JPH0547575B2 - - Google Patents
Info
- Publication number
- JPH0547575B2 JPH0547575B2 JP1003669A JP366989A JPH0547575B2 JP H0547575 B2 JPH0547575 B2 JP H0547575B2 JP 1003669 A JP1003669 A JP 1003669A JP 366989 A JP366989 A JP 366989A JP H0547575 B2 JPH0547575 B2 JP H0547575B2
- Authority
- JP
- Japan
- Prior art keywords
- polyester resin
- foam
- thermoplastic polyester
- extruder
- compound
- 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 - Fee Related
Links
- 239000006260 foam Substances 0.000 claims description 41
- 229920006230 thermoplastic polyester resin Polymers 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 25
- 125000004018 acid anhydride group Chemical group 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000004604 Blowing Agent Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 9
- -1 glycidyl ester Chemical class 0.000 description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 16
- 239000000155 melt Substances 0.000 description 12
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000010097 foam moulding Methods 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 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
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- BXIIJPAVISPOGI-UHFFFAOYSA-N 1,1,2-trimethylcyclopropane Chemical compound CC1CC1(C)C BXIIJPAVISPOGI-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- HSMXEPWDIJUMSS-UHFFFAOYSA-K aluminum;tetradecanoate Chemical compound [Al+3].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O HSMXEPWDIJUMSS-UHFFFAOYSA-K 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 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
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 0.000 description 1
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
- NDWWLJQHOLSEHX-UHFFFAOYSA-L calcium;octanoate Chemical compound [Ca+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O NDWWLJQHOLSEHX-UHFFFAOYSA-L 0.000 description 1
- LSFBQOPXRBJSSI-UHFFFAOYSA-L calcium;tetradecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O LSFBQOPXRBJSSI-UHFFFAOYSA-L 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- VAROLYSFQDGFMV-UHFFFAOYSA-K di(octanoyloxy)alumanyl octanoate Chemical compound [Al+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VAROLYSFQDGFMV-UHFFFAOYSA-K 0.000 description 1
- UMNKXPULIDJLSU-UHFFFAOYSA-N dichlorofluoromethane Chemical compound FC(Cl)Cl UMNKXPULIDJLSU-UHFFFAOYSA-N 0.000 description 1
- 229940099364 dichlorofluoromethane Drugs 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- LRUDDHYVRFQYCN-UHFFFAOYSA-L dipotassium;terephthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 LRUDDHYVRFQYCN-UHFFFAOYSA-L 0.000 description 1
- VIQSRHWJEKERKR-UHFFFAOYSA-L disodium;terephthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 VIQSRHWJEKERKR-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- NEZRFXZYPAIZAD-UHFFFAOYSA-N ethylcyclobutane Chemical compound CCC1CCC1 NEZRFXZYPAIZAD-UHFFFAOYSA-N 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229940105112 magnesium myristate Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- HPBJPFJVNDHMEG-UHFFFAOYSA-L magnesium;octanoate Chemical compound [Mg+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HPBJPFJVNDHMEG-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- DMRBHZWQMKSQGR-UHFFFAOYSA-L magnesium;tetradecanoate Chemical compound [Mg+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O DMRBHZWQMKSQGR-UHFFFAOYSA-L 0.000 description 1
