CN101374893A - Polyester foam sheet and method for producing same - Google Patents
Polyester foam sheet and method for producing same Download PDFInfo
- Publication number
- CN101374893A CN101374893A CNA2007800032301A CN200780003230A CN101374893A CN 101374893 A CN101374893 A CN 101374893A CN A2007800032301 A CNA2007800032301 A CN A2007800032301A CN 200780003230 A CN200780003230 A CN 200780003230A CN 101374893 A CN101374893 A CN 101374893A
- Authority
- CN
- China
- Prior art keywords
- weight
- foamed polyester
- polyester sheet
- bubble
- sheet
- 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.)
- Pending
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- 229920000728 polyester Polymers 0.000 title claims abstract description 105
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000006260 foam Substances 0.000 title abstract description 44
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims abstract description 84
- -1 polytrimethylene terephthalate Polymers 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims description 127
- 238000000034 method Methods 0.000 claims description 58
- 239000000155 melt Substances 0.000 claims description 44
- 238000002425 crystallisation Methods 0.000 claims description 32
- 230000008025 crystallization Effects 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 238000005187 foaming Methods 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000007924 injection Substances 0.000 claims description 25
- 238000002347 injection Methods 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000004458 analytical method Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- 238000001579 optical reflectometry Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 description 37
- 229920000139 polyethylene terephthalate Polymers 0.000 description 19
- 239000005020 polyethylene terephthalate Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 210000004899 c-terminal region Anatomy 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000005452 bending Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000654 additive Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004567 concrete Substances 0.000 description 8
- 235000011089 carbon dioxide Nutrition 0.000 description 7
- 238000000113 differential scanning calorimetry Methods 0.000 description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
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- 238000002310 reflectometry Methods 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
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- 229960001701 chloroform Drugs 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 4
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 4
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000000546 pharmaceutical excipient Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
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- 239000000454 talc Substances 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 4
- 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 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 231100000241 scar Toxicity 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- WSNJABVSHLCCOX-UHFFFAOYSA-J trilithium;trimagnesium;trisodium;dioxido(oxo)silane;tetrafluoride Chemical compound [Li+].[Li+].[Li+].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O WSNJABVSHLCCOX-UHFFFAOYSA-J 0.000 description 3
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
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- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 2
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- 238000002955 isolation Methods 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
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- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
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- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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- 239000001530 fumaric acid Substances 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
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- 239000003112 inhibitor Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 230000035924 thermogenesis Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Classifications
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/35—Component parts; Details or accessories
- B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
- B29C44/356—Characteristics of the foam, e.g. having particular surface properties or structure having a porous surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/10—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels flexible, e.g. blown foils
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/25—Solid
- B29K2105/253—Preform
- B29K2105/256—Sheets, plates, blanks or films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Disclosed is a polyester foam sheet containing 50-100% by weight of polytrimethylene terephthalate and having an apparent density of 0.05-1.25 g/cm<3>. The polyester foam sheet contains bubbles having an average bubble size of 0.01-50 [mu]m, and the ratio between the average size (S) of the bubbles in the surface direction and the average size (T) of the bubbles in the thickness direction (S/T) is 0.05-10. Also disclosed is a method for producing such a polyester foam sheet.
Description
Technical field
The present invention relates to the Poly(Trimethylene Terephthalate) is the foamed polyester sheet of principal constituent and manufacture method thereof and the light reflecting board that formed by above-mentioned foamed polyester sheet.In more detail, the present invention relates to owing to inner that what have that trickle bubble has excellent light reflective, flexibility, heat insulating ability, lightweight is the foamed polyester sheet of principal constituent and manufacture method thereof and the light reflecting board that formed by above-mentioned foam piece with the Poly(Trimethylene Terephthalate).
Background technology
With polyethylene terephthalate (being designated hereinafter simply as " PET ") resin, polybutylene terephthalate (hereinafter to be referred as " PBT ") resin is that the thermoplastic polyester of representative utilizes features such as its excellent thermotolerance, reagent resistance, weathering resistance, mechanical and physical performance to be widely used in fields such as fiber, formed body.Particularly extrusion moulding such as film, sheet material body has excellent feature at aspects such as reagent resistance, weathering resistance, mechanical and physical performances, expect to be used as the material of various uses such as packaging vessel towards food, daily necessities, packing timber, building materials, light reflecting board.
In these purposes,,, expect that always sheet material or film contain the very trickle bubble below tens microns in inside perhaps in order to give its excellent luminous reflectance function in order to improve flexibility, heat insulating ability, lightweight.
