JP4448310B2 - Polyester resin composition - Google Patents
Polyester resin composition Download PDFInfo
- Publication number
- JP4448310B2 JP4448310B2 JP2003351489A JP2003351489A JP4448310B2 JP 4448310 B2 JP4448310 B2 JP 4448310B2 JP 2003351489 A JP2003351489 A JP 2003351489A JP 2003351489 A JP2003351489 A JP 2003351489A JP 4448310 B2 JP4448310 B2 JP 4448310B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- film
- polyester resin
- acid
- neck
- 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.)
- Expired - Lifetime
Links
- 229920001225 polyester resin Polymers 0.000 title claims description 81
- 239000004645 polyester resin Substances 0.000 title claims description 72
- 239000000203 mixture Substances 0.000 title claims description 39
- 229920000728 polyester Polymers 0.000 claims description 41
- 229920000098 polyolefin Polymers 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 29
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- 229920001577 copolymer Polymers 0.000 claims description 13
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 4
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 claims description 3
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 39
- 239000011347 resin Substances 0.000 description 39
- 239000008188 pellet Substances 0.000 description 35
- 238000002844 melting Methods 0.000 description 29
- 230000008018 melting Effects 0.000 description 29
- 239000010410 layer Substances 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 238000001816 cooling Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- -1 polyethylene terephthalate Polymers 0.000 description 15
- 239000011342 resin composition Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 13
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 13
- 229920001684 low density polyethylene Polymers 0.000 description 13
- 239000004702 low-density polyethylene Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 4
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- 239000004135 Bone phosphate Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PRPINYUDVPFIRX-UHFFFAOYSA-N 1-naphthaleneacetic acid Chemical compound C1=CC=C2C(CC(=O)O)=CC=CC2=C1 PRPINYUDVPFIRX-UHFFFAOYSA-N 0.000 description 1
- KAUVYPZCBVZESR-UHFFFAOYSA-N 2-methylidene-4-oxo-4-prop-2-enoxybutanoic acid Chemical compound OC(=O)C(=C)CC(=O)OCC=C KAUVYPZCBVZESR-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- 239000001273 butane Substances 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
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005520 cutting process Methods 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
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VVYDVQWJZWRVPE-UHFFFAOYSA-L dimethyltin(2+);diiodide Chemical compound C[Sn](C)(I)I VVYDVQWJZWRVPE-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FFYWKOUKJFCBAM-UHFFFAOYSA-N ethenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC=C FFYWKOUKJFCBAM-UHFFFAOYSA-N 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000014214 soft drink Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は溶融押出し成形性に優れたポリエステル系樹脂組成物、特に、清涼飲料、ビール、缶詰等の金属容器の腐蝕防止等の目的で使用されるポリエステル系樹脂フィルムに好適なポリエステル系樹脂組成物に関するものである。さらに詳細には、フィルム高速製膜時のネックインやサージング（耳ゆれ）が少ないポリエステル系樹脂組成物に関するものである。 The present invention is a polyester resin composition excellent in melt extrusion moldability, particularly a polyester resin composition suitable for a polyester resin film used for the purpose of preventing corrosion of metal containers such as soft drinks, beer and canned foods. It is about. More specifically, the present invention relates to a polyester resin composition with less neck-in and surging (ear fluctuation) during high-speed film formation.
近年、紙、木材、織布、不織布等の布帛、樹脂フィルム、金属シート等の表面に、種々の機能を付与する目的で、熱可塑性樹脂を溶融状態またはシート状で被覆する技術が種々の用途で利用されてきている。例えば、金属缶の缶内面及び缶外面の腐蝕防止を目的として、従来からエポキシ系，フェノール系等の各種熱硬化性樹脂を溶剤に溶解又は分散させたものを塗布し、金属表面を被覆することが広く行われてきたが、この熱硬化性樹脂の被覆方法では塗料の乾燥に長時間を要するため生産性が低下したり、また、多量の有機溶剤を使用することによる人体および環境への影響など好ましくない問題があった。 In recent years, various techniques for coating thermoplastic resins in a molten state or in a sheet form for the purpose of imparting various functions to the surface of fabrics such as paper, wood, woven fabric, and nonwoven fabric, resin films, metal sheets, etc. Has been used in. For example, for the purpose of preventing corrosion of the inner surface and outer surface of a metal can, a conventional solution in which various thermosetting resins such as epoxy and phenol are dissolved or dispersed in a solvent is coated to coat the metal surface. However, with this thermosetting resin coating method, it takes a long time to dry the paint, resulting in decreased productivity, and the use of a large amount of organic solvent has an impact on the human body and the environment. There was an unfavorable problem.
このような問題を解決するため、金属板に熱可塑性樹脂を溶融押出法で被覆する方法が開示されている。（例えば特許文献１参照。）又、溶融押出した熱可塑性樹脂を一旦冷却固化させた後、加熱された金属板に圧着する方法が開示されている。（例えば、特許文献２参照。）
しかしながら、上記公報による熱可塑性樹脂の被覆方法では、熱可塑性樹脂として特にポリエステル系樹脂を用いた場合に、Ｔダイから層状に溶融樹脂を押出す際、溶融樹脂膜の巾減少（ネックインと称す）が大きく、被覆に必要な樹脂巾に対して数１０ｃｍ広い巾で製膜する必要があり、経済性の点から満足される方法ではなかった。また、上記方法でポリエステル系樹脂を溶融押出する際、製膜速度を上げるに従ってＴダイから吐出された溶融樹脂膜の耳部が揺れ動く現象（サージングと称する）が発生し安定に製膜できないため、生産性が上げられないという問題があった。 However, in the method of coating a thermoplastic resin according to the above publication, when a polyester resin is used as the thermoplastic resin, when the molten resin is extruded in a layer form from a T die, the width of the molten resin film is reduced (referred to as neck-in). ) Is large, and it is necessary to form a film with a width that is several tens of centimeters wider than the resin width necessary for coating. In addition, when the polyester resin is melt-extruded by the above method, a phenomenon in which the ears of the molten resin film discharged from the T die swing as the film forming speed is increased (referred to as surging) occurs, and the film cannot be stably formed. There was a problem that productivity could not be increased.
上記の問題を解決するため、三官能以上の多塩基酸又は多価アルコール成分を共重合させたポリエステルを配合してなるポリエステルを使用することによりネックインを小さくする方法が開示されている。（例えば、特許文献３、特許文献４参照。）
しかしながら、上記方法では、たしかにネックインを小さくする効果は認められるものの、サージングの抑制に関しては未だ十分ではなく、また、三官能以上の多塩基酸又は多価アルコール成分を共重合させたポリエステルが押出機からＴダイに至る溶融工程で熱劣化しやすく、熱安定剤を併用しても得られた溶融樹脂膜に異物（例えば、ゲル状異物又は劣化物を核とした異物）が発生しやすく、金属缶に用いた場合には製缶時に樹脂被覆層に異物を起点とした亀裂が入るため実用上満足されるものではなかった。 However, in the above method, although the effect of reducing the neck-in is certainly recognized, the suppression of surging is not yet sufficient, and a polyester obtained by copolymerizing a tribasic or higher polybasic acid or polyhydric alcohol component is extruded. It is prone to thermal degradation in the melting process from the machine to the T-die, and foreign matter (for example, foreign matter having a gel-like foreign matter or a degradation product as a core) is likely to occur in the molten resin film obtained even when a heat stabilizer is used in combination. When used in a metal can, the resin coating layer was cracked starting from a foreign substance at the time of can making, so that it was not satisfied in practice.