- 239000012803 melt mixture Substances 0.000 description 1
- VNXBKJFUJUWOCW-UHFFFAOYSA-N methylcyclopropane Chemical compound CC1CC1 VNXBKJFUJUWOCW-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229940114930 potassium stearate Drugs 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229960004249 sodium acetate Drugs 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229960005480 sodium caprylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229940045845 sodium myristate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- BYKRNSHANADUFY-UHFFFAOYSA-M sodium octanoate Chemical compound [Na+].CCCCCCCC([O-])=O BYKRNSHANADUFY-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- JUQGWKYSEXPRGL-UHFFFAOYSA-M sodium;tetradecanoate Chemical compound [Na+].CCCCCCCCCCCCCC([O-])=O JUQGWKYSEXPRGL-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229940035339 tri-chlor Drugs 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
〔産業上の利用分野〕
本発明は、ポリエステル系樹脂発泡体の製造法
に関し、詳しくは、押出し成形により、発泡倍率
が高く、また均一で細かい気泡を有し、さらに引
張強度、引張伸び、耐熱性、耐薬品性、断熱性、
剛性および緩衝性の優れた発泡体をつくることが
できるポリエステル系樹脂発泡体の製造法に関す
る。
本発明によるポリエステル系樹脂発泡体は、そ
れ自体を射出成形品、押出成形品、ブロー成形
品、発泡シート、または発泡ボードとして使用す
ることができるだけでなく、優れた引張強度およ
び引張伸びを有する特性によつて、発泡シート、
発泡ボードまたは発泡プレートを二次成形加工の
材料として利用することができる。
〔技術の背景および従来技術の説明〕
熱可塑性ポリエステル系樹脂は、中空成形品、
繊維およびフイルムなどの広範囲の用途に利用さ
れているが、これを発泡成形に利用すると、均一
な細かい気泡ができずにガスが抜け易いために、
熱可塑性ポリエステル系樹脂の押出し発泡成形
は、ほとんど不可能に近いくらいに難かしい。
これまでに、ポリエステルの押出し発泡成形に
おいて、ジエポキシ化合物およびステアリン酸カ
ルシウムまたは炭酸ナトリウムを加えて、ポリエ
ステルの溶融粘度を増大することが提案されてい
る。（特開昭53−24364号公報）また熱可塑性芳香
族ポリエステルの発泡成形において、多官能グリ
シジルエステルおよび多官能カルボン酸を熱可塑
性芳香族ポリエステルに加えて、溶融粘度を向上
することが提案されている。（特開昭59−210955
号公報）さらに熱可塑性ポリエステル系樹脂の発
泡成形において、１分子中に２以上の酸無水物基
を有する化合物を加えて、着色異物の混在するこ
とがない熱可塑性ポリエステル系樹脂発泡体の製
造法が提案されている。
本発明者はさらに研究を続け、その研究におい
て、熱可塑性ポリエステル系樹脂に、１分子中に
２以上の酸無水物基を有する化合物および周期律
表の、または族に属する金属の化合物を加
えると、溶融物の粘弾性が向上すること以外に引
張強度が大きく、引張伸びも大きい発泡成形体が
得られることを見出し、その知見に基づいて本発
明に到達した。
〔発明の目的および発明の要約〕
本発明の目的は、発泡倍率が高く、均一で微細
な気泡を有し、さらに引張強度および引張伸びの
向上した発泡成形体を得ることができる熱可塑性
ポリエステル系樹脂発泡体の製造法を提供するこ
とにある。
本発明は、熱可塑性ポリエステル系樹脂、１分
子中に２以上の酸無水物基を有する化合物および
易揮発性発泡剤の溶融配合物を低圧帯域に押出し
て、熱可塑性ポリエステル系樹脂発泡体を製造す
る方法において、その溶融配合物が、周期律表の
、または族に属する金属の化合物の加えら
れたものであつて、引張強度および引張伸びの大
きい発泡体をつくることができることを特徴とす
る熱可塑性ポリエステル系樹脂発泡体の製造法で
ある。
〔発明の具体的な説明〕
本発明においては、熱可塑性ポリエステル系樹
脂、１分子中に２以上の酸無水物基を有する化合
物、周期律表の、または族に属する金属の
化合物およびその他の添加物を混合して樹脂配合
物を調製するが、その樹脂配合物の調製に先立つ
て、それぞれの材料を充分に乾燥しておくべきで
ある。
この樹脂配合物を押出成形機のホツパーに供給
する。押出成形機において、樹脂配合物をスクリ
ユーにより押出ヘツド部側に送りながら加熱し、
溶融する。この溶融した樹脂配合物に発泡剤を注
入し、発泡剤を、この溶融した樹脂配合物相に均
一に分散混合し、その溶融物を押出機のヘツドに
取り付けられた金型より外界の低圧帯域に押出す
が、押出成形機中の溶融物は加圧状態にあるか
ら、溶融物が金型から外界に出た瞬間に溶融物は
低圧状態に押出され、発泡剤が膨張し、微細な気
泡を均一に分散した熱可塑性ポリエステル系樹脂
発泡体を形成する。
本発明の熱可塑性ポリエステル系樹脂発泡体の
製造法における熱可塑性ポリエステル系樹脂は、
芳香族ジカルボン酸成分とジオール成分の重縮合
体の線状ポリエステルである。
そのジカルボン酸成分は、テレフタル酸、イソ
フタル酸、ナフタレンジカルボン酸、ジフエニー
ルエーテルカルボン酸、ジフエニルスルホンジカ
ルボン酸またはジフエノキシエタンジカルボン酸
を使用することができる。
またジオール成分は、エチレングリコール、ト
リメチレングリコール、テトラメチレングリコー
ル、ネオペンチレングリコール、ヘキサメチレン
グリコール、シクロヘキサンジメタノール、トリ
シクロデカンジメタノール、２，２−ビス（４−
β−ヒドロキシエトキシフエニル）プロパン、
