 A JP 2003099323A JP 2004307553 A JP2004307553 A JP 2004307553A
- Authority
- JP
- Japan
- Prior art keywords
- polytrimethylene terephthalate
- extruder
- ptt
- acid
- solvent
- 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.)
- Granted
Links
- 229920002215 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 76
- -1 polytrimethylene terephthalate Polymers 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000011342 resin composition Substances 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910001867 inorganic solvent Inorganic materials 0.000 claims abstract description 12
- 239000003049 inorganic solvent Substances 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 24
- 229920005989 resin Polymers 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004898 kneading Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 11
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 230000006866 deterioration Effects 0.000 abstract description 8
- 239000008188 pellet Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-M octacosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O UTOPWMOLSKOLTQ-UHFFFAOYSA-M 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002667 nucleating agent Substances 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
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 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
- 229920000642 polymer Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- CJWNFAKWHDOUKL-UHFFFAOYSA-N 2-(2-phenylpropan-2-yl)phenol Chemical compound C=1C=CC=C(O)C=1C(C)(C)C1=CC=CC=C1 CJWNFAKWHDOUKL-UHFFFAOYSA-N 0.000 description 1
- FVEAIIZMVQXSQE-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-2-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=CC(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O FVEAIIZMVQXSQE-UHFFFAOYSA-N 0.000 description 1
- ROVLJQDICPLANK-UHFFFAOYSA-N 2-ethoxy-3-hydroxybenzoic acid Chemical compound CCOC1=C(O)C=CC=C1C(O)=O ROVLJQDICPLANK-UHFFFAOYSA-N 0.000 description 1
- MFJDFPRQTMQVHI-UHFFFAOYSA-N 3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound O=C1OCOC(=O)C2=CC=C1C=C2 MFJDFPRQTMQVHI-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical class OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229950002083 octabenzone Drugs 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、押出機を用いて、ポリトリメチレンテレフタレートを改質するにあたり、押出機内での滞留による樹脂劣化を抑え、色調に優れたポリトリメチレンテレフタレートを供給する製造方法およびその改質ポリトリメチレンテレフタレートに関するものである。
【０００２】
【従来の技術】
ポリエチレンテレフタレート（以下ＰＥＴと略称することがある。）やポリブチレンテレフタレート（以下ＰＢＴと略称することがある。）に代表される熱可塑性ポリエステルは、多くの優れた特性を有しているため、衣料用繊維、工業用繊維、フィルム、樹脂、その他の成形品用の素材として広く利用されている。一方で、ＰＥＴやＰＢＴは、加水分解しやすく、溶融する前には「絶乾」といわれる極微量水分率まで乾燥する必要がある。
【０００３】
また、添加剤、強化材、他の熱可塑性樹脂などによるポリトリメチレンテレフタレートの改質に、押出機を用いることは既に公知である。（例えば特許文献１〜２参照）
また、製糸性および色調の改良を目的に、ベント付き押出機を用いてポリトリメチレンテレフタレートの改質を行っている例もあるが、ポリトリメチレンテレフタレートの含有する水分率については開示されておらず、効果として色調の改良はある程度みられるものの、押出機での溶融滞留による粘度低下の抑制については、満足できるものではない。（例えば特許文献３参照）
さらに、押出機による溶融混練前に乾燥を実施している例もあるが、該方法ではポリマー色調および樹脂の粘度低下の抑制ともに不十分である。（例えば特許文献４参照）
【０００４】
【特許文献１】
特開２００２−３５８９号公報
【特許文献２】
特開２００２−４７３９７号公報
【特許文献３】
特開２００２−３５８９号公報
【特許文献４】
特開２００２−４７３９７号公報
【０００５】
【発明が解決しようとする課題】