また、飽和ポリエステルからなる外層とポリエチレンテレフタレートと特定のポリオレフィンとからなり、外層のポリエステルより高メルトテンションを有する樹脂組成物からなる接着層を持つネックインの少ない樹脂積層体の製造方法が開示されている。（例えば、特許文献５参照。）
しかし、上記樹脂組成物を以ってしても製膜速度が８０ｍ／分を超えるような高速製膜の場合はネックイン低減および、サージング抑制に十分な効果が得られないことがわかった。しかも、上記公報の実施例に開示されたアイオノマーを用いた場合には溶融樹脂膜に金属原子を核とする異物が発生しやすく実用上満足できるものではなかった。 However, even with the above resin composition, it was found that in the case of high-speed film formation in which the film formation speed exceeds 80 m / min, sufficient effects for neck-in reduction and surging suppression cannot be obtained. Moreover, when the ionomers disclosed in the examples of the above publication are used, foreign substances having metal atoms as nuclei are easily generated in the molten resin film, which is not satisfactory in practice.
本発明は前記従来技術の問題点を解消することを目的とするものである。即ち、溶融押出時のネックインが小さく、サージング（耳ゆれ）の発生が少なく、均一引取り性にも優れ、高速での製膜の安定性に優れたポリエステル系樹脂組成物を提供するものである。 The object of the present invention is to solve the problems of the prior art. That is, it provides a polyester-based resin composition having a small neck-in at the time of melt extrusion, little occurrence of surging, excellent uniform take-up property, and excellent film formation stability at high speed. is there.
前記課題を解決するために、本発明の態様は、
（１）主たる構成単位がエチレンテレフタレート単位からなり、かつ製造時に添加する総リン量と総金属イオン量とのモル比が０．４〜１．０の範囲のポリエステルおよびオレフィン系ポリマーを７０／３０〜９９／１（重量％）の比率でブレンドしてなるポリエステル系樹脂組成物であって、該ポリエステル中に該オレフィン系ポリマーが微分散しており、分散粒子の平均粒径が０．１〜２．０μｍの範囲であることを特徴とするポリエステル系樹脂組成物である。
上記の構成からなる本発明のポリエステル系樹脂組成物は、ネックインが小さく、サージングの抑制効果がある。
In order to solve the above problems, an aspect of the present invention provides:
(1) Ri main structural units Do ethylene terephthalate units, and the molar ratio of total phosphorus and total quantity of metal ions added during manufacture of the polyester and olefin-based polymer in the range of 0.4 to 1.0 70 / A polyester-based resin composition blended at a ratio of 30 to 99/1 (% by weight), wherein the olefin-based polymer is finely dispersed in the polyester, and the average particle size of the dispersed particles is 0.1. It is the range of -2.0 micrometer, It is a polyester-type resin composition characterized by the above-mentioned.
The polyester-based resin composition of the present invention having the above-described configuration has a small neck-in and an effect of suppressing surging.
（２）上記（１）において、ポリエステル系樹脂にブレンドされるオレフィン系ポリマーが、少なくとも１種以上の炭素数２〜６のα−オレフィン、及び、エチレン結合形成性α，β−不飽和カルボン酸又はそのエステル形成性誘導体を主たる構成単位とする共重合体、または、それを含む他のポリマーとの混合体であることができる。
上記の構成からなる本発明のポリエステル系樹脂組成物は、ネックインの低減、及び、サージングの抑制に有効な実現手段を与えるものである。
(2) In the above (1), the olefin polymer blended with the polyester resin is at least one α-olefin having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid. Alternatively, it can be a copolymer having an ester-forming derivative as a main structural unit, or a mixture with another polymer containing the copolymer.
The polyester-based resin composition of the present invention having the above configuration provides an effective means for reducing neck-in and suppressing surging.
（３）さらに、上記（１）において、ポリエステル系樹脂にブレンドされるオレフィン系ポリマーが（Ａ）少なくとも１種以上の炭素数２〜６のα−オレフィンを主たる構成単位とする重合体、および、（Ｂ）少なくとも１種以上の炭素数２〜６のα−オレフィンとエチレン結合形成性α，β−不飽和カルボン酸又はそのエステル形成性誘導体を主たる構成単位とする共重合体からなることができる。
上記の構成からなる本発明のポリエステル系樹脂組成物は、ネックインの低減、及び、サージングの抑制にさらに有効な実現手段を与えるものである。
(3) Furthermore, in the above (1), the olefin polymer blended with the polyester-based resin is (A) a polymer having at least one kind of α-olefin having 2 to 6 carbon atoms as a main structural unit, and (B) It can be composed of a copolymer having at least one α-olefin having 2 to 6 carbon atoms and an ethylene bond-forming α, β-unsaturated carboxylic acid or an ester-forming derivative thereof as main structural units. .
The polyester-based resin composition of the present invention having the above-described configuration provides a more effective means for reducing neck-in and suppressing surging.
本発明によるポリエステル系樹脂組成物は、ポリエステル樹脂及びオレフィン系樹脂のブレンド物であり、ポリエステル樹脂中にオレフィン系樹脂が分散し、その分散粒子系が特定の範囲を満足することによって、溶融製膜時の溶融樹脂膜のネックイン低減及び溶融樹脂膜のサージング抑制、機械特性と熱安定性に優れた効果が得られ、本発明のポリエステル系樹脂を用いたフィルムは金属板等の各種基材に被覆する用途に利用することができる。 The polyester-based resin composition according to the present invention is a blend of a polyester resin and an olefin-based resin. When the olefin-based resin is dispersed in the polyester resin and the dispersed particle system satisfies a specific range, melt film formation is performed. It is possible to reduce the neck-in of the molten resin film at the time, suppress the surging of the molten resin film, and have excellent effects on mechanical properties and thermal stability. Films using the polyester resin of the present invention can be applied to various substrates such as metal plates. It can be used for coating purposes.
以下、本発明を詳細に説明する。
本発明におけるポリエステルとは、ジカルボン酸成分とジオール成分からなるポリマーである。ジカルボン酸成分としては、テレフタル酸，イソフタル酸，オルソフタル酸，ナフタレンジカルボン酸，ジフェニルスルホンジカルボン酸，５−ナトリウムスルホイソフタル酸等の芳香族ジカルボン酸、シュウ酸、コハク酸、アジピン酸、セバシン酸、デカンジカルボン酸、マレイン酸、フマル酸、ダイマー酸等の脂肪族ジカルボン酸、ｐ−オキシ安息香酸等のオキシカルボン酸、シクロヘキサンジカルボン酸等の脂環族ジカルボン酸及びそれらのエステル誘導体が使用できるが、本発明の目的を達成するために、ジカルボン酸成分としては、テレフタル酸，イソフタル酸、ナフタレンジカルボン酸からなる群から選ばれるジカルボン酸およびそれらのエステル誘導体を主として用いることが好ましく、上記のジカルボン酸及びそれらのエステル誘導体を合計で８０モル％以上用いることがさらに好ましい。それ以外のジカルボン酸及びそれらのエステル誘導体を用いる場合は２０モル％以下が好ましく、さらには１０モル％以下が好ましい。他のジカルボン酸及びそれらのエステル誘導体の使用量が２０モル％を超えるとポリエステルの熱安定性が悪くなり好ましくない。
Hereinafter, the present invention will be described in detail.