In the past, the expanded polyester sheet that contains trickle bubble as inside, the known polyester film that following formation is arranged: with polyethylene terephthalate (PET) resin and resin inconsistent fine behind the decentralized system film with it, by single shaft or biaxial stretch-formed, formation is the trickle cavity (for example, referring to patent documentation 1) of nuclear with inconsistent resin.
In addition, also have motion to propose, in the high pressure container, after making carbonic acid gas be impregnated in the spool of PET sheet, be heated to 240 ℃, make the gas foaming that soaks into into, obtaining having following trickle bubble of average bubble footpath 50 μ m and thickness is that 200 μ m are above, proportion is the thermoplastic polyester foam (for example, referring to patent documentation 2) below 0.7.
As similar techniques, also proposed to use the technology (for example, referring to patent documentation 3) of Poly(Trimethylene Terephthalate) (being designated hereinafter simply as " the PTT ") resin of the fiber that can access the elastic recovery excellence.
As the problem that can improve poor in processability, bubble breaks easily, form the technology of the shortcoming of folding line or scar easily, following white films has been proposed, wherein, after the carbonic acid gas injection and being dissolved into the thermoplastic resin of molten state, be shaped to the flaky carbon dioxide dissolved foaming that makes simultaneously in die orifice portion, with the sheet material cooling on the cast drum that so obtains, thereafter, drawn, thermal treatment obtains described white films, it is characterized in that described white films has specific bubble, is a kind of thermoplastic resin more than 95% among the film forming composition of structure, and this film on the single shaft direction, be stretched at least (for example, referring to patent documentation 4).
In addition, also proposed a kind of foam, it is by being that terephthalic acid propylene glycol ester unit and the terephthalic acid propylene glycol ester based polymer with specific intrinsic viscosity, terminal carboxylic acid amount constitute more than the 30 weight %, and the apparent density of this foam is 0.001g/cm
3～1.2g/cm
3(for example, referring to patent documentation 5).
On the other hand, consider to utilize its high luminous reflectance factor and high diffuse and the expanded polyester sheet that trickle bubble is contained in inside is used for the lighting fixturess such as lamp box, luminescent lamp etc. of liquid crystal indicator.As such light reflecting board, following light reflecting board has been proposed, it is after making carbonic acid gas be impregnated in the spool of PET sheet in the high pressure container, be heated to 240 ℃, the gas foaming that soaks into is into obtained, trickle bubble, thickness below 50 μ m of average bubble footpath is more than the 200 μ m by having for it, proportion is that thermoplastic polyester foam below 0.7 forms (for example, referring to patent documentation 2).
In addition, also proposed the foaming sheet or the film that use as light reflecting board, it has specific apparent specific gravity and specific void fraction (for example referring to patent documentation 6) by obtaining containing PET and stretching with the resin of the polymethylpentene of PET non-conforming.
Patent documentation 1: No. 3018539 communiques of Japanese Patent
Patent documentation 2: No. 2925745 communiques of Japanese Patent
Patent documentation 3: Japanese kokai publication hei 11-268212 communique
Patent documentation 4: Japanese kokai publication hei 11-300814 communique
Patent documentation 5: TOHKEMY 2002-226619 communique
Patent documentation 6: TOHKEMY 2005-281396 communique
Summary of the invention
But in the foam films of above-mentioned patent documentation 1, the stretching by film making process has formed bubble, so film carries out to oriented crystallineization, has that ductility is low, the problem of poor in processability.In addition, for foam films,, have the structure of the bubble of gap-like because resin is at face direction lamination, thus its when existing in bending or from the face direction when stressed bubble break easily or occur the shortcoming of folding line or scar easily.In addition, be difficult to independence, can only obtain stretchable film as formed body.
Discover through the inventor, utilize flexibility, the insufficient formability of the sheet material that the technology of patent documentation 2 obtains.And, even this technology is directly used in Poly(Trimethylene Terephthalate) (PTT), gas is soaked into after, because the sheet material crystallization no longer foams, the sheet material of flexibility and good forming ability can not be obtained, moreover, even the sheet material of trickle foaming can not be obtained having.
In the technology of patent documentation 3, the space of Poly(Trimethylene Terephthalate) (PTT) mixed with resin non-conforming is formed the inorganic particles that plastic resin hot in nature and/or bubble-shaped become second nature, in the stretching process of film, form bubble at interface with resin boundary surface or inorganic particles.But, according to discovering of the inventor, by using the low PTT resin of crystallization Young's modulus, flexibility more or less increases, but,, and still be difficult to obtain thick film so its effect is insufficient because the oriented crystallineization of film and gap-like bubble aspect do not change.Even so use the technology of patent documentation 3, the problem that produces in the time of can not solving above-mentioned use polyethylene terephthalate (PET) resin.