本発明は、この様な現状に鑑み、上記の問題点のない、即ち、押出機内での滞留による樹脂劣化を抑え、かつ色調に優れたポリトリメチレンテレフタレートの製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明者は、上記課題を解決すべく鋭利検討した結果、ポリトリメチレンテレフタレートに沸点が３０〜２００℃の有機及び／又は無機溶媒を０．０２〜５ｗｔ％含有した状態で押出機に供給し溶融混練することによって、押出機内での滞留による樹脂劣化を抑え、かつ色調に優れた改質ポリトリメチレンテレフタレートを得られることを見出し、本発明に至った。
【０００７】
すなわち本発明は、以下のとおりである。
１．ポリトリメチレンテレフタレートに、沸点が３０〜２００℃の有機及び／又は無機溶媒を０．０１〜５ｗｔ％含有させた状態で、押出機に供給し、溶融混練して得ることを特徴とする改質ポリトリメチレンテレフタレートの製造方法。
２．該溶媒を０．０２〜３ｗｔ％含有させることを特徴とする上記１に記載の製造方法。
３．該溶媒が、水であることを特徴とする、上記１又は２に記載の製造方法。
４．該押出機のダイスより排出される該ポリトリメチレンテレフタレートの樹脂温度が、２４０〜３５０℃であることを特徴とする上記１〜３のいずれかに記載の製造方法。
【０００８】
５．該押出機がベント付き２軸押出機であり、Ｌ／Ｄ＝２０〜６０であることを特徴とする上記１から４のいずれかに記載の製造方法。
６．上記１〜５のいずれかに記載の方法によって得られた、改質ポリトリメチレンテレフタレート。
７．該改質ポリトリメチレンテレフタレートが、さらに強化材を配合してなることを特徴とする上記６に記載の改質ポリトリメチレンテレフタレート。
【０００９】
【発明の実施の形態】
以下、本発明に関して具体的に説明する。
まず、本発明のポリトリメチレンテレフタレートについて詳述する。
本発明におけるポリトリメチレンテレフタレート（以下、ＰＴＴと略称することがある。）とは、酸成分には主としてテレフタル酸を用い、グリコール成分には主としてトリメチレングリコールからなるポリエステルポリマーである。
【００１０】
テレフタル酸以外の芳香族ジカルボン酸、例えばフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、ジフェニルジカルボン酸、ジフェニルエーテルジカルボン酸、ジフェノキシエタンジカルボン酸、ジフェニルメタンジカルボン酸、ジフェニルケトンジカルボン酸、ジフェニルスルフォンジカルボン酸等；コハク酸、アジピン酸、セバシン酸等の脂肪族ジカルボン酸；シクロヘキサンジカルボン酸等の脂環族ジカルボン酸；ε−オキシカプロン酸、ヒドロキシ安息香酸、ヒドロキシエトキシ安息香酸等のオキシジカルボン酸が例示される。テレフタル酸成分は、酸成分の８０モル％以上である。
【００１１】
本発明においてトリメチレングリコールとしては、１，３−プロパンジオール、１，２−プロパンジオール、１，１−プロパンジオール、２，２−プロパンジオール、あるいはこれらの混合物の中から選ばれるが、安定性の観点から１，３−プロパンジオールが特に好ましく、グリコール成分の８０モル％以上である。
他のグリコール成分としてはエチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、オクタメチレングリコール、ネオペンチルグリコール、シクロヘキサンジメタノール、キシリレングリコール、ジエチレングリコール、ポリオキシアルキレングリコール、ハイドロキノンなどが例示される。
【００１２】
また、上述のポリエステル成分に分岐成分、例えばトリカルバリル酸、トリメシン酸、トリメリット酸等の三官能または四官能のエステル形成能を持つ酸またはグリセリン、トリメチロールプロパン、ペンタエリトリットなどの三官能または四官能のエステル形成能を持つアルコールを共重合してもよく、その場合にそれらは全ジカルボン酸成分の１．０モル％以下、好ましくは、０．５モル％以下、さらに好ましくは、０．３モル％以下である。
更に、ＰＴＴはこれら共重合成分を２種類以上組み合わせて使用しても構わない。
【００１３】
本発明のＰＴＴは、その極限粘度［η］が０．６０以上であることが機械特性の面から好ましく、［η］が０．７０以上であることがより好ましく、［η］が０．８０以上であることが最も好ましい。
極限粘度［η］についてはオストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中での比粘度ηｓｐと濃度Ｃ（ｇ／１００ｍｌ）の比ηｓｐ／Ｃを濃度ゼロに外挿し、以下の式により求めることが出来る。
［η］＝ｌｉｍ（ηｓｐ／Ｃ） Ｃ→０
【００１４】
本発明に用いられるＰＴＴの製造方法は、特に限定されるものではないが、例えば、特開昭５１−１４０９９２号公報、特開平５−２６２８６２号公報、特開平８−３１１１７７号公報等に記載されている方法によって、テレフタル酸またはそのエステル形成性誘導体（例えばジメチルエステル、モノメチルエステル等の低級アルキルエステル）とトリメチレングリコールまたはそのエステル形成性誘導体とを、触媒の存在下、好適な温度・時間で加熱反応させ、更に得られるテレフタル酸のグリコールエステルを触媒の存在下、好適な温度・時間で所望の重合度まで重縮合反応させる方法が挙げられる。
【００１５】
次に本発明の製造方法において用いる押出機には、単軸あるいは２軸押出機が用いられるが、ベント付き２軸押出機が好ましく、混練性能を高めるために少なくともニーディングディスク及び／又はローターディスクが装着されていることが好ましい。ニーディングディスクとは、略楕円形のディスクを数枚、一定の位相でずらしながら組み合わせた混練用のスクリューセグメントであり、スクリューの回転にともなってＰＴＴを細いクリアランスへ通すことで極めて高い剪断力を付与することができる。
【００１６】
一方、ローターディスクとは、多角形の稜線を回転軸に対して一定の角度でねじってあるスクリューセグメントであり、クリアランスがセグメントの全位置で一定であるという特徴がある。スクリュー軸に対する稜線のねじりの向きに順送りと逆送りのセグメントがあり、これらを組み合わせることで、高い剪断力を均質に付与することができる。
ニーディングセグメント及び／又はローターディスクは、所望の添加剤や強化材などの分散及び固有粘度等のＰＴＴ樹脂物性の目標により、適切に選ぶことができ、その範囲に特に制限はないが、装着数をディスク又はセグメント長（Ｌ）とスクリュー径（Ｄ）との比Ｌ／Ｄで表したとき、ニーディングディスク及びローターディスクの装着量はそれぞれ、Ｌ／Ｄ＝２〜６０の範囲が好ましく、より好ましくはＬ／Ｄ＝１０〜５０の範囲である。Ｌ／Ｄが上記の範囲にあるときが、十分な混練効果を発揮できる。
【００１７】
また、押出機内の温度は供給するポリトリメチレンテレフタレートの融点より１０℃以上高い温度に設定することが好ましいが、特に押出機ダイスより排出されるＰＴＴ樹脂温度を２４０〜３５０℃に制御することが好ましい。より好ましくは、２６０〜３３０℃である。充分な混練及び安定した運転を考慮にいれると樹脂温度が２４０℃以上であることが好ましく、また樹脂の分解を考慮すると３５０℃以下であることが好ましい。
【００１８】
また、ポリトリメチレンテレフタレート及び／又は改質材が溶融混合している領域において、一箇所以上のベント孔を設けるのが好ましく、真空ポンプ、スチームエジェクター等を用いて減圧下にすることが好ましい。通常は１０ｋＰａ以下、好ましくは５ｋＰａ以下、更に好ましくは１ｋＰａ以下であり、ＰＴＴの溶融時に発生する有機及び／又は無機の蒸気、あるいは極少量生成する副反応物であるアリルアルコール、アクロレイン等を留去することが好ましい。