The polyester in the present invention is a polymer composed of a dicarboxylic acid component and a diol component. Dicarboxylic acid components include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, 5-sodium sulfoisophthalic acid and other aromatic dicarboxylic acids, oxalic acid, succinic acid, adipic acid, sebacic acid, decane Aliphatic dicarboxylic acids such as dicarboxylic acid, maleic acid, fumaric acid and dimer acid, oxycarboxylic acids such as p-oxybenzoic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and ester derivatives thereof can be used. to achieve the object of the invention, the dicarboxylic acid component, terephthalic acid, isophthalic acid, mainly it is preferable to use dicarboxylic acids and their ester derivatives selected from the group consisting of naphthalene dicarboxylic acid, said dicarboxylic acids and their S It is more preferable to use 80 mol% or more of Le derivative in total. When other dicarboxylic acids and their ester derivatives are used, the amount is preferably 20 mol% or less, more preferably 10 mol% or less. If the amount of other dicarboxylic acids and their ester derivatives used exceeds 20 mol%, the thermal stability of the polyester is deteriorated, which is not preferable.
また、ジオール成分としては、エチレングリコール、１，２−プロパンジオール、１，３−プロパンジオール、１，４−ブタンジオ−ル，ペンタンジオール、ヘキサンジオール，ネオペンチルグリコール等の脂肪族グリコール、シクロヘキサンジメタノール等の脂環族グリコール、ビスフェノールＡのエチレンオキサイド付加物，ビスフェノールＳのエチレンオキサイド付加物等の芳香族グリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等が使用できる。このほか少量のアミド結合、ウレタン結合、エーテル結合、カーボネート結合等を含有する化合物を含んでいてもよい。ここで、本発明の目的を達成するために、ジオール成分としてはエチレングリコール、１，４−ブタンジオールを主として用いることが好ましく、エチレングリコールおよび／または１，４−ブタンジオールを合計８０モル％以上とすることがさらに好ましい。それ以外のジオール成分の使用量が２０モル％を超えるとポリエステルの熱安定性が悪くなり好ましくない。 Examples of the diol component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentanediol, hexanediol, neopentylglycol and other aliphatic glycols, cyclohexanedimethanol An aromatic glycol such as alicyclic glycol such as bisphenol A, an ethylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol S, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like can be used. In addition, a small amount of a compound containing an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be included. Here, in order to achieve the object of the present invention, it is preferable to mainly use ethylene glycol and 1,4-butanediol as the diol component, and a total of 80 mol% or more of ethylene glycol and / or 1,4-butanediol. More preferably. If the amount of the other diol component used exceeds 20 mol%, the thermal stability of the polyester deteriorates, which is not preferable.
上記の好ましいジカルボン酸成分の群、及び、好ましいジオール成分の群中の各成分の使用比率は、本発明のポリエステル系樹脂組成物を用いる用途における必要特性を確保するために任意に選択できる。本発明の樹脂組成物を用いてフィルムを成形する場合、一般的にエチレンテレフタレート単位が８０モル％以上であることが機械的強度、熱安定性を確保するために好ましい。 The use ratio of each component in the group of said preferable dicarboxylic acid component and the preferable diol component can be arbitrarily selected in order to ensure the required characteristic in the use which uses the polyester-type resin composition of this invention. When a film is formed using the resin composition of the present invention, it is generally preferable that the ethylene terephthalate unit is 80 mol% or more in order to ensure mechanical strength and thermal stability.
本発明におけるポリエステルには、必要に応じて酸化防止剤、熱安定剤、紫外線吸収剤、可塑剤、顔料、帯電防止剤、潤滑剤、結晶核剤、無機又は有機粒子よりなる滑剤等を配合させてもよい。 In the polyester in the present invention, an antioxidant, a heat stabilizer, an ultraviolet absorber, a plasticizer, a pigment, an antistatic agent, a lubricant, a crystal nucleating agent, a lubricant composed of inorganic or organic particles, and the like are blended as necessary. May be.
本発明におけるポリエステルの製造方法については特に限定しない。即ち、エステル交換法又は直接重合法のいずれの方法で製造されたものであっても使用できる。又、分子量を高めるために固相重合法で製造されたものであってもかまわない。さらに、本発明のポリエステル系樹脂組成物を製缶用に用いた場合、缶に内容物を充填後にレトルト処理等を実施した時のポリエステル樹脂からのオリゴマーの析出量を少なくするために、不活性ガス雰囲気下または減圧下での固相重合法で製造されたオリゴマー含有量が低いポリエステルを使用することは好ましい。 The method for producing the polyester in the present invention is not particularly limited. That is, it can be used even if it is produced by either the transesterification method or the direct polymerization method. Further, it may be produced by a solid phase polymerization method in order to increase the molecular weight. Furthermore, when the polyester-based resin composition of the present invention is used for making cans, in order to reduce the amount of oligomers precipitated from the polyester resin when the retort treatment is performed after filling the contents in the can, it is inactive. It is preferable to use a polyester having a low oligomer content produced by a solid phase polymerization method under a gas atmosphere or under reduced pressure.
本発明におけるポリエステルの製造の際には重合触媒としては酸化アンチモン、酸化ゲルマニウム、チタン化合物等が用いられるほか、重合触媒以外に本発明のポリエステル系樹脂組成物を用いて溶融押出しフィルムを成形する際の静電密着性を付与するために、酢酸マグネシウム、塩化マグネシウム等のＭｇ塩、酢酸カルシウム、塩化カルシウム等のＣａ塩、酢酸マンガン、塩化マンガン等のＭｎ塩、塩化亜鉛、酢酸亜鉛等のＺｎ塩、塩化コバルト、酢酸コバルト等のＣｏ塩を各々の金属イオンの総量として３００ｐｐｍ以下、リン酸またはリン酸トリメチルエステル、リン酸トリエチルエステル等のリン酸エステル誘導体をリン原子として２００ｐｐｍ以下の範囲で添加することも可能である。
上記重合触媒以外の金属イオンの総量が３００ｐｐｍ、またリン量が２００ｐｐｍを越えると、得られたポリエステルの着色が顕著になるのみならず，ポリエステルの耐熱性及び耐加水分解性も低下する場合があるので好ましくない。
このとき、添加する総リン量と総金属イオン量とのモル比が０．４〜１．０であるときに、耐熱性、耐加水分解性及び、静電密着性のバランスが最も優れたポリエステルが得られるので好ましい。ここで、添加量のモル比＝（リン酸、リン酸アルキルエステル、またはその誘導体中のリンの総量（モル原子））／（Ｍｇイオン、Ｃａイオン、Ｍｎイオン、Ｚｎイオン、Ｃｏイオンの総量（モル原子））である。
上記モル比が０．４未満の場合には、本発明の組成物の着色が顕著となり，耐熱性、耐加水分解性が低下する。１．０を超える場合には、十分な静電密着性が得られない。
In the production of the polyester in the present invention, as the polymerization catalyst, antimony oxide, germanium oxide, titanium compound, etc. are used. In addition to the polymerization catalyst, the polyester resin composition of the present invention is used to form a melt-extruded film. Mg salt such as magnesium acetate and magnesium chloride, Ca salt such as calcium acetate and calcium chloride, Mn salt such as manganese acetate and manganese chloride, Zn salt such as zinc chloride and zinc acetate Co salt such as cobalt chloride and cobalt acetate is added in the range of 300 ppm or less as the total amount of each metal ion, and phosphoric acid derivatives such as phosphoric acid or phosphoric acid trimethyl ester and phosphoric acid triethyl ester are added in the range of 200 ppm or less as phosphorus atoms. It is also possible.