In the technology of patent documentation 4,5, in resin, inject volatile foaming agent more than the dissolving 1 weight %, the specifically two acidifying carbon of 20 weight % or the normal butane of 4 weight %, thereby obtain foam.But, according to discovering of the inventor,, can not make the bubble granular though utilize these technology to obtain foam, still can not solve the above problems.
As mentioned above, there is the problem of the sheet material can not obtain having excellent flexibility, heat insulating ability, lightweight, light reflective in prior art so far.
On the other hand, consider as under the situation of light reflecting board, owing to used PET in the technology of patent documentation 2, so flexibility is poor, be difficult to be processed into and the light source corresponding shape, and, in the time will being processed into the curved surface of corresponding light source, there is the problem that bending takes place or form fold because elastic recovery is poor.
In addition, even the sheet material thin thickness that obtains with the technology of patent documentation 6 also has high reflectivity, so can easily make its distortion by thickness thinning, but, the cavity of being contained obtains by stretching, so these cavities are flat, when reducing the curvature when being processed into the curved surface shape, there is the problem that is bent into acute angle easily or produces a large amount of folds.
As mentioned above, in the prior art so far, existence can not obtain easily being processed into shape that is fit to various light sources and the light reflecting board that can make the shape of the little a wider range such as curved surface of curvature.
The present invention is used to solve above-mentioned problem, its objective is provides a kind of foamed polyester sheet and manufacture method and light reflecting board, described foamed polyester sheet is principal constituent with the Poly(Trimethylene Terephthalate), have excellent light reflective, flexibility, heat insulating ability, lightweight, described light reflecting board is formed by above-mentioned foam piece, have excellent light reflective, can easily be processed into the shape that is fit to light source and can not produce fold.
The inventor furthers investigate for solving above-mentioned problem, found that, can solve above-mentioned problem by be formed in the superfine foam piece that inside has the trickle bubble of specified shape by the resin combination that with Poly(Trimethylene Terephthalate) (PTT) is principal constituent, thereby finish the present invention.That is, by following foamed polyester sheet with and manufacture method realized purpose of the present invention.
(1) a kind of foamed polyester sheet, it contains 50 weight %～100 weight % Poly(Trimethylene Terephthalate), and apparent density is 0.05g/cm
3～1.25g/cm
3, wherein, described foamed polyester sheet comprises the bubble that average bubble size is 0.01 μ m～50 μ m, and the ratio (S/T) of the mean sizes (T) of the mean sizes (S) of the face direction of described bubble and thickness direction is 0.05～10.
(2) as (1) described foamed polyester sheet, wherein, the thickness of described foamed polyester sheet is 1 μ m～10mm.
(3) as (1) or (2) described foamed polyester sheet, wherein, the average bubble size of described bubble is 0.01 μ m～30 μ m, and the mean sizes (S) of the face direction of described bubble is 0.7～3 with the ratio (S/T) of the mean sizes (T) of thickness direction.
(4) as each the described foamed polyester sheet in (1)～(3), wherein, described foamed polyester sheet is-2%～5% at 150 ℃ percent thermal shrinkage.
(5) as each the described foamed polyester sheet in (1)～(4), wherein, described foamed polyester sheet is more than 80% to the average light reflectivity of the light of wavelength with 400nm～700nm.
(6) as each the described foamed polyester sheet in (1)～(5), it is to utilize to melt extrude manufactured.
(7), wherein, when utilizing power compensation differential scanning calorimeter to carry out the heat analysis, between 0 ℃～150 ℃, observed the exothermic peak that produces by crystallization as each the described foamed polyester sheet in (1)～(6).
(8) as each the described foamed polyester sheet in (1)～(7), wherein, the appearance time of the isothermal crystalization of described foamed polyester sheet is that 1～60 second temperature is present in 100 ℃～150 ℃ scope.
(9) a kind of light reflecting board, it is made of each the described described foamed polyester sheet in (1)～(8).
(10) as the light reflecting board of (9), wherein, when utilizing power compensation differential scanning calorimeter to carry out the heat analysis, the observed exothermic peak that is produced by crystallization is 0J/g～3J/g between 0 ℃～150 ℃.
(11) a kind of manufacture method of foamed polyester sheet, wherein, the melt temperature at this melts is the gasiform material under injection 0.01 weight %～3 weight % normal pressures in the melts that contains 50 weight %～100 weight % Poly(Trimethylene Terephthalate), after mixing, dissolving obtain melts, the described melts that obtains is extruded the material foaming that makes described injection when carrying out moulding, cooling curing then with the extrusion pressure of 5MPa～100MPa from