【００１９】
さらに、押出機内での平均滞留時間は０．１〜３０分であり、０．２〜１５分であることが好ましく、特に、０．３〜１０分がより好ましい。押出機のスクリューの回転数は、２０〜５００ｒｐｍ程度に設定すればよく、好ましくは５０〜３００ｒｐｍである。押出機として２軸型の押出機を用いる場合には、２軸の回転方向は同一方向でも逆方向でもよいが、同一方向の回転とした方が熱劣化を抑える観点から好ましい。
【００２０】
上記押出機を用いて、ＰＴＴの改質を行う際、供給するＰＴＴには、沸点が３０〜２００℃の有機及び／又は無機の溶媒を、０．０１〜５ｗｔ％含有させることが必要である。好ましくは沸点が５０〜１５０℃の有機及び／又は無機の溶媒であり、含有量については、好ましくは０．０２〜３ｗｔ％、より好ましくは０．０５〜１．０ｗｔ％である。
有機及び／又は無機溶媒の沸点は、溶媒の取り扱いを考慮すると３０℃以上が好ましく、樹脂中に残存し品質上問題が起こることを考慮すると２００℃以内が好ましい。また、該溶媒の含有量は、本発明の効果を考慮すると、０．０１ｗｔ％以上が好ましく、押出機内での蒸発ガス量が多くなりバックフローによって安定押出しが困難となることを考慮すると５ｗｔ％以内が好ましい。
【００２１】
有機及び／又は無機溶媒の添加方法については、特に制限はなく、予めＰＴＴと所定量混合した後に押出機へ供給してもよく、また、該溶媒とＰＴＴを別フィードで供給してもよい。別フィードの場合の添加位置についても、ＰＴＴ供給口あるいは、ＰＴＴ供給口からベント孔の間が好ましい。
有機溶媒の具体例としては、メタノールやエタノールなどのアルコール類、トリエチルアミン、モノ−ｎ−ブチルアミンなどのアミン類、ジエチルエーテル、ジブチルエーテルなどのエーテル類、などが挙げられる。
【００２２】
無機溶媒の具体例としては、水、酸またはアルカリ水溶液などが挙げられるが、当然、有機溶媒と無機溶媒の混合でもよく、トリエチルアミン水溶液やアンモニア水溶液なども本発明の溶媒に含まれる。
好ましい溶媒としては、メタノールやエタノールなどのアルコール類、トリエチルアミン水溶液やアンモニア水溶液、水が挙げられるが、中でもベント孔より排出される溶媒蒸気の回収のしやすさから、水がより好ましい。
溶媒が本発明の効果に与えるメカニズムについては、詳細は不明だが、溶媒が押出機内で蒸発する際に、押出機内の混入空気をより強制排出することで、樹脂の着色や酸化劣化を抑制することが考えられる。さらに、ＰＴＴの残留重合触媒を失活する働きがあると考えられる。
【００２３】
また、ＰＴＴの改良には様々な目的や手法があるが、強化剤等を添加する方法が挙げられる。例えば、ＰＴＴの熱安定性向上を目的とした、テトラキス（２，４−ジ−ｔ−ブチルフェニル）［１，１−ビフェニ］−４，４‘−ジイルビスホスフォナイトやトリス（２，４−ジ−ｔ−ブチルフェニル）フォスファイトなどの熱安定剤、エチレンビス（オキシエチレン）ビス［３−（５−ｔ−ブチル−４−ヒドロキシ−ｍ−トリル）プロピオネート］などの酸化防止剤などを配合する方法、光安定性向上を目的とした、２−（２Ｈ−ベンゾトリアゾール−２−イル）−４−６−ビス（１−メチル−１−フェニルエチル）フェノールや２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノールやオクタベンゾンなどの各種紫外線吸収剤などを配合する方法、成形加工性向上を目的とした、タルクや窒化ホウ素や脂肪酸金属塩（モンタン酸Ｎａやモンタン酸Ｃａ）などの核剤、脂肪酸（ステアリン酸など）や脂肪酸エステルやワックスなどの滑剤などを配合する方法、着色を目的とした、カーボンブラックやアルミ粉などの顔料、フタロシアニンなどの染料などを配合する方法、機械的特性向上を目的とした、ガラスファイバー、カーボンファイバー、タルク、ウオラストナイト、ハイドロタルサイトなどの無機フィラーなどを配合する方法、難燃性付与を目的とした、臭素化ポリスチレンなどのハロゲン系難燃剤、ポリリン酸メラミンや赤燐などの非ハロゲン系難燃剤などを配合する方法、耐衝撃性や耐熱性向上などを目的とした、ポリカーボネート樹脂やＡＢＳ樹脂などの熱可塑性樹脂、ポリエステルポリエーテルエラストマーなどのエラストマーなどを配合する方法が挙げられる。
特に、ガラスファイバーなどの無機フィラーを用いた改質の場合、樹脂温度が高くなり、滞留劣化や着色が起こりやすく、本発明の効果が顕著となる。
【００２４】
【実施例】
以下、実施例などを用いて本発明を更に詳細に説明するが、本発明は実施例などにより何ら限定されるものではない。
なお実施例中に用いた、ポリトリメチレンテレフタレート、有機及び無機溶媒、改良材及び主な評価方法は以下の通りである。
（１）ポリトリメチレンテレフタレート
ａ−１：極限粘度１．０のポリトリメチレンテレフタレート
ａ−２：極限粘度１．０のポリブチレンテレフタレート
（２）溶媒
ｂ−１：無機溶媒として、イオン交換水
ｂ−２：有機溶媒として、エタノール
【００２５】
（３）改良材
ｃ−１：モンタン酸Ｎａ（クラリアントジャパン社（株）製。Ｌｉｃｏｍｏｎｔ ＮａＶ１０１）
ｃ−２：ガラス繊維（日本電気硝子社（株）製。０３Ｔ−１８７／ＰＬ）
ｃ−３：臭素化ポリスチレン（フェロ社（株）製。パイロチェック６８ＰＢ−ＬＭ）
【００２６】
（４）極限粘度［η］
オストワルド粘度計を用い、３５℃、ｏ−クロロフェノール中での比粘度ηｓｐと濃度Ｃ（ｇ／１００ｍｌ）の比ηｓｐ／Ｃを濃度ゼロに外挿し、以下の式により求めた。
［η］＝ｌｉｍ（ηｓｐ／Ｃ） Ｃ→０
（５）水分率［％］
カールフィッシャー法により求めた。
（６）色調（ｂ値）
色差計（日本電色工業社製 ＮＤ−Σ８０型）を用いて測定した。
【００２７】
【実施例１】
極限粘度１．０のポリトリメチレンテレフタレートを１２０℃、５ｈｒで乾燥を行った。乾燥後のＰＴＴペレット中の水分率は、０．００５ｗｔ％であった。上記乾燥ＰＴＴペレットを１５０ｋｇ／ｈｒ、結晶核剤としてモンタン酸Ｎａを０．１５ｋｇ／ｈｒで、スクリュー径５８ｍｍ、Ｌ／Ｄ＝４５のベント付き二軸押出機（東芝機械（株）社製ＴＥＭ−５８ＢＳ）に供給した。また同時に、液添ポンプにて、イオン交換水を１５０ｇ／ｈｒで、ＰＴＴ供給口に供給した。混練条件として、シリンダー設定温度２６０℃、スクリュー回転数１５０ｒｐｍで溶融混練、ペレット化した。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度は２６７℃であり、押出機内の平均滞留時間は５６秒であった。このペレットを１２０℃×５時間乾燥させた後、各評価を行った。その結果を表１に示す。
【００２８】
【実施例２】
実施例１で使用した乾燥ＰＴＴペレットを１０５ｋｇ／ｈｒで、ベント付き二軸押出機に供給した。また同時に、液添ポンプにて、イオン交換水を１０５ｇ／ｈｒで、ＰＴＴ供給口に供給した。さらに改質としてサイドよりガラスファイバー０３Ｔ−１８７／ＰＬを４５ｋｇ／ｈｒでフィードし、シリンダー設定温度２６０℃、スクリュー回転数１５０ｒｐｍで溶融混練、ペレット化した。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度は２８１℃であり、押出機内の平均滞留時間は５４秒であった。このペレットを１２０℃×５時間乾燥させた後、各評価を行った。その結果を表１に示す。
【００２９】
【実施例３および４】