４，４−ビス（β−ヒドロキシエトキシ）ジフエ
ニルスルホンまたはジエチレングリコールを使用
することができる。
これらのジカルボン酸成分およびジオール成分
からなるポリエステルにおいて、ポリエチレンテ
レフタレート、ポリブチレンテレフタレート、ポ
リブチレンテレフタレートエラストマー、非晶性
ポリエステル、ポリシクロヘキサンテレフタレー
トなどおよびそれらの混合物を使用するのが好ま
しく、さらにこれらの熱可塑性ポリエステル系樹
脂を50％以上含む変性樹脂を使用することができ
る。
本発明の熱可塑性ポリエステル系樹脂発泡体の
製造法における１分子中に２以上の酸無水物基を
有する化合物は、１分子中に２以上の酸無水物基
を有する限りにおいて、芳香族酸無水物、環状脂
肪族酸無水物、脂肪族酸無水物、ハロゲン化酸無
水物などのようなものであつても、これを使用す
ることができ、さらにこれらの混合物あるいは変
性物であつても、これを使用することができる
が、無水ピロメリツト酸、ベンゾフエノンテトラ
カルボン酸二無水物、シクロペンタンテトラカル
ボン酸二無水物、ジフエニルスルホンテトラカル
ボン酸二無水物を使用するのが好ましく、無水ピ
ロメリツト酸を使用するのがさらに好ましい。
１分子中に２以上の酸無水物基を有する化合物
は、熱可塑性ポリエステル系樹脂100重量部に対
して、0.50〜5.0重量部の量において使用するの
が好ましい。１分子中に２以上の酸無水物基を有
する化合物を熱可塑性ポリエステル系樹脂100重
量部に対して、0.05重量部未満の量において使用
すると、熱可塑性ポリエステル系樹脂の溶融時の
粘弾性的特性の改善が充分でなく、良好な発泡体
を形成することができず、またその使用量が5.0
重量部を超えると、熱可塑性ポリエステル系樹脂
の溶融物のゲル化が進行して、発泡成形を行なう
ことができない。
周期律表の、または族に属する金属の化
合物は、これらの金属原子を構成原子とする限り
において、無機化合物および有機化合物のどのよ
うなものであつても、これを使用することができ
るが、無機物化合物は、塩化カリウム、塩化ナト
リウム、炭酸水素ナトリウム、炭酸ナトリウム、
炭酸カリウム、炭酸亜鉛、炭酸マグネシウム、炭
酸カルシウム、炭酸アルミニウム、酸化ナトリウ
ム、酸化カリウム、酸化亜鉛、酸化マグネシウ
ム、酸化カルシウム、酸化アルミニウムおよびこ
れらの水酸化物を例示することができ、また有機
化合物は、ステアリン酸ナトリウム、ステアリン
酸カリウム、ステアリン酸亜鉛、ステアリン酸マ
グネシウム、ステアリン酸カルシウム、ステアリ
ン酸アルミニウム、モンタン酸ナトリウム、モン
タン酸カルシウム、酢酸リチウム、酢酸ナトリウ
ム、酢酸亜鉛、酢酸マグネシウム、酢酸カルシウ
ム、カプリル酸ナトリウム、カプリル酸亜鉛、カ
プリル酸マグネシウム、カプリル酸カルシウム、
カプリル酸アルミニウム、ミリスチン酸ナトリウ
ム、ミリスチン酸亜鉛、ミリスチン酸マグネシウ
ム、ミリスチン酸カルシウム、ミリスチン酸アル
ミニウム、安息香酸カルシウム、テレフタル酸カ
リウム、テレフタル酸ナトリウム、ナトリウムエ
トキシドおよびカリウムフエノキシドを例示する
ことができる。これらの化合物において、周期律
表の族または族に属する金属の化合物を使用
するのが好ましく、また周期律表の族に属する
金属の化合物を使用するのが好ましい。周期律表
の、または族に属する金属の化合物を使用
することによつて、熱可塑性ポリエステル系樹脂
発泡体における気泡を微細にするだけでなく、１
分子中に２以上の酸無水物基を有する化合物によ
る溶融物の増粘効果を増大することもできる。
周期律表の、または族に属する金属の化
合物は、熱可塑性ポリエステル系樹脂100重量部
に対して、0.05〜5.0重量部の量において、使用
する。その使用量が0.05重量部未満であると、熱
可塑性ポリエステル系樹脂発泡体の気泡を微細に
する効果および１分子中に２以上の酸無水物基を
有する化合物の添加による熱可塑性ポリエステル
系樹脂の溶融物の増粘効果を増大する効果の発現
が充分でなく、またその使用量が5.0重量部を超
えると、発泡体が着色し、また熱可塑性ポリエス
テル系樹脂の溶融物の粘度が却つて低下する。
本発明の熱可塑性ポリエステル系樹脂発泡体の
製造における発泡剤は、加熱によりガス化ないし
膨張するものである限り、どのようなものであつ
ても、これを使用することができるが、易蒸発性
発泡剤、たとえば、不活性ガス、飽和脂肪族炭化
水素、飽和脂環族炭化水素、芳香族炭化水素、ハ
ロゲン化炭化水素、エーテルまたはケトンを使用
するのが好ましい。これらの易蒸発性発泡剤は、
炭酸ガス、窒素、メタン、エタン、プロパン、ブ
タン、ペンタン、ヘキサン、メチルペンタン、ジ
メチルブタン、メチルシクロプロパン、シクロペ
ンタン、シクロヘキサン、メチルシクロペンタ
ン、エチルシクロブタン、１，１，２−トリメチ
ルシクロプロパン、トリクロルモノフルオロメタ
ン、ジクロルフルオロメタン、モノクロルジフル
オロメタン、トリクロルトリフルオロエタン、ジ
クロルテトラフルオロエタン、ジクロルトリフル
オロエタン、モノクロルジフルオロエタン、テト
ラフルオロエタン、ジメチルエーテル、２−エト
キシエタノール、アセトン、メチルエチルケトン
またはアセチルアセトンを例示することができ
る。
本発明の熱可塑性ポリエステル系樹脂発泡体の
製造法において、樹脂配合物に、安定剤、発泡核
剤、顔料、充填剤、難燃剤または帯電防止剤を加
えて、熱可塑性ポリエステル系樹脂発泡体および
その成形物の物性を改善することができる。
また本発明の熱可塑性ポリエステル系樹脂発泡
体の製造法において、発泡成形は、単軸押出機、
多軸押出機およびタンデム押出機による押出成形
法および中空成形法、射出成形法などのいずれの
方法によることができ、押出成形法または中空成
形法に使用する金型は、フラツト金型、サーキユ
ラ金型、ノズル金型のいずれであつてもよい。
以下において、試験例および実施例により本発
明をさらに詳しく説明する。
実験例 １
ポリエチレンテレフタレートに対する無水ピロ
メリツト酸および炭酸ナトリウムの添加による押
出機のヘツド圧力に対する影響について試験を行
つた。
（試験方法）
ポリエチレンテレフタレート（PET 9902イー
ストマンコダツク社製）100重量部に、第１図に
示す量の無水ピロメリツト酸および炭酸ナトリウ
ムを加えた試料を押出機（口径：40mm、Ｌ／Ｄ：
30、金型口径：５mm）のホツパーに供給し、次の
条件において押出し成形を行ない、押出機のヘツ
ド圧力（Kg／cm2）を測定した。
押出機供給部温度：270℃
押出機圧縮部温度：290℃
押出機溶融部温度：280℃
押出機ヘツドの温度：280℃
押出機金型温度：280℃
スクリユー回転数：32rpm
（試験の結果）
試験の結果は第１図に示すとおりであつた。
（考察）
第１図によると、ポリエチレンテレフタレート
の押出し成形において、無水ピロメリツト酸およ
び炭酸ナトリウムの両者をポリエチレンテレフタ
レートに加えると、押出機ヘツド圧力は、それぞ
れの単独をポリエチレンテレフタレートに加えた
ときよりも高くなる。
押出機のヘツド圧力の上昇は溶融物の粘弾性の
増大であるから、ポリエチレンテレフタレートに
無水ピロメリツト酸および炭酸ナトリウムの両者
を加えることが、ポリエチレンテレフタレートの