When the total amount of metal ions other than the above polymerization catalyst exceeds 300 ppm and the amount of phosphorus exceeds 200 ppm, not only is the resulting polyester colored significantly, but the heat resistance and hydrolysis resistance of the polyester may also decrease. Therefore, it is not preferable.
At this time, when the molar ratio of the total phosphorus amount to be added and the total metal ion amount is 0.4 to 1.0, the polyester having the best balance of heat resistance, hydrolysis resistance, and electrostatic adhesion Is preferable. Here, molar ratio of addition amount = (total amount of phosphorus in phosphoric acid, phosphoric acid alkyl ester or derivative thereof (molar atom)) / (total amount of Mg ion, Ca ion, Mn ion, Zn ion, Co ion ( Mole atom)).
When the molar ratio is less than 0.4, the composition of the present invention is markedly colored, and heat resistance and hydrolysis resistance are lowered. If it exceeds 1.0, sufficient electrostatic adhesion cannot be obtained.
本発明のポリエステル系樹脂にブレンドされるオレフィン系ポリマーは特に限定するものではない。オレフィン系ポリマーの例としては、低密度ポリエチレン，中密度ポリエチレン，高密度ポリエチレン，直鎖状低密度ポリエチレン，超高分子量ポリエチレン，ポリプロピレン，エチレン−プロピレン共重合体，エチレン−ブテン共重合体等のエチレン−α−オレフィン共重合体，エチレン−酢酸ビニル共重合体，エチレン−アクリレート共重合体、エチレン−メタアクリレート共重合体，エチレン−メチルアクリレート共重合体，エチレン−エチルアクリレート共重合体，エチレン−メチルメタアクリレート共重合体，エチレン−ビニルアルコール共重合体，エチレン−グリシジルアクリレート共重合体、エチレン−グリシジルメタクリレート共重合体、エチレン−無水マレイン酸共重合体等が使用できる。 The olefin polymer blended with the polyester resin of the present invention is not particularly limited. Examples of olefin polymers include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, ultrahigh molecular weight polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, and other ethylene. -Α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl A methacrylate copolymer, an ethylene-vinyl alcohol copolymer, an ethylene-glycidyl acrylate copolymer, an ethylene-glycidyl methacrylate copolymer, an ethylene-maleic anhydride copolymer, or the like can be used.
本発明のオレフィン系ポリマーは上記の中から選択された１種類の樹脂を単独で用いることも出来るが、２種類以上の樹脂を併用することもでき、本発明の目的を達成するためにその種類及び添加量を適宜選択することができる。 As the olefin polymer of the present invention, one kind of resin selected from the above can be used alone, but two or more kinds of resins can be used in combination, and the kind thereof is used to achieve the object of the present invention. And the addition amount can be selected suitably.
本発明のポリエステルとオレフィン系ポリマーのブレンド比率は、７０／３０〜９９／１（重量％）の範囲であることが必要である。オレフィン系ポリマーの比率が３０重量％を超えると本発明のポリエステル系樹脂組成物を用いて得られたフィルムの機械的強度や耐熱性が劣るため好ましくない。又、オレフィン系ポリマーの比率が１％未満の場合は本発明のネックイン低減及びサージング抑制効果が十分に発揮されないので好ましくない。 The blend ratio of the polyester of the present invention and the olefin polymer needs to be in the range of 70/30 to 99/1 (% by weight). When the ratio of the olefin polymer exceeds 30% by weight, the film obtained by using the polyester resin composition of the present invention is inferior in mechanical strength and heat resistance, which is not preferable. Moreover, when the ratio of the olefin polymer is less than 1%, the neck-in reduction and surging suppressing effects of the present invention are not sufficiently exhibited, which is not preferable.
本発明のポリエステル系樹脂組成物は、その目的を達成するために、ポリエステル樹脂中にオレフィン系ポリマーが微分散し、オレフィン系ポリマーの分散径が実質的に平均径で０．１〜２．０μｍの範囲内となることが必要である。このようにオレフィン系ポリマーがポリエステル樹脂に微分散することで、少ないオレフィン量でもオレフィン系ポリマーとポリエステルとの界面での分子間相互作用が増大し、優れた溶融特性が効果的に発揮される。ポリエステル樹脂中のオレフィン系ポリマーの平均粒径が２．０μｍを超える場合、ポリエステル樹脂とオレフィン系ポリマーとの相互作用が小さいため、ネックイン低減及びサージング抑制に十分な効果が得られない。また、ポリエステル樹脂中のオレフィン系ポリマーの平均粒径が０．１μｍ未満の場合、オレフィン系ポリマーの一部がポリエステル樹脂中に見かけ上均一に溶解した状態になってしまい、オレフィン分散粒子の特性が十分に発揮されない他、ポリエステル樹脂本来の特性、例えば、機械的強度や熱特性等が損なわれてしまう恐れがあり好ましくない。 In order to achieve the object of the polyester resin composition of the present invention, the olefin polymer is finely dispersed in the polyester resin, and the dispersion diameter of the olefin polymer is substantially 0.1 to 2.0 μm in average diameter. It is necessary to be within the range. Thus, by finely dispersing the olefin polymer in the polyester resin, even when the amount of olefin is small, the intermolecular interaction at the interface between the olefin polymer and the polyester is increased, and excellent melting characteristics are effectively exhibited. When the average particle size of the olefin polymer in the polyester resin exceeds 2.0 μm, the interaction between the polyester resin and the olefin polymer is small, so that sufficient effects for reducing neck-in and suppressing surging cannot be obtained. In addition, when the average particle size of the olefin polymer in the polyester resin is less than 0.1 μm , part of the olefin polymer is apparently uniformly dissolved in the polyester resin, and the characteristics of the olefin dispersed particles Is not preferable, and the inherent properties of the polyester resin, such as mechanical strength and thermal properties, may be impaired.
本発明のポリエステル系樹脂組成物の目的とする効果を得るために、好適なオレフィン系ポリマーの選択の例として、下記式（I）を満足する樹脂組成物を選択することができる。
０．１５≦（Ｍｉ−Ｍｆ）／ｍ≦１．０ （I）
（式中、Ｍｉは結晶性ポリエステルの融点＋３０℃の温度で測定した結晶性ポリエステルのメルトフローレート（ＭＦＲ、ｇ／１０ｍｉｎ）。Ｍｆは結晶性ポリエステルの融点＋３０℃の温度で測定した結晶性ポリエステルとオレフィン系ポリマーのブレンド物のＭＦＲ（ｇ／１０ｍｉｎ）。ｍはブレンド物中のオレフィン系ポリマーの含有量（重量％）である。）
ここでいうメルトフローレート（ＭＦＲ）とは、ＪＩＳ Ｋ７２１０に規定された方法に従い溶融指数測定装置（ＭＥＬＴ ＩＮＤＥＸＥＲ、東洋精機製）で、オリフィス径２．０９ｍｍ、加重２．１６ｋｇｆの条件で測定した樹脂組成物の溶融特性を示す値であり、この値を上式に示す特定の範囲内に入るようにオレフィン系ポリマーの種類及び量を設定することによって、本発明の優れた効果が実現される。上記式（I）において、（Ｍｉ−Ｍｆ）／ｍの値が上記範囲の場合、溶融樹脂膜を引き取る際の溶融張力（引き取りに対する抵抗）が適度な値になり、膜厚の減少（ドローダウン）が樹脂膜全体で均一に起こることによりネックイン低減効果及びサージング抑制効果が有効に発現される。
In order to obtain the desired effect of the polyester resin composition of the present invention, a resin composition satisfying the following formula (I) can be selected as an example of selection of a suitable olefin polymer.