実施例１において、イオン交換水の添加量を変更した以外は、同様な操作を行い、各評価を行った。その結果を表１に示す。
【００３０】
【実施例５】
実施例１における乾燥ＰＴＴペレットを、２３℃ＲＨ５０％の雰囲気中に７日間放置し、水分率を測定し０．１５ｗｔ％であった該ＰＴＴペレットを１０５ｋｇ／ｈｒで、上記押出機に供給した。また、液添微量ポンプでの、イオン交換水の供給は実施しなかった。さらに改良としてサイドよりガラスファイバー０３Ｔ−１８７／ＰＬを４５ｋｇ／ｈｒでフィードし、シリンダー設定温度２６０℃、スクリュー回転数１５０ｒｐｍで溶融混練、ペレット化した。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度は２８０℃であった。このペレットを１２０℃×５時間乾燥させた後、各評価を行った。その結果を表２に示す。
【００３１】
【実施例６および７】
実施例５における水分率０．１５ｗｔ％のＰＴＴペレットを用いて、運転条件を変更して実施例５と同様な操作を行い、各評価を行った。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度はそれぞれ３０７、３２２℃であり、押出機内の平均滞留時間はそれぞれ３７秒と２９秒であった。その結果を表２に示す。
【００３２】
【実施例８】
実施例５における水分率０．１５ｗｔ％のＰＴＴペレットを用いて、改質材として更に、臭素化ポリスチレンを追加し、実施例５と同様な操作を行い、各評価を行った。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度はそれぞれ２７７℃であり、押出機内の平均滞留時間はそれぞれ５９秒であった。その結果を表２に示す。
【００３３】
【実施例９】
実施例１における乾燥後ＰＴＴペレットを、２３℃ＲＨ９０％の雰囲気中に１５日間放置し、水分率を測定し０．２３ｗｔ％であった該ＰＴＴペレットを用いて、実施例５と同様な操作を行い、各評価を行った。その結果を表３に示す。
【００３４】
【実施例１０】
実施例２において、イオン交換水をエタノールに変更し、１０５ｇ／ｈｒで供給した以外は実施例２と同様な操作を行い、各評価を行った。その結果を表３に示す。
【００３５】
【比較例１】
実施例１における乾燥ＰＴＴペレットを、そのまま１５０ｋｇ／ｈｒ、結晶核剤としてモンタン酸Ｎａを０．１５ｋｇ／ｈｒで、上記押出機に供給した。また、液添微量ポンプでの、イオン交換水の供給は実施しなかった。混練条件として、シリンダー設定温度２６０℃、スクリュー回転数１５０ｒｐｍで溶融混練、ペレット化した。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度は２６９℃であった。このペレットを１２０℃×５時間乾燥させた後、各評価を行った。その結果を表４に示す。
【００３６】
【比較例２】
実施例２における乾燥ＰＴＴペレットを、そのまま１０５ｋｇ／ｈｒで、上記押出機に供給した。また、液添微量ポンプでの、イオン交換水の供給は実施しなかった。さらに改質としてサイドよりガラスファイバー０３Ｔ−１８７／ＰＬを４５ｋｇ／ｈｒでフィードし、シリンダー設定温度２６０℃、スクリュー回転数１５０ｒｐｍで溶融混練、ペレット化した。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度は２８２℃であった。このペレットを１２０℃×５時間乾燥させた後、各評価を行った。その結果を表４に示す。
【００３７】
【比較例３および４】
比較例１において、運転条件を変更した以外は、同様な操作を行い、各評価を行った。このとき、押出し機ダイスより排出されるポリトリメチレンテレフタレート樹脂組成物の樹脂温度はそれぞれ３０６、３２１℃であり、押出機内の平均滞留時間はそれぞれ３７秒と２９秒であった。その結果を表１に示す。その結果を表４に示す。
【００３８】
【比較例５】
実施例２において、イオン交換水の添加量を７３００ｇ／ｈｒに変更した以外は、同様な操作を行ったが、スクリューモーターの変動が激しく、安定運転ができなかった。そのため評価を断念した。
【００３９】
【比較例６】
実施例２において、ＰＴＴをＰＢＴに変更した以外は、同様な操作を行い、各評価を行った。その結果を表５に示す。なお、１２０℃、５ｈｒ乾燥後のＰＢＴの水分率は、０．００５％であった。
【００４０】
【表１】
【表２】
【表３】
【表４】
【表５】
【発明の効果】
本発明のポリトリメチレンテレフタレートに関する製造方法は、押出機内での滞留による劣化を抑制するとともに、色調に優れたポリトリメチレンテレフタレートを提供できる。さらには、本発明の製造方法で得られた改質ポリトリメチレンテレフタレートは、衣料用繊維、工業用繊維、フィルム、樹脂、その他の成形品用の素材として広く利用される。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for supplying polytrimethylene terephthalate having excellent color tone by suppressing resin deterioration due to stagnation in the extruder and modifying the polytrimethylene terephthalate when modifying polytrimethylene terephthalate using an extruder. It relates to methylene terephthalate.
[0002]
[Prior art]
BACKGROUND ART Thermoplastic polyesters represented by polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polybutylene terephthalate (hereinafter sometimes abbreviated as PBT) have many excellent properties, and therefore, they are used for clothing. It is widely used as a material for industrial fibers, industrial fibers, films, resins, and other molded products. On the other hand, PET and PBT are easily hydrolyzed, and need to be dried to a trace moisture content called “absolutely dry” before melting.
[0003]
It is already known to use an extruder for modifying polytrimethylene terephthalate with additives, reinforcing materials, other thermoplastic resins, and the like. (See, for example, Patent Documents 1 and 2)