押出し成形における溶融物の粘弾性の向上に効果
のあることがわかる。
実施例 １〜８
第１表のポリエチレンテレフタレートを除湿乾
燥機において、160℃の温度および−30℃の露点
の熱風により４時間乾燥した後、100重量部のポ
リエチレンテレフタレート、第１表に示す量の無
水ピロメリツト酸、第１表に示す量の第１表に示
す金属化合物および0.6重量部のタルク（発泡核
剤）をタンブラーにおいて混合し、５mmの口径の
ノズル金型を装着した単軸スクリユー押出機（口
径：40mm、Ｌ／Ｄ：30）のホツパーにその混合物
を投入し、その溶融物に、2.0％（重量）のｎ−
ペンタンを注入し、次の条件において、その溶融
物を押出し、ロツド状の発泡成形物を得た。
押出機供給部温度：268〜280℃
押出機圧縮部温度：285〜290℃
押出機溶融部温度：275〜285℃
押出機ヘツドの温度：275〜285℃
押出機金型温度：275〜285℃
スクリユー回転数：32rpm
発泡成形物の発泡倍率および気泡の状態は第１
表に示すとおりであつた。
比較例１および２
第１表に示すとおりのポリエチレンテレフタレ
ートおよび無水ピロメリツト酸を使用し、金属化
合物を使用しなかつたこと以外は実施例１〜８と
同様にして、ロツド状の発泡成形物を得た。
発泡成形物の発泡倍率および気泡の状態は第１
表に示すとおりであつた。
実施例 ９〜11
第２表に示すとおりのポリエチレンテレフタレ
ート、酸無水物および金属化合物を使用したこと
以外は実施例１と同様にして、発泡成形物を得
た。
発泡成形物の発泡倍率および気泡の状態は第２
表に示すとおりであつた。
比較例 ３および４
第２表に示すとおりのポリエチレンテレフタレ
ート、酸無水物およびジグリシジルテレフタレー
トを使用し、金属化合物を使用しなかつたこと以
外は、実施例１と同様にして、発泡成形物を得
た。
発泡成形物の発泡倍率および気泡の状態は第２
表に示すとおりであつた。
実施例 12
第３表のポリエチレンテレフタレートを除湿乾
燥機において、160℃の温度および−30℃の露点
の熱風により４時間乾燥した後、100重量部のポ
リエチレンテレフタレート、0.5重量部の無水ピ
ロメリツト酸、0.1重量部の炭酸ナトリウムおよ
び0.6重量部のタルク（発泡核剤）をタンブラー
において混合し、60mmの口径および0.65mmの出口
間隙のサーキユラ金型、ならびに205mmの口径お
よび1.5のＬ／Ｄの円筒形マンドレルを装着した
単軸スクリユー押出機（口径：65mm、Ｌ／Ｄ：
35）のホツパーに投入し、その溶融物に、1.7％
（重量）のブタンを注入し、次の条件において、
その溶融物をサーキユラ金型より押出し、これを
円筒形マンドレルに引取り、成形した後、その円
筒形発泡成形体の一部を切開し、シートの発泡成
形体を巻取つた。
押出機供給部温度：280℃
押出機圧縮部温度：290℃
押出機溶融部温度：280℃
押出機ヘツドの温度：280℃
押出機金型温度：270℃
発泡剤の注入圧力：80Kg／cm2
押出圧力（ヘツド部）：115Kg／cm2
スクリユー回転数：30rpm
押出量：24Kg／時
シート状の発泡成形体の発泡倍率、気泡の状
態、23℃における引張強度および23℃における引
張破断点は第３表に示すとおりであつた。
比較例 ５
実施例12において、無水ピロメリツト酸および
炭酸ナトリウムを使用することなく、第３表に示
す量のジグリシジルテレフタレートおよびモンタ
ン酸ナトリウムを使用したこと以外は、実施例12
と同様にして、シート状の発泡成形体を巻取つ
た。
シート状の発泡成形体の発泡倍率、気泡の状
態、23℃における引張強度および23℃における引
張破断点は第３表に示すとおりであつた。
比較例 ６
実施例12において、炭酸ナトリウムを使用する
ことなく、第３表に示す量のジグリシジルテレフ
タレートを使用したこと、ブタンの注入量を0.9
％（重量）としたこと、ならびに押出しの条件を
下記のとおりにしたこと以外は実施例12と同様に
して、シート状の発泡成形体を巻取つた。
押出機供給部温度：280℃
押出機圧縮部温度：290℃
押出機溶融部温度：280℃
押出機ヘツドの温度：285℃
押出機金型温度：275℃
発泡剤の注入圧力：40Kg／cm2
押出圧力（ヘツド部）：90Kg／cm2
スクリユー回転数：25rpm
押出量：24Kg／時
シート状の発泡成形体の発泡倍率、気泡の状
態、23℃における引張強度および23℃における引
張破断点は第３表に示すとおりであつた。
[Industrial Field of Application] The present invention relates to a method for producing polyester resin foam, and more specifically, the present invention relates to a method for producing a polyester resin foam, in particular, by extrusion molding, it has a high expansion ratio, uniform and fine cells, and has good tensile strength, tensile elongation, and heat resistance. properties, chemical resistance, insulation properties,
This invention relates to a method for producing polyester resin foam that can produce a foam with excellent rigidity and cushioning properties. The polyester resin foam according to the present invention can not only be used as an injection molded product, extrusion molded product, blow molded product, foam sheet, or foam board by itself, but also has the properties of excellent tensile strength and tensile elongation. By foam sheet,
Foam board or foam plate can be used as a material for the post-forming process. [Technical background and explanation of conventional technology] Thermoplastic polyester resin is used for blow molded products,
It is used for a wide range of applications such as fibers and films, but when used for foam molding, gas easily escapes without forming uniform fine bubbles.