0.15 ≦ (Mi−Mf) /m≦1.0 (I)
(In the formula, Mi is the melting point of the crystalline polyester + melting rate of the crystalline polyester measured at a temperature of 30 ° C. (MFR, g / 10 min). Mf is the crystalline polyester measured at the melting point of the crystalline polyester + 30 ° C.) MFR of blend of olefin polymer and olefin polymer (g / 10 min), where m is the content (% by weight) of olefin polymer in the blend.
The melt flow rate (MFR) here is a resin measured with a melt index measuring device (MELT INDEXER, manufactured by Toyo Seiki Co., Ltd.) according to the method specified in JIS K7210 under the conditions of an orifice diameter of 2.09 mm and a load of 2.16 kgf. It is a value indicating the melting characteristics of the composition, and the excellent effect of the present invention is realized by setting the type and amount of the olefin polymer so that this value falls within the specific range represented by the above formula. In the above formula (I), when the value of (Mi−Mf) / m is in the above range, the melt tension (resistance to take-off) when taking the molten resin film becomes an appropriate value, and the film thickness is reduced (draw down). ) Occur uniformly throughout the resin film, the neck-in reducing effect and the surging suppressing effect are effectively expressed.
本発明のポリエステル系樹脂組成物の目的とする効果を得るために、好適なオレフィン系ポリマーの選択の例として、オレフィン系ポリマー中の官能基の含有量が２００〜２０００等量／トン（オレフィン系ポリマー全体の重量１トン中に存在する官能基のモル等量）の範囲にあるときに、本発明の効果が有効に発現されるので好ましい。オレフィン系ポリマー中の官能基の含有量が上記好適な範囲内にあるとき、オレフィン系ポリマーのポリエステル樹脂に対する親和性が適度に増し、オレフィン系ポリマーとポリエステルの分子鎖同士が化学的に相互作用することにより優れた溶融特性が発揮される。 In order to obtain the desired effect of the polyester resin composition of the present invention, as an example of selection of a suitable olefin polymer, the content of functional groups in the olefin polymer is 200 to 2000 equivalents / ton (olefin type). In the range of the molar equivalent of the functional groups present in 1 ton of the total weight of the polymer, the effect of the present invention is effectively exhibited, which is preferable. When the content of the functional group in the olefin polymer is within the above preferred range, the affinity of the olefin polymer to the polyester resin is moderately increased, and the molecular chains of the olefin polymer and the polyester interact chemically. As a result, excellent melting characteristics are exhibited.
好ましい官能基としては極性を有し、ブレンドするポリエステル樹脂との親和性を高める効果のある官能基を用いることができる。例えば、カルボキシル基、グリシジル基、酸無水物基等があげられる。具体的には各種製法及び触媒により製造されたエチレン−（メタ）アクリレート共重合体、エチレン−（メタ）アクリル酸エステル共重合体等のエチレン−α，β−不飽和カルボン酸共重合体を例示することができる。 As a preferable functional group, a functional group having polarity and having an effect of increasing the affinity with the polyester resin to be blended can be used. Examples thereof include a carboxyl group, a glycidyl group, and an acid anhydride group. Specific examples include ethylene-α, β-unsaturated carboxylic acid copolymers such as ethylene- (meth) acrylate copolymers and ethylene- (meth) acrylic acid ester copolymers produced by various production methods and catalysts. it can be.
また、本発明の目的とする効果を得るために、他の好適なオレフィン系ポリマーの例として、架橋構造及び／又は枝分かれ構造を形成し得るモノマー成分を各々５％未満の範囲で含有するポリマーを例示することができる。このようなモノマーとしては２つ以上の付加重合性の反応基をもつ不飽和モノマーがあげられる。架橋結合性モノマーの例としては、ブチレンジアクリレート、ブチレンジメタクリレート、トリメチロールプロパントリメタクリレート、ジビニルベンゼン、トリビニルベンゼン、ビニルアクリレート、ビニルメタクリレート等が使用できる。好ましくはブチレンジアクリレート、ブチレンジメタクリレートが使用できる。グラフト結合性モノマーの例としては、アリルアクリレート、アリルメタクリレート、マレイン酸ジアリル、フマル酸ジアリル、イタコン酸ジアリル、マレイン酸モノアリル、フマル酸モノアリル、イタコン酸モノアリル等が使用できる。好ましくはアリルメタクリレート、ジアリルメタクリレートが使用できる。 In addition, in order to obtain the intended effect of the present invention, as another example of a suitable olefin-based polymer, a polymer containing a monomer component capable of forming a crosslinked structure and / or a branched structure in a range of less than 5% each. It can be illustrated. Examples of such a monomer include unsaturated monomers having two or more addition polymerizable reactive groups. Examples of the crosslinkable monomer include butylene diacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, divinylbenzene, trivinylbenzene, vinyl acrylate, vinyl methacrylate and the like. Preferably, butylene diacrylate and butylene dimethacrylate can be used. Examples of the graft-bonding monomer include allyl acrylate, allyl methacrylate, diallyl maleate, diallyl fumarate, diallyl itaconate, monoallyl maleate, monoallyl fumarate, monoallyl itaconate, and the like. Preferably, allyl methacrylate and diallyl methacrylate can be used.
本発明のポリエステル樹脂とオレフィン系ポリマーのブレンド方法は、公知の樹脂混合方法を広く用いることができる。例えば、ポリエステル樹脂のペレットとオレフィン系ポリマーのペレットをブレンダー等で均一にドライブレンドした後、１軸もしくは２軸押出機等で溶融混練する方法が挙げられる。また、本発明のポリエステル系樹脂組成物を溶融押出してフィルムを製膜する方法としては、公知の製膜方法を用いることができる。例えば溶融樹脂をＴダイから層状に押出すＴダイ法、溶融樹脂をサーキュラーダイから円筒状に押出し空気圧により膨らませるインフレーション法等を用いることができる。この場合、ドライブレンドしたポリエステル樹脂とオレフィン系ポリマーを溶融混練して得られた溶融ブレンド物のペレットをフィルム製膜用押出機に投入してフィルムを製膜することもできるが、ドライブレンドした両者の混合ペレットをフィルム製膜用押出機に直接投入してフィルムを製膜することもできる。前者の場合、あらかじめ溶融混練して得られた溶融プレンド物のペレットと他のポリエステル樹脂とを混合した後、フィルム製膜用押出機に投入してフィルムを製膜することもできる。 As a blending method of the polyester resin and the olefin polymer of the present invention, known resin mixing methods can be widely used. For example, a polyester resin pellet and an olefin polymer pellet are uniformly dry blended with a blender or the like, and then melt-kneaded with a single or twin screw extruder. In addition, as a method of forming a film by melt extrusion of the polyester resin composition of the present invention, a known film forming method can be used. For example, a T-die method in which a molten resin is extruded in a layer form from a T-die, an inflation method in which a molten resin is extruded from a circular die into a cylindrical shape, and inflated by air pressure, or the like can be used. In this case, the dry blended polyester resin and the olefin polymer are melt-kneaded to obtain a melt blended pellet into a film-forming extruder to form a film. It is also possible to directly form the mixed pellets into a film-forming extruder to form a film. In the former case, the melt-blended pellets obtained by melt-kneading in advance and other polyester resins can be mixed and then put into a film-forming extruder to form a film.