In some cases, polytrimethylene terephthalate is modified using a vented extruder for the purpose of improving the yarn formability and color tone.However, the moisture content of polytrimethylene terephthalate is not disclosed. Although the color tone can be improved to some extent as an effect, the suppression of the decrease in viscosity due to the stagnation of the melt in the extruder is not satisfactory. (For example, see Patent Document 3)
Further, in some cases, drying is performed before melt-kneading by an extruder, but this method is insufficient for suppressing both the color tone of the polymer and the decrease in the viscosity of the resin. (For example, see Patent Document 4)
[0004]
[Patent Document 1]
Japanese Patent Application Laid-Open No. 2002-3589 [Patent Document 2]
JP 2002-47397 A [Patent Document 3]
JP 2002-3589 A [Patent Document 4]
JP-A-2002-47397
[Problems to be solved by the invention]
In view of the above situation, an object of the present invention is to provide a method for producing polytrimethylene terephthalate which does not have the above-mentioned problems, that is, suppresses resin deterioration due to stagnation in an extruder, and has excellent color tone. I do.
[0006]
[Means for Solving the Problems]
As a result of sharp studies to solve the above problems, the present inventor supplied polytrimethylene terephthalate to an extruder in a state where 0.02 to 5 wt% of an organic and / or inorganic solvent having a boiling point of 30 to 200 ° C was contained. It has been found that by melt-kneading, it is possible to obtain a modified polytrimethylene terephthalate which suppresses resin deterioration due to stagnation in an extruder and has excellent color tone.
[0007]
That is, the present invention is as follows.
1. A modification in which polytrimethylene terephthalate contains 0.01 to 5% by weight of an organic and / or inorganic solvent having a boiling point of 30 to 200 ° C., is supplied to an extruder, and is obtained by melt-kneading. A method for producing polytrimethylene terephthalate.
2. 2. The method according to the above item 1, wherein the solvent is contained in an amount of 0.02 to 3% by weight.
3. 3. The method according to the above item 1 or 2, wherein the solvent is water.
4. 4. The method according to any one of the above items 1 to 3, wherein the resin temperature of the polytrimethylene terephthalate discharged from the die of the extruder is 240 to 350 ° C.
[0008]
5. The method according to any one of the above items 1 to 4, wherein the extruder is a twin-screw extruder with a vent, and L / D = 20 to 60.
6. A modified polytrimethylene terephthalate obtained by the method according to any one of the above 1 to 5.
7. 7. The modified polytrimethylene terephthalate according to the above item 6, wherein the modified polytrimethylene terephthalate further comprises a reinforcing material.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically.
First, the polytrimethylene terephthalate of the present invention will be described in detail.
The polytrimethylene terephthalate (hereinafter sometimes abbreviated as PTT) in the present invention is a polyester polymer mainly composed of terephthalic acid for the acid component and mainly composed of trimethylene glycol for the glycol component.