Extrusion foam molding of thermoplastic polyester resins is extremely difficult. It has been previously proposed to add diepoxy compounds and calcium stearate or sodium carbonate to increase the melt viscosity of polyester in extrusion foam molding of polyester. (Japanese Unexamined Patent Publication No. 53-24364) It has also been proposed to improve the melt viscosity by adding polyfunctional glycidyl ester and polyfunctional carboxylic acid to thermoplastic aromatic polyester in foam molding of thermoplastic aromatic polyester. There is. (Unexamined Japanese Patent Publication No. 59-210955
Publication No. 2) Furthermore, in the foam molding of thermoplastic polyester resin, a compound having two or more acid anhydride groups is added in one molecule to produce a thermoplastic polyester resin foam that does not contain colored foreign matter. is proposed. The present inventor continued research and found that when a compound having two or more acid anhydride groups in one molecule and a metal compound belonging to a group of the periodic table were added to a thermoplastic polyester resin, It was discovered that, in addition to improving the viscoelasticity of the melt, a foamed molded article with high tensile strength and high tensile elongation can be obtained, and based on this knowledge, the present invention was achieved. [Object of the Invention and Summary of the Invention] The object of the present invention is to provide a thermoplastic polyester-based product that has a high expansion ratio, has uniform and fine cells, and can obtain a foamed molded product with improved tensile strength and tensile elongation. An object of the present invention is to provide a method for producing a resin foam. The present invention produces a thermoplastic polyester resin foam by extruding a melt blend of a thermoplastic polyester resin, a compound having two or more acid anhydride groups in one molecule, and an easily volatile blowing agent into a low pressure zone. A process characterized in that the melt mixture is capable of producing foams with high tensile strength and tensile elongation, to which a compound of a metal of the periodic table or group is added. This is a method for producing a plastic polyester resin foam. [Specific Description of the Invention] In the present invention, a thermoplastic polyester resin, a compound having two or more acid anhydride groups in one molecule, a compound of a metal in the periodic table or belonging to a group, and other additives are used. Before preparing the resin blend, each material should be thoroughly dried. This resin blend is fed into the hopper of an extruder. In an extrusion molding machine, the resin compound is heated while being sent to the extrusion head side by a screw,
melt. A blowing agent is injected into this molten resin compound, the blowing agent is uniformly dispersed and mixed in this molten resin compound phase, and the melt is passed through a mold attached to the head of an extruder into a low pressure zone in the outside world. However, the molten material in the extruder is under pressure, so the moment the molten material exits the mold, it is extruded to a low pressure state, the blowing agent expands, and fine bubbles are created. A thermoplastic polyester resin foam is formed in which the polyester resin is uniformly dispersed. The thermoplastic polyester resin in the method for producing a thermoplastic polyester resin foam of the present invention is:
It is a linear polyester of a polycondensate of an aromatic dicarboxylic acid component and a diol component. As the dicarboxylic acid component, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether carboxylic acid, diphenylsulfone dicarboxylic acid or diphenoxyethane dicarboxylic acid can be used. Diol components include ethylene glycol, trimethylene glycol, tetramethylene glycol, neopentylene glycol, hexamethylene glycol, cyclohexanedimethanol, tricyclodecane dimethanol, 2,2-bis(4-
β-hydroxyethoxyphenyl)propane,
4,4-bis(β-hydroxyethoxy)diphenylsulfone or diethylene glycol can be used. In these polyesters consisting of a dicarboxylic acid component and a diol component, it is preferable to use polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate elastomer, amorphous polyester, polycyclohexane terephthalate, etc., and mixtures thereof. A modified resin containing 50% or more of polyester resin can be used. In the method for producing thermoplastic polyester resin foam of the present invention, the compound having two or more acid anhydride groups in one molecule is an aromatic acid anhydride, as long as it has two or more acid anhydride groups in one molecule. Even if it is something such as a compound, a cyclic aliphatic acid anhydride, an aliphatic acid anhydride, a halogenated acid anhydride, or a mixture or modified product of these, Although this can be used, it is preferable to use pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, diphenylsulfone tetracarboxylic dianhydride, and pyromellitic anhydride More preferably, acids are used. The compound having two or more acid anhydride groups in one molecule is preferably used in an amount of 0.50 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. When a compound having two or more acid anhydride groups in one molecule is used in an amount less than 0.05 parts by weight per 100 parts by weight of thermoplastic polyester resin, the viscoelastic properties of the thermoplastic polyester resin when melted The improvement was not sufficient and a good foam could not be formed, and the amount used was 5.0
If the amount exceeds parts by weight, gelation of the melted thermoplastic polyester resin will proceed, making it impossible to perform foam molding. Compounds of metals in the periodic table or groups can be any inorganic or organic compounds, as long as these metal atoms are constituent atoms. Inorganic compounds include potassium chloride, sodium chloride, sodium hydrogen carbonate, sodium carbonate,
Potassium carbonate, zinc carbonate, magnesium carbonate, calcium carbonate, aluminum carbonate, sodium oxide, potassium oxide, zinc oxide, magnesium oxide, calcium oxide, aluminum oxide and their hydroxides can be exemplified, and organic compounds include: Sodium stearate, potassium stearate, zinc stearate, magnesium stearate, calcium stearate, aluminum stearate, sodium montanate, calcium montanate, lithium acetate, sodium acetate, zinc acetate, magnesium acetate, calcium acetate, sodium caprylate, Zinc caprylate, Magnesium caprylate, Calcium caprylate,
Examples may include aluminum caprylate, sodium myristate, zinc myristate, magnesium myristate, calcium myristate, aluminum myristate, calcium benzoate, potassium terephthalate, sodium terephthalate, sodium ethoxide and potassium phenoxide. . Among these compounds, it is preferable to use a group or a compound of a metal belonging to a group of the periodic table, and it is also preferable to use a compound of a metal belonging to a group of the periodic table. By using compounds of metals belonging to the periodic table or groups, not only can the cells in the thermoplastic polyester resin foam be made fine, but also 1