以下、実施例をもとに本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail based on examples.
以下に本発明における評価方法を示す。
（１）ポリエステルの融点
ポリエステル組成物を３００℃で５分間加熱溶融した後、液体窒素で急冷して得たサンプル１０ｍｇを用い、窒素気流中、示差走査型熱量計（ＤＳＣ）を用いて１０℃／分の昇温速度で発熱・吸熱曲線（ＤＳＣ曲線）を測定したときの、融解に伴う吸熱ピークの頂点温度を融点（℃）とした。
The evaluation method in the present invention is shown below.
(1) Melting point of polyester After heating and melting the polyester composition at 300 ° C. for 5 minutes, 10 mg of a sample obtained by quenching with liquid nitrogen was used, and 10 ° C. using a differential scanning calorimeter (DSC) in a nitrogen stream. The peak temperature of the endothermic peak accompanying melting when the exothermic / endothermic curve (DSC curve) was measured at a rate of temperature rise per minute was defined as the melting point (° C.).
（２）オレフィン系ポリマーの平均粒径
ポリエステル樹脂およびオレフィン系ポリマーを押出機で溶融混練して得られたポリエステル系樹脂組成物ペレットまたはフィルムをエポキシ樹脂に包埋して硬化させものをクライオミクロトームにて切開し超薄切片を作製した。これを酸化ルテニウムで染色したのち室温で１０分間保持し、次いでカーボン蒸着して透過型電子顕微鏡で観察した。分散粒子の平均径は画像解析装置（東洋紡績製、Ｖ１０）を用いて円相当径により求めた。
(2) Average particle size of olefin polymer Polyester resin composition pellets or film obtained by melting and kneading polyester resin and olefin polymer with an extruder are embedded in an epoxy resin and cured into a cryomicrotome An incision was made to produce an ultrathin section. This was dyed with ruthenium oxide, held at room temperature for 10 minutes, then carbon-deposited and observed with a transmission electron microscope. The average diameter of the dispersed particles was determined from the equivalent circle diameter using an image analyzer (Toyobo, V10).
（３）ネックイン量
樹脂を溶融した後、Ｔダイを用いて層状に押し出した際のＴダイの吐出口巾（６０ｃｍ）とｎ＝３で測定した冷却固化後の樹脂膜巾（両端部を切断除去する前の樹脂膜巾）の平均値（Ａｃｍ）を用い、次式でネックイン量（ｃｍ）を求めた。ネックイン量が５ｃｍ以下を実用性ありと評価した。
ネックイン量（ｃｍ）＝６０−Ａ
(3) Neck-in amount After the resin is melted, the width of the outlet of the T die when extruded in a layer form using the T die (60 cm) and the width of the resin film after cooling and solidification measured at n = 3 (both ends) Using the average value (Acm) of the resin film width before cutting and removing, the neck-in amount (cm) was determined by the following equation. A neck-in amount of 5 cm or less was evaluated as practical.
Neck-in amount (cm) = 60-A
（４）サージング性
樹脂を溶融した後、Ｔダイを用いて層状に押出した際の樹脂膜の巾の変動、端部の安定性（耳ゆれ）を評価した。樹脂膜の巾の変動、耳ゆれがなく安定している場合にサージング性良好と評価した。
○：サージング性良好
△：やや耳ゆれあり
×：耳ゆれ、樹脂膜の巾変動あり
(4) Surging property After the resin was melted, the fluctuation of the width of the resin film and the stability of the end (ear fluctuation) were evaluated when it was extruded into a layer using a T-die. It was evaluated that the surging property was good when the width of the resin film was stable and there was no fluctuation of the ear.
○: Good surging property △: Slight ear shake ×: Ear shake and resin film width fluctuation
次に、実施例、比較例に用いたポリエステル及びオレフィン系ポリマーの内容について説明する。 Next, the contents of the polyester and olefin polymer used in Examples and Comparative Examples will be described.
（１）ポリエチレンテレフタレート（ＰＥＴ）樹脂
投入口、温度計、圧力計及び精留塔付留出管、撹拌翼を備えた反応装置にテレフタル酸１００重量部に対して、エチレングリコール８２重量部（エチレングリコール／テレフタル酸のモル比＝２．２）、酸成分に対して酸化ゲルマニウムをＧｅ元素として０．０５モル％、酢酸マグネシウムをＭｇ元素として０．０５モル％、そして、平均粒径１．２μｍの無定形シリカ粒子０．２３重量部を仕込み、撹拌しながら窒素を導入し系内の圧力を０．３ＭＰａに保ち、温度２３０℃〜２５０℃で生成する水を系外に留去しながらエステル化反応を行った。反応終了後、２５０℃にて、リン酸トリメチルをＰ量として０．０４モル％加え、昇温しながら徐々に減圧し、２７５℃、１．０ｈＰａ以下の真空下で重縮合反応を行い、得られた固有粘度０．７３のポリエステル（ＰＥＴ）樹脂を用いた。
(1) Polyethylene terephthalate (PET) resin 82 parts by weight of ethylene glycol (100 parts by weight of ethylene glycol with respect to 100 parts by weight of terephthalic acid in a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade Glycol / terephthalic acid molar ratio = 2.2), 0.05 mol% of germanium oxide as the Ge element, 0.05 mol% of magnesium acetate as the Mg element, and an average particle diameter of 1.2 μm with respect to the acid component The amorphous silica particles of 0.23 parts by weight were charged, nitrogen was introduced with stirring, the pressure inside the system was kept at 0.3 MPa, and the water produced at a temperature of 230 ° C. to 250 ° C. was distilled out of the system while the ester was distilled off. The reaction was carried out. After completion of the reaction, 0.04 mol% of trimethyl phosphate as P amount was added at 250 ° C., the pressure was gradually reduced while the temperature was raised, and a polycondensation reaction was performed under a vacuum of 275 ° C. and 1.0 hPa or less. The obtained intrinsic viscosity 0.73 polyester (PET) resin was used.
（２）ポリエチレンテレフタレート・イソフタレート樹脂（ＰＥＴ−Ｉ（１０）、エチレンイソフタレート繰り返し単位１０モル％）
テレフタル酸９０重量部、イソフタル酸１０重量部を用いた以外はポリエチレンテレフタレート（ＰＥＴ）の製造方法と同様な方法により製造し、得られたポリエステル（ＰＥＴ−Ｉ（１０）、固有粘度０．７３）を用いた。
(2) Polyethylene terephthalate / isophthalate resin (PET-I (10), ethylene isophthalate repeating unit 10 mol%)
Polyester (PET-I (10), intrinsic viscosity 0.73) obtained by the same method as that for polyethylene terephthalate (PET) except that 90 parts by weight of terephthalic acid and 10 parts by weight of isophthalic acid were used. Was used.