[0010]
Aromatic dicarboxylic acids other than terephthalic acid, such as phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylketonedicarboxylic acid, diphenylsulfonedicarboxylic acid Acids; aliphatic dicarboxylic acids such as succinic acid, adipic acid and sebacic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; oxydicarboxylic acids such as ε-oxycaproic acid, hydroxybenzoic acid, and hydroxyethoxybenzoic acid. Is done. The terephthalic acid component is at least 80 mol% of the acid component.
[0011]
In the present invention, the trimethylene glycol is selected from 1,3-propanediol, 1,2-propanediol, 1,1-propanediol, 2,2-propanediol, and a mixture thereof. In view of the above, 1,3-propanediol is particularly preferable, and is 80 mol% or more of the glycol component.
Examples of other glycol components include ethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol, cyclohexane dimethanol, xylylene glycol, diethylene glycol, polyoxyalkylene glycol, hydroquinone, and the like. .
[0012]
Further, a branched component to the above-mentioned polyester component, for example, tricarballylic acid, trimesic acid, an acid having a trifunctional or tetrafunctional ester-forming ability such as trimellitic acid or glycerin, trimethylolpropane, trifunctional such as pentaerythritol Alcohols having tetrafunctional ester-forming ability may be copolymerized, in which case they are 1.0 mol% or less, preferably 0.5 mol% or less, more preferably 0.1 mol% or less of the total dicarboxylic acid component. 3 mol% or less.
Further, PTT may be used in combination of two or more of these copolymer components.
[0013]
The intrinsic viscosity [η] of the PTT of the present invention is preferably 0.60 or more from the viewpoint of mechanical properties, more preferably [η] is 0.70 or more, and [η] is 0.80 or more. It is most preferred that this is the case.
For intrinsic viscosity [η], an Ostwald viscometer was used to extrapolate the specific viscosity η sp in o-chlorophenol and the ratio η sp / C of concentration C (g / 100 ml) to zero in 35 ° C. It can be obtained by the formula.
[Η] = lim (η sp / C) C → 0
[0014]
The method for producing PTT used in the present invention is not particularly limited, and is described in, for example, JP-A-51-140992, JP-A-5-262882, JP-A-8-31177, and the like. Terephthalic acid or an ester-forming derivative thereof (eg, a lower alkyl ester such as dimethyl ester or monomethyl ester) and trimethylene glycol or an ester-forming derivative thereof at a suitable temperature and time in the presence of a catalyst. A method in which the reaction is carried out by heating, and the resulting glycol ester of terephthalic acid is subjected to a polycondensation reaction in the presence of a catalyst at a suitable temperature and time to a desired polymerization degree.
[0015]
Next, as the extruder used in the production method of the present invention, a single-screw or twin-screw extruder is used, and a twin-screw extruder with a vent is preferable. In order to enhance the kneading performance, at least a kneading disk and / or a rotor disk Is preferably mounted. A kneading disk is a kneading screw segment that combines several elliptical disks while shifting them at a constant phase, and by passing the PTT through a small clearance with the rotation of the screw, extremely high shearing force is achieved. Can be granted.
[0016]
On the other hand, the rotor disk is a screw segment in which a polygonal ridge is twisted at a fixed angle with respect to the rotation axis, and has a feature that the clearance is constant at all positions of the segment. There are forward and reverse feed segments in the direction of the ridge torsion with respect to the screw shaft, and by combining these, a high shearing force can be applied uniformly.
The kneading segment and / or the rotor disk can be appropriately selected according to the desired dispersion of additives and reinforcing materials, and the PTT resin properties such as intrinsic viscosity, and the range is not particularly limited. Is represented by the ratio L / D of the disk or segment length (L) to the screw diameter (D), the mounting amount of the kneading disk and the rotor disk is preferably in the range of L / D = 2 to 60, respectively. Preferably, L / D is in the range of 10 to 50. When L / D is in the above range, a sufficient kneading effect can be exhibited.
[0017]
In addition, the temperature in the extruder is preferably set at a temperature higher than the melting point of the supplied polytrimethylene terephthalate by 10 ° C. or more. In particular, it is preferable to control the temperature of the PTT resin discharged from the extruder die to 240 to 350 ° C. preferable. More preferably, it is 260-330 ° C. In consideration of sufficient kneading and stable operation, the resin temperature is preferably 240 ° C. or higher, and in consideration of the decomposition of the resin, the resin temperature is preferably 350 ° C. or lower.
[0018]
Further, it is preferable to provide one or more vent holes in a region where the polytrimethylene terephthalate and / or the modifier is melted and mixed, and it is preferable to reduce the pressure using a vacuum pump, a steam ejector, or the like. Usually, it is 10 kPa or less, preferably 5 kPa or less, more preferably 1 kPa or less, and distills off organic and / or inorganic vapors generated when PTT is melted, or allyl alcohol, acrolein, etc., which are by-products produced in a very small amount. Is preferred.
[0019]
Further, the average residence time in the extruder is 0.1 to 30 minutes, preferably 0.2 to 15 minutes, and more preferably 0.3 to 10 minutes. The rotation speed of the screw of the extruder may be set to about 20 to 500 rpm, preferably 50 to 300 rpm. When a two-screw extruder is used as the extruder, the directions of rotation of the two shafts may be the same or opposite, but it is preferable to rotate in the same direction from the viewpoint of suppressing thermal deterioration.
[0020]
When the PTT is reformed using the above extruder, it is necessary that the PTT to be supplied contains 0.01 to 5 wt% of an organic and / or inorganic solvent having a boiling point of 30 to 200 ° C. . Preferably, it is an organic and / or inorganic solvent having a boiling point of 50 to 150 ° C, and its content is preferably 0.02 to 3 wt%, more preferably 0.05 to 1.0 wt%.