It is also possible to increase the thickening effect of the melt by compounds having two or more acid anhydride groups in the molecule. The compound of a metal belonging to a group of the periodic table is used in an amount of 0.05 to 5.0 parts by weight based on 100 parts by weight of the thermoplastic polyester resin. If the amount used is less than 0.05 part by weight, the effect of making the cells of the thermoplastic polyester resin foam finer and the addition of a compound having two or more acid anhydride groups in one molecule will improve the thermoplastic polyester resin foam. If the effect of increasing the viscosity of the melt is not sufficiently expressed and the amount used exceeds 5.0 parts by weight, the foam will be colored and the viscosity of the thermoplastic polyester resin melt will decrease. do. As the blowing agent for producing the thermoplastic polyester resin foam of the present invention, any blowing agent can be used as long as it gasifies or expands when heated. Preference is given to using blowing agents, such as inert gases, saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, ethers or ketones. These easily evaporable blowing agents are
Carbon dioxide, nitrogen, methane, ethane, propane, butane, pentane, hexane, methylpentane, dimethylbutane, methylcyclopropane, cyclopentane, cyclohexane, methylcyclopentane, ethylcyclobutane, 1,1,2-trimethylcyclopropane, trichlor Examples include monofluoromethane, dichlorofluoromethane, monochlorodifluoromethane, trichlorotrifluoroethane, dichlorotetrafluoroethane, dichlorotrifluoroethane, monochlorodifluoroethane, tetrafluoroethane, dimethyl ether, 2-ethoxyethanol, acetone, methyl ethyl ketone, or acetylacetone. can do. In the method for producing a thermoplastic polyester resin foam of the present invention, a stabilizer, a foam nucleating agent, a pigment, a filler, a flame retardant, or an antistatic agent are added to the resin mixture, and the thermoplastic polyester resin foam and The physical properties of the molded product can be improved. In addition, in the method for producing a thermoplastic polyester resin foam of the present invention, foam molding is carried out using a single screw extruder,
Extrusion molding using a multi-screw extruder or tandem extruder, blow molding, injection molding, etc. can be used. The molds used for extrusion molding or blow molding are flat molds, circular molds, etc. It may be either a mold or a nozzle mold. In the following, the present invention will be explained in more detail by means of test examples and examples. Experimental Example 1 A test was conducted to determine the effect of adding pyromellitic anhydride and sodium carbonate to polyethylene terephthalate on extruder head pressure. (Test method) A sample prepared by adding pyromellitic anhydride and sodium carbonate in the amounts shown in Figure 1 to 100 parts by weight of polyethylene terephthalate (PET 9902 manufactured by Eastman Kodak Co., Ltd.) was placed in an extruder (diameter: 40 mm, L/D:
30, mold diameter: 5 mm), extrusion molding was performed under the following conditions, and the extruder head pressure (Kg/cm 2 ) was measured. Extruder supply section temperature: 270℃ Extruder compression section temperature: 290℃ Extruder melting section temperature: 280℃ Extruder head temperature: 280℃ Extruder mold temperature: 280℃ Screw rotation speed: 32rpm (Test results) The results of the test were as shown in Figure 1. (Considerations) According to Figure 1, in extrusion molding of polyethylene terephthalate, when both pyromellitic anhydride and sodium carbonate are added to polyethylene terephthalate, the extruder head pressure is higher than when each is added alone to polyethylene terephthalate. Become. Since an increase in extruder head pressure increases the viscoelasticity of the melt, adding both pyromellitic anhydride and sodium carbonate to polyethylene terephthalate is effective in improving the viscoelasticity of the melt during extrusion molding of polyethylene terephthalate. It turns out that there is. Examples 1 to 8 After drying the polyethylene terephthalate shown in Table 1 for 4 hours with hot air at a temperature of 160°C and a dew point of -30°C in a dehumidifying dryer, 100 parts by weight of polyethylene terephthalate and the amount shown in Table 1 were added. Pyromellitic anhydride, the metal compound shown in Table 1 in the amount shown in Table 1, and 0.6 parts by weight of talc (foaming nucleating agent) were mixed in a tumbler, and a single screw extruder equipped with a nozzle mold with a diameter of 5 mm was used. The mixture was poured into a hopper (diameter: 40 mm, L/D: 30), and 2.0% (weight) of n-
Pentane was injected and the melt was extruded under the following conditions to obtain a rod-shaped foam molded product. Extruder supply section temperature: 268-280℃ Extruder compression section temperature: 285-290℃ Extruder melting section temperature: 275-285℃ Extruder head temperature: 275-285℃ Extruder mold temperature: 275-285℃ Screw rotation speed: 32rpm The expansion ratio and bubble condition of the foam molding are
It was as shown in the table. Comparative Examples 1 and 2 Rod-shaped foam molded products were obtained in the same manner as Examples 1 to 8, except that polyethylene terephthalate and pyromellitic anhydride as shown in Table 1 were used, and no metal compound was used. Ta. The expansion ratio and the state of the cells in the foamed molded product are
It was as shown in the table. Examples 9 to 11 Foam molded products were obtained in the same manner as in Example 1, except that polyethylene terephthalate, acid anhydride, and metal compound as shown in Table 2 were used. The expansion ratio and the state of the bubbles in the foamed molded product are determined by the second
It was as shown in the table. Comparative Examples 3 and 4 Foam molded products were obtained in the same manner as in Example 1, except that polyethylene terephthalate, acid anhydride, and diglycidyl terephthalate as shown in Table 2 were used, and no metal compound was used. Ta. The expansion ratio and the state of the bubbles in the foamed molded product are determined by the second
It was as shown in the table. Example 12 After drying the polyethylene terephthalate shown in Table 3 in a dehumidifying dryer for 4 hours with hot air at a temperature of 160°C and a dew point of -30°C, 100 parts by weight of polyethylene terephthalate, 0.5 parts by weight of pyromellitic anhydride, and 0.1 parts by weight of polyethylene terephthalate were dried. Parts by weight of sodium carbonate and 0.6 parts by weight of talc (foam nucleating agent) are mixed in a tumbler into a circular mold with a diameter of 60 mm and an exit gap of 0.65 mm, and a cylindrical mandrel with a diameter of 205 mm and an L/D of 1.5. Single screw extruder equipped with (diameter: 65mm, L/D:
35) into the hopper and add 1.7% to the melt.