（３）ポリエチレンテレフタレート・イソフタレート樹脂（ＰＥＴ−Ｉ（１５）、エチレンイソフタレート繰り返し単位１５モル％）
テレフタル酸８５重量部、イソフタル酸１５重量部を用いた以外はポリエチレンテレフタレート（ＰＥＴ）の製造方法と同様な方法により製造し、得られたポリエステル（ＰＥＴ−Ｉ（１５）、固有粘度０．７３）を用いた。
(3) Polyethylene terephthalate / isophthalate resin (PET-I (15), ethylene isophthalate repeating unit 15 mol%)
Polyester (PET-I (15), intrinsic viscosity 0.73) obtained by the same method as that for polyethylene terephthalate (PET) except that 85 parts by weight of terephthalic acid and 15 parts by weight of isophthalic acid were used. Was used.
（４）ポリブチレンテレフタレート（ＰＢＴ）樹脂
投入口、温度計、圧力計及び精留塔付留出管、撹拌翼を備えた反応装置に、テレフタル酸１００重量部に対して、１，４−ブタンジオール８６重量部（１，４−ブタンジオール／テレフタル酸のモル比＝１．６）、テトラノルマルブチルチタネート０．０５重量部、ブチルヒドロキシスズオキサイド０．０２５重量部を仕込み、１９０℃〜２３０℃で生成する水を系外に留出しながらエステル化反応を行った。反応終了後、テトラノルマルブチルチタネート０．０５重量部、およびリン酸０．０２５重量部を添加し２５０℃、減圧下（１．０ｈＰａ以下）で重縮合反応を行い、得られたポリエステル（ＰＢＴ、固有粘度０．８５）を用いた。
(4) Polybutylene terephthalate (PBT) resin 1,4-butane with respect to 100 parts by weight of terephthalic acid in a reactor equipped with an inlet, a thermometer, a pressure gauge, a distillation tube with a rectifying column, and a stirring blade 86 parts by weight of diol (molar ratio of 1,4-butanediol / terephthalic acid = 1.6), 0.05 part by weight of tetranormal butyl titanate, 0.025 part by weight of butylhydroxytin oxide were charged at 190 ° C. to 230 ° C. The esterification reaction was carried out while distilling out the water produced in the above. After completion of the reaction, 0.05 part by weight of tetranormal butyl titanate and 0.025 part by weight of phosphoric acid were added, and a polycondensation reaction was performed at 250 ° C. under reduced pressure (1.0 hPa or less). The resulting polyester (PBT, An intrinsic viscosity of 0.85) was used.
（５）低密度ポリエチレン（ＬＤＰＥ）：住友化学製、スミカセンＧ４０１を用いた。
（６）エチレン−アクリル酸共重合体（ＥＡＡ）：ダウ・ケミカル日本製、プリマコール３４４０を用いた。
（７）エチレン−メタクリル酸共重合体（ＥＭＡＡ）：三井デュポンポリケミカル製、ニュクレルＮ１１０８Ｃを用いた。
（８）エチレン−エチルアクリレート共重合体（ＥＥＡ）：三井デュポンポリケミカル製、エバフレックスＡ７１２を用いた。
（９）エチレン−メチルアクリレート共重合体（ＥＭＡ）：イーストマンケミカル製、ＥＭＡＣ２２６０を用いた。
（１０）エチレン系アイオノマー：三井デュポンポリケミカル製、ハイミラン１７０６を用いた。
（１１）エチレン−１−ブテン共重合体（ＥＢＭ）：ＪＳＲ製、ＥＢＭ２０４１Ｐを用いた。
（１２）ポリブチルアクリレート−ポリメタクリル酸メチル共重合体（ＭＢＡ）：呉羽化学製、パラロイドＥＸＬ２３１４を用いた。
(5) Low density polyethylene (LDPE): Sumikasen G401 manufactured by Sumitomo Chemical was used.
(6) Ethylene-acrylic acid copolymer (EAA): Dow Chemical Japan, Primacol 3440 was used.
(7) Ethylene-methacrylic acid copolymer (EMAA): Nucleel N1108C manufactured by Mitsui DuPont Polychemicals was used.
(8) Ethylene-ethyl acrylate copolymer (EEA): Evaflex A712 manufactured by Mitsui DuPont Polychemicals was used.
(9) Ethylene-methyl acrylate copolymer (EMA): EMAC2260 manufactured by Eastman Chemical was used.
(10) Ethylene ionomer: High Milan 1706 manufactured by Mitsui DuPont Polychemicals was used.
(11) Ethylene-1-butene copolymer (EBM): ESR2041P manufactured by JSR was used.
(12) Polybutylacrylate-polymethyl methacrylate copolymer (MBA): Kureha Chemical Co., Ltd., Paraloid EXL2314 was used.
（実施例１）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＡＡ＝９０／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
Example 1
PET-I (10) / LDPE / EAA = 90/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例２）
ＰＥＴ−Ｉ（１０）／ＥＡＡ＝８５／１５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 2)
PET-I (10) / EAA = 85/15 (% by weight) was melt extruded at 270 ° C. using a twin screw vent type extruder, discharged into a strand, cooled in water, then cut with a strand cutter and pelleted A product was obtained. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例３）
ＰＥＴ−Ｉ（１０）／ＥＢＭ／ＥＡＡ＝９０／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
Example 3
PET-I (10) / EBM / EAA = 90/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent type extruder, discharged into a strand form, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例４）
ＰＥＴ−Ｉ（１０）／ＭＢＡ＝８５／１５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 4)
PET-I (10) / MBA = 85/15 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand, cooled in water, then cut with a strand cutter and pelleted A product was obtained. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（参考例５）
ＰＥＴ／ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＡＡ＝４５／４５／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本参考例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
( Reference Example 5)
PET / PET-I (10) / LDPE / EAA = 45/45/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent type extruder, discharged in the form of a strand, and cooled in water. Then, it was cut with a strand cutter to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this reference example had few neck-ins and good surging properties.
（参考例６）
ＰＥＴ／ＰＥＴ−Ｉ（１０）／ＥＡＡ＝４２／４２／１６（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本参考例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
( Reference Example 6)
PET / PET-I (10) / EAA = 42/42/16 (% by weight) was melt extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this reference example had few neck-ins and good surging properties.
（実施例７）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＡＡ＝９５／２．５／２．５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 7)
After PET-I (10) /LDPE/EAA=95/2.5/2.5 (wt%) was melt extruded at 270 ° C. using a twin screw vent type extruder, discharged into a strand and cooled in water Then, it was cut with a strand cutter to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例８）
ＰＥＴ−Ｉ（１０）／ＥＢＭ／ＥＡＡ＝９５／２．５／２．５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性、）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 8)
After PET-I (10) /EBM/EAA=95/2.5/2.5 (wt%) was melt extruded at 270 ° C. using a twin screw vent type extruder, discharged into a strand and cooled in water Then, it was cut with a strand cutter to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and characteristics (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例９）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＭＡＡ＝９０／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
Example 9
PET-I (10) / LDPE / EMAA = 90/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例１０）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＥＡ＝９０／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 10)
PET-I (10) / LDPE / EEA = 90/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（実施例１１）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＡＡ＝９０／８／２（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 11)
PET-I (10) / LDPE / EAA = 90/8/2 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent type extruder, discharged in the form of strands, cooled in water, and then with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（参考例１２）
ＰＥＴ／ＰＢＴ／ＬＤＰＥ／ＥＡＡ＝４５／４５／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本参考例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
( Reference Example 12)
PET / PBT / LDPE / EAA = 45/45/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged in a strand form, cooled in water, and then cut with a strand cutter. To obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this reference example had few neck-ins and good surging properties.