The boiling point of the organic and / or inorganic solvent is preferably 30 ° C. or higher in consideration of handling of the solvent, and is preferably 200 ° C. or less in consideration of remaining in the resin and causing a problem in quality. Further, the content of the solvent is preferably 0.01 wt% or more in consideration of the effect of the present invention, and 5 wt% in consideration of the fact that the amount of evaporative gas in the extruder increases and stable extrusion becomes difficult due to backflow. Is preferably within.
[0021]
The method of adding the organic and / or inorganic solvent is not particularly limited, and may be mixed with PTT in a predetermined amount in advance and then supplied to the extruder, or the solvent and PTT may be supplied in separate feeds. Regarding the addition position in the case of a separate feed, it is preferable that the addition position is between the PTT supply port and the PTT supply port to the vent hole.
Specific examples of the organic solvent include alcohols such as methanol and ethanol, amines such as triethylamine and mono-n-butylamine, and ethers such as diethyl ether and dibutyl ether.
[0022]
Specific examples of the inorganic solvent include water, an acid or an alkali aqueous solution, and of course, a mixture of an organic solvent and an inorganic solvent may be used, and a triethylamine aqueous solution, an ammonia aqueous solution, and the like are also included in the solvent of the present invention.
Preferred solvents include alcohols such as methanol and ethanol, aqueous triethylamine solutions and aqueous ammonia solutions, and water. Among them, water is more preferred because of the ease of recovery of the solvent vapor discharged from the vent hole.
The mechanism by which the solvent gives the effect of the present invention is not known in detail.However, when the solvent evaporates in the extruder, the air mixed in the extruder is forcibly discharged to suppress coloring and oxidative deterioration of the resin. Can be considered. Further, it is considered that there is a function of deactivating the residual polymerization catalyst of PTT.
[0023]
Further, there are various purposes and methods for improving PTT, and examples thereof include a method of adding a reinforcing agent and the like. For example, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite or tris (2,4) for the purpose of improving the thermal stability of PTT Heat stabilizers such as -di-t-butylphenyl) phosphite and antioxidants such as ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate]. For the purpose of compounding and improving light stability, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol and 2- (4,6- A method of blending various ultraviolet absorbers such as diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol and octabenzone, and a method for improving moldability. A method of blending a nucleating agent such as luc, boron nitride, or a fatty acid metal salt (Na montanate or Ca montanic acid), a method of blending a lubricant such as a fatty acid (such as stearic acid), a fatty acid ester or a wax, and carbon black for coloring. For blending pigments such as aluminum and aluminum powder, dyes such as phthalocyanine, and blending inorganic fillers such as glass fiber, carbon fiber, talc, wollastonite and hydrotalcite for the purpose of improving mechanical properties A method of blending halogen-based flame retardants such as brominated polystyrene and non-halogen-based flame retardants such as melamine polyphosphate and red phosphorus for the purpose of imparting flame retardancy, with the aim of improving impact resistance and heat resistance Thermoplastic resin such as polycarbonate resin and ABS resin, polyester polyether elastomer A method of blending any elastomers and the like.
In particular, in the case of modification using an inorganic filler such as glass fiber, the resin temperature increases, retention deterioration and coloring easily occur, and the effect of the present invention becomes remarkable.
[0024]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the present invention is not limited to the examples and the like.
The polytrimethylene terephthalate, organic and inorganic solvents, modifiers and main evaluation methods used in the examples are as follows.
(1) Polytrimethylene terephthalate a-1: polytrimethylene terephthalate a-2 having an intrinsic viscosity of 1.0: polybutylene terephthalate having an intrinsic viscosity of 1.0 (2) Solvent b-1: ion-exchanged water b as an inorganic solvent -2: ethanol as an organic solvent
(3) Improved material c-1: sodium montanate (manufactured by Clariant Japan Co., Ltd. Licomont NaV101)
c-2: glass fiber (manufactured by Nippon Electric Glass Co., Ltd. 03T-187 / PL)
c-3: Brominated polystyrene (manufactured by Ferro Co., Ltd., Pyrocheck 68PB-LM)
[0026]
(4) Intrinsic viscosity [η]
Using an Ostwald viscometer, the ratio η sp / C of the specific viscosity η sp and the concentration C (g / 100 ml) in o-chlorophenol at 35 ° C. was extrapolated to a concentration of zero, and determined by the following equation.
[Η] = lim (η sp / C) C → 0
(5) Moisture percentage [%]
It was determined by the Karl Fischer method.
(6) Color tone (b value)
It measured using the color difference meter (ND- # 80 type made by Nippon Denshoku Industries Co., Ltd.).
[0027]
Embodiment 1
Polytrimethylene terephthalate having an intrinsic viscosity of 1.0 was dried at 120 ° C. for 5 hours. The moisture content in the dried PTT pellet was 0.005 wt%. The dry PTT pellets were 150 kg / hr, Na montanate as a crystal nucleating agent was 0.15 kg / hr, a screw-diameter of 58 mm, L / D = 45, and a twin-screw extruder (vented by Toshiba Machine Co., Ltd.) 58BS). At the same time, ion-exchanged water was supplied to the PTT supply port at 150 g / hr by a liquid addition pump. As the kneading conditions, the mixture was melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 150 rpm, and pelletized. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 267 ° C., and the average residence time in the extruder was 56 seconds. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 1 shows the results.
[0028]
Embodiment 2
The dried PTT pellets used in Example 1 were fed at 105 kg / hr to a vented twin screw extruder. At the same time, ion exchanged water was supplied to the PTT supply port at 105 g / hr by the liquid addition pump. Further, as reforming, glass fiber 03T-187 / PL was fed from the side at a rate of 45 kg / hr, melt-kneaded at a cylinder set temperature of 260 ° C. and a screw rotation speed of 150 rpm, and pelletized. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 281 ° C., and the average residence time in the extruder was 54 seconds. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 1 shows the results.