(by weight) of butane is injected and under the following conditions:
The melt was extruded from a circular mold, taken up by a cylindrical mandrel and molded, and then a part of the cylindrical foam molded product was cut open and a sheet foam molded product was wound up. Extruder supply section temperature: 280℃ Extruder compression section temperature: 290℃ Extruder melting section temperature: 280℃ Extruder head temperature: 280℃ Extruder mold temperature: 270℃ Foaming agent injection pressure: 80Kg/cm 2 Extrusion pressure (head): 115Kg/cm 2 screw rotation speed: 30rpm Extrusion rate: 24Kg/hour It was as shown in Table 3. Comparative Example 5 Example 12 except that the amounts of diglycidyl terephthalate and sodium montanate shown in Table 3 were used without using pyromellitic anhydride and sodium carbonate.
In the same manner as above, a sheet-shaped foam molded product was wound up. The foaming ratio, cell condition, tensile strength at 23°C, and tensile breaking point at 23°C of the sheet-shaped foam molded product were as shown in Table 3. Comparative Example 6 In Example 12, diglycidyl terephthalate was used in the amount shown in Table 3 without using sodium carbonate, and the amount of butane injected was 0.9
% (weight) and the extrusion conditions were as follows, in the same manner as in Example 12, to roll up a sheet-shaped foam molded product. Extruder supply section temperature: 280℃ Extruder compression section temperature: 290℃ Extruder melting section temperature: 280℃ Extruder head temperature: 285℃ Extruder mold temperature: 275℃ Foaming agent injection pressure: 40Kg/cm 2 Extrusion pressure (head): 90Kg/cm 2 screw rotation speed: 25rpm Extrusion rate: 24Kg/hour It was as shown in Table 3.
【表】【table】
【表】【table】
【表】【table】
発泡倍率が大きく、気泡が細かく、均一に分散
した発泡成形体をつくることができる。
引張強度および引張破断時の伸びの大きい発泡
成形体をつくることができる。
耐熱強度の大きい発泡成形体をつくることがで
きる。
It is possible to create a foam molded product with a large expansion ratio and fine, uniformly dispersed cells. A foamed molded article with high tensile strength and elongation at break can be produced. It is possible to make a foamed molded product with high heat resistance strength.
第１図は試験例１の結果を示す図表であり、第
２図は試験例２の結果を示す図表である。
FIG. 1 is a chart showing the results of Test Example 1, and FIG. 2 is a chart showing the results of Test Example 2.
Claims (1)
以上の酸無水物基を有する化合物および発泡剤の
樹脂配合物を低圧帯域に押出すことからなる熱可
塑性ポリエステル系樹脂発泡体の製造法におい
て、熱可塑性ポリエステル系樹脂、１分子中に２
以上の酸無水物基を有する化合物および発泡剤の
樹脂配合物が、周期律表の、または族に属
する金属の化合物の加えられたものであることを
特徴とする熱可塑性ポリエステル系樹脂発泡体の
製造法。1 Thermoplastic polyester resin, 2 in 1 molecule
In the method for producing a thermoplastic polyester resin foam, which comprises extruding a resin blend of a compound having an acid anhydride group and a blowing agent into a low-pressure zone, the thermoplastic polyester resin contains 2
The thermoplastic polyester resin foam is characterized in that the resin mixture of the compound having an acid anhydride group and the blowing agent is added with a compound of a metal belonging to a group or group of the periodic table. Manufacturing method.