（実施例１３）
ＰＥＴ−Ｉ（１５）／ＬＤＰＥ／ＥＡＡ＝９０／５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本実施例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。
(Example 13)
PET-I (15) / LDPE / EAA = 90/5/5 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent type extruder, discharged into a strand, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this example had little neck-in and good surging properties.
（比較例１）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ／ＥＡＡ＝６０／２０／２０（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本比較例のポリエステル系樹脂は、ネックインが少なく、サージング性も良好であった。しかし、フィルム製膜時に樹脂膜と冷却ロールとの密着性が悪いため、樹脂膜に横段スジが発生しやすく不安定な製膜状態であった。
(Comparative Example 1)
PET-I (10) / LDPE / EAA = 60/20/20 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent type extruder, discharged into a strand form, cooled in water, and then washed with a strand cutter. Cut to obtain a pellet. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this comparative example had few neck-ins and good surging properties. However, since the adhesiveness between the resin film and the cooling roll is poor at the time of film formation, horizontal streaks are likely to occur in the resin film, resulting in an unstable film formation state.
（比較例２）
ＰＥＴ−Ｉ（１０）＝１００（重量％）を、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本比較例のポリエステル系樹脂は、ネックインが大きく、サージング性が不良であった。
(Comparative Example 2)
PET-I (10) = 100 (% by weight) was charged into an extruder, melted at 270 ° C., extruded in layers from a T die, and 200 mesh (average roughness Ra = 1.0) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 0 μm), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this comparative example had a large neck-in and poor surging properties.
（比較例３）
ＰＥＴ−Ｉ（１０）／ＬＤＰＥ＝９０／１０（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性）を表１に示す。本比較例のポリエステル系樹脂は、ネックインが大きく、サージング性も不良であった。
(Comparative Example 3)
PET-I (10) / LDPE = 90/10 (% by weight) was melt-extruded at 270 ° C. using a twin-screw vent extruder, discharged into a strand shape, cooled in water, then cut with a strand cutter and pelleted A product was obtained. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and properties (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this comparative example had a large neck-in and poor surging properties.
（比較例４）
ＰＥＴ−Ｉ（１０）／ＥＭＡ＝９５／５（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、官能基濃度、ネックイン量、サージング性）を表１に示す。本比較例のポリエステル系樹脂は、ネックインがやや大きく、サージング性もやや不良であった。
(Comparative Example 4)
PET-I (10) / EMA = 95/5 (% by weight) was melt-extruded at 270 ° C. using a biaxial vent type extruder, discharged into a strand shape, cooled in water, then cut with a strand cutter and pelleted A product was obtained. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and characteristics (melting point, functional group concentration, neck-in amount, surging property) of this polyester resin. The polyester resin of this comparative example had a slightly large neck-in and a slightly poor surging property.
（比較例５）
ＰＥＴ−Ｉ（１０）／アイオノマー＝９０／１０（重量％）を２軸ベント式押出機を用いて２７０℃で溶融押出し、ストランド状に吐出させ水中で冷却した後、ストランドカッターによりカットしてペレット状物を得た。上記ペレット状物を真空下で加熱乾燥した後、押出機に投入して２７０℃で溶融しＴダイより層状に押出し、バキュームチャンバー及びワイヤーピニングを付設した２００メッシュ（平均粗さＲａ＝１．０μｍ）の梨地冷却ロール上に５ｃｍの空間距離を置いて密着させながら、１００ｍ／ｍｉｎの速度で巻き取り、厚み２５μｍの未延伸フィルムを製膜し、その際の膜の成形性を評価した。
このポリエステル系樹脂の組成及び特性（融点、粒子径、ネックイン量、サージング性、）を表１に示す。本比較例のポリエステル系樹脂は、ネックインがやや大きく、サージング性もやや不良であった。また得られた膜には異物が多数混在していた。
(Comparative Example 5)
PET-I (10) / ionomer = 90/10 (% by weight) was melt extruded at 270 ° C. using a twin-screw vent type extruder, discharged into a strand, cooled in water, then cut with a strand cutter and pelleted A product was obtained. The pellets were heated and dried under vacuum, then put into an extruder, melted at 270 ° C., extruded in layers from a T-die, and 200 mesh (average roughness Ra = 1.0 μm) provided with a vacuum chamber and wire pinning. The film was wound at a speed of 100 m / min while being closely adhered to a satin cooling roll of 5), and an unstretched film having a thickness of 25 μm was formed, and the moldability of the film at that time was evaluated.
Table 1 shows the composition and characteristics (melting point, particle diameter, neck-in amount, surging property) of this polyester resin. The polyester resin of this comparative example had a slightly large neck-in and a slightly poor surging property. Moreover, many foreign materials were mixed in the obtained film.
上記結果を表１に示す。 The results are shown in Table 1.
本発明によるポリエステル系樹脂組成物は、溶融製膜時の溶融樹脂膜のネックイン低減及び溶融樹脂膜のサージング抑制、機械特性と熱安定性に優れた効果が得られ、本発明のポリエステル系樹脂を用いたフィルムは金属板等の各種基材に被覆する用途に利用することができる。 The polyester-based resin composition according to the present invention is effective in reducing the neck-in of the molten resin film during melt film formation, suppressing the surging of the molten resin film, and excellent in mechanical properties and thermal stability. The film using can be used for applications where various substrates such as metal plates are coated.
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| US7358322B2 (en) | 2004-03-09 | 2008-04-15 | Eastman Chemical Company | High IV melt phase polyester polymer catalyzed with antimony containing compounds |
| US20060047102A1 (en) | 2004-09-02 | 2006-03-02 | Stephen Weinhold | Spheroidal polyester polymer particles |
| JP4701662B2 (en) * | 2004-09-27 | 2011-06-15 | 東レ株式会社 | Polyester resin composition |
| US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| JP5031211B2 (en) * | 2005-09-08 | 2012-09-19 | 三井化学株式会社 | Polyester composition and film |
| US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
| US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
| US7838596B2 (en) | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
| US7655746B2 (en) | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US9267007B2 (en) | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
| JP2007297419A (en) * | 2006-04-27 | 2007-11-15 | Nippon Steel Corp | Resin film for coating metal plate, multi-layered resin film for coating metal plate, resin-coated metal plate and resin-coated metal container |
| US8901272B2 (en) | 2007-02-02 | 2014-12-02 | Grupo Petrotemex, S.A. De C.V. | Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration |
| JP5653731B2 (en) * | 2010-11-22 | 2015-01-14 | 古河電気工業株式会社 | Resin composition and molded product thereof |
| US20220212444A1 (en) | 2019-05-20 | 2022-07-07 | Toyo Kohan Co., Ltd. | Resin film for laminating metal plate and laminated metal plate using the same |
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