[0029]
Embodiments 3 and 4
The same operation was performed in Example 1 except that the amount of ion-exchanged water was changed, and each evaluation was performed. Table 1 shows the results.
[0030]
Embodiment 5
The dried PTT pellets in Example 1 were left in an atmosphere of 23 ° C. and 50% RH for 7 days, and the PTT pellets whose water content was measured and was 0.15 wt% were supplied to the extruder at 105 kg / hr. In addition, the supply of ion-exchanged water by the liquid addition minute pump was not performed. As a further improvement, glass fiber 03T-187 / PL was fed from the side at a rate of 45 kg / hr, melt-kneaded at a cylinder set temperature of 260 ° C. and a screw rotation speed of 150 rpm, and pelletized. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 280 ° C. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 2 shows the results.
[0031]
Embodiments 6 and 7
Using PTT pellets having a water content of 0.15 wt% in Example 5, the same operation as in Example 5 was performed by changing the operating conditions, and each evaluation was performed. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 307 and 322 ° C., respectively, and the average residence time in the extruder was 37 seconds and 29 seconds, respectively. Table 2 shows the results.
[0032]
Embodiment 8
Using the PTT pellets having a water content of 0.15 wt% in Example 5 and further adding brominated polystyrene as a modifier, the same operation as in Example 5 was performed, and each evaluation was performed. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 277 ° C., respectively, and the average residence time in the extruder was 59 seconds. Table 2 shows the results.
[0033]
Embodiment 9
The dried PTT pellets in Example 1 were allowed to stand in an atmosphere at 23 ° C. and 90% RH for 15 days, and the same operation as in Example 5 was performed using the PTT pellets whose moisture content was measured and was 0.23 wt%. Each evaluation was performed. Table 3 shows the results.
[0034]
Embodiment 10
In Example 2, each evaluation was performed by performing the same operation as in Example 2 except that the ion-exchanged water was changed to ethanol and supplied at 105 g / hr. Table 3 shows the results.
[0035]
[Comparative Example 1]
The dried PTT pellets in Example 1 were supplied to the extruder at 150 kg / hr as it was, and Na montanate as a nucleating agent at 0.15 kg / hr. In addition, the supply of ion-exchanged water by the liquid addition minute pump was not performed. As the kneading conditions, the mixture was melt-kneaded at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 150 rpm, and pelletized. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 269 ° C. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 4 shows the results.
[0036]
[Comparative Example 2]
The dried PTT pellets in Example 2 were directly supplied to the above extruder at 105 kg / hr. In addition, the supply of ion-exchanged water by the liquid addition minute pump was not performed. Further, as reforming, glass fiber 03T-187 / PL was fed from the side at a rate of 45 kg / hr, melt-kneaded at a cylinder set temperature of 260 ° C. and a screw rotation speed of 150 rpm, and pelletized. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 282 ° C. After the pellets were dried at 120 ° C. for 5 hours, each evaluation was performed. Table 4 shows the results.
[0037]
[Comparative Examples 3 and 4]
In Comparative Example 1, the same operation was performed except that the operating conditions were changed, and each evaluation was performed. At this time, the resin temperature of the polytrimethylene terephthalate resin composition discharged from the extruder die was 306 and 321 ° C., respectively, and the average residence time in the extruder was 37 seconds and 29 seconds, respectively. Table 1 shows the results. Table 4 shows the results.
[0038]
[Comparative Example 5]
A similar operation was performed in Example 2 except that the amount of ion-exchanged water was changed to 7300 g / hr. However, the screw motor greatly fluctuated, and stable operation could not be performed. Therefore, the evaluation was abandoned.
[0039]
[Comparative Example 6]
The same operation was performed in Example 2 except that PTT was changed to PBT, and each evaluation was performed. Table 5 shows the results. The moisture content of the PBT after drying at 120 ° C. for 5 hours was 0.005%.
[0040]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
【The invention's effect】
The production method for polytrimethylene terephthalate of the present invention can provide a polytrimethylene terephthalate having excellent color tone while suppressing deterioration due to stagnation in an extruder. Furthermore, the modified polytrimethylene terephthalate obtained by the production method of the present invention is widely used as a material for clothing fibers, industrial fibers, films, resins, and other molded products.
Claims (7)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329885A (en) * | 1993-05-18 | 1994-11-29 | Toray Ind Inc | Production of polyester composition |
| JP2001247754A (en) * | 2000-03-08 | 2001-09-11 | Teijin Ltd | Resin pellet mixture for connector, and method of producing the same |
| JP2002060476A (en) * | 2000-08-17 | 2002-02-26 | Teijin Ltd | Method for producing polytrimethylene terephthalate having improved heat resistance |
| JP2002307434A (en) * | 2001-02-09 | 2002-10-23 | Toyobo Co Ltd | Method for manufacturing polyester molded object |
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2003
- 2003-04-02 JP JP2003099323A patent/JP4610165B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06329885A (en) * | 1993-05-18 | 1994-11-29 | Toray Ind Inc | Production of polyester composition |
| JP2001247754A (en) * | 2000-03-08 | 2001-09-11 | Teijin Ltd | Resin pellet mixture for connector, and method of producing the same |
| JP2002060476A (en) * | 2000-08-17 | 2002-02-26 | Teijin Ltd | Method for producing polytrimethylene terephthalate having improved heat resistance |
| JP2002307434A (en) * | 2001-02-09 | 2002-10-23 | Toyobo Co Ltd | Method for manufacturing polyester molded object |
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