Priority Applications (31)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP366989A JPH02251543A (en) | 1989-01-12 | 1989-01-12 | Production of foamed polyester resin |
| CA 2004300 CA2004300C (en) | 1988-12-01 | 1989-11-30 | Process for producing polyester resin foam and polyester resin foam sheet |
| US07443416 US5000991B2 (en) | 1988-12-01 | 1989-11-30 | Process for producing polyester resin foam and polyester resin foam sheet |
| CA002214570A CA2214570C (en) | 1988-12-01 | 1989-11-30 | Food container produced from polyester resin foam sheet |
| TW80103098A TW212806B (en) | 1988-12-01 | 1989-12-01 | |
| DE1989626219 DE68926219T2 (en) | 1988-12-01 | 1989-12-01 | Process for the production of a polyester resin foam |
| ES93102840T ES2104973T3 (en) | 1988-12-01 | 1989-12-01 | METHOD FOR PRODUCING A CONTAINER FOR FOOD PRODUCTS. |
| AT93102832T ATE165611T1 (en) | 1988-12-01 | 1989-12-01 | METHOD FOR PRODUCING A POLYESTER RESIN FOAM |
| AT89312548T ATE136562T1 (en) | 1988-12-01 | 1989-12-01 | METHOD FOR PRODUCING A POLYESTER RESIN FOAM |
| EP19890312548 EP0372846B1 (en) | 1988-12-01 | 1989-12-01 | Process for producing polyester resin foam |
| DE1989628588 DE68928588T3 (en) | 1988-12-01 | 1989-12-01 | Polyester resin foam sheet |
| TW78109281A TW197457B (en) | 1988-12-01 | 1989-12-01 | |
| ES89312548T ES2086320T3 (en) | 1988-12-01 | 1989-12-01 | PROCEDURE FOR PRODUCING POLYESTER RESIN FOAM. |
| ES93102832T ES2118150T3 (en) | 1988-12-01 | 1989-12-01 | PROCEDURE FOR PRODUCING POLYESTER RESIN FOAM. |
| DE1989628659 DE68928659T2 (en) | 1988-12-01 | 1989-12-01 | Process for the production of a polyester resin foam |
| SG1996006167A SG46581A1 (en) | 1988-12-01 | 1989-12-01 | Process for producing polyester resin foam and polyester resin foam sheet |
| EP19930102832 EP0552813B1 (en) | 1988-12-01 | 1989-12-01 | Process for producing polyester resin foam |
| AU45797/89A AU635230B2 (en) | 1988-12-01 | 1989-12-01 | Process for producing polyester resin foam and polyester resin foam sheet |
| EP19930102839 EP0547032B2 (en) | 1988-12-01 | 1989-12-01 | Polyester resin foam sheet |
| KR1019890017952A KR0118112B1 (en) | 1988-12-01 | 1989-12-01 | Process for producing thermoplastic polyester resin foam |
| AT93102840T ATE155757T1 (en) | 1988-12-01 | 1989-12-01 | METHOD FOR PRODUCING A FOOD CONTAINER |
| EP19930102840 EP0547033B1 (en) | 1988-12-01 | 1989-12-01 | Method of producing a food container |
| ES93102839T ES2112344T5 (en) | 1988-12-01 | 1989-12-01 | POLYESTER RESIN FOAM SHEET. |
| AT93102839T ATE163442T1 (en) | 1988-12-01 | 1989-12-01 | POLYESTER RESIN FOAM SHEET |
| DE1989628205 DE68928205T2 (en) | 1988-12-01 | 1989-12-01 | Process for manufacturing a food container |
| AU35469/93A AU643402B2 (en) | 1988-12-01 | 1993-03-25 | Process for producing a shaped article |
| AU35473/93A AU650812B2 (en) | 1988-12-01 | 1993-03-25 | Process for producing polyester resin foam sheet |
| AU35468/93A AU652512B2 (en) | 1988-12-01 | 1993-03-25 | Process for producing polyester resin foam |
| KR1019960046181A KR19980027409A (en) | 1988-12-01 | 1996-10-16 | Manufacturing method of thermoplastic polyester resin foam |
| KR1019960046183A KR0118103B1 (en) | 1988-12-01 | 1996-10-16 | Food container |
| KR1019960046182A KR0118102B1 (en) | 1988-12-01 | 1996-10-16 | Thermoplastic polyester resin foam sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP366989A JPH02251543A (en) | 1989-01-12 | 1989-01-12 | Production of foamed polyester resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02251543A JPH02251543A (en) | 1990-10-09 |
| JPH0547575B2 true JPH0547575B2 (en) | 1993-07-19 |
Family
ID=11563840
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP366989A Granted JPH02251543A (en) | 1988-12-01 | 1989-01-12 | Production of foamed polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02251543A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202196A (en) * | 2009-02-27 | 2010-09-16 | Mitsubishi Plastics Inc | Interleaving paper for glass substrate transportation |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000035650A1 (en) | 1998-12-11 | 2000-06-22 | Sekisui Plastics Co., Ltd. | Method for producing foamed-in-mold product of aromatic polyester based resin |
| US11230418B2 (en) * | 2016-09-30 | 2022-01-25 | Huvis Corporation | Food container with reduced elution of hazardous substances |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5450062A (en) * | 1977-09-02 | 1979-04-19 | Rohm & Haas | Method of improving melt strength of polyethylene terephthalate |
| JPS59210955A (en) * | 1983-05-16 | 1984-11-29 | Sekisui Chem Co Ltd | Production of thermoplastic polyester resin foam |
| JPS624729A (en) * | 1985-07-02 | 1987-01-10 | Teijin Ltd | Thermoplastic polyester foam |
-
1989
- 1989-01-12 JP JP366989A patent/JPH02251543A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5450062A (en) * | 1977-09-02 | 1979-04-19 | Rohm & Haas | Method of improving melt strength of polyethylene terephthalate |
| JPS59210955A (en) * | 1983-05-16 | 1984-11-29 | Sekisui Chem Co Ltd | Production of thermoplastic polyester resin foam |
| JPS624729A (en) * | 1985-07-02 | 1987-01-10 | Teijin Ltd | Thermoplastic polyester foam |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010202196A (en) * | 2009-02-27 | 2010-09-16 | Mitsubishi Plastics Inc | Interleaving paper for glass substrate transportation |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02251543A (en) | 1990-10-09 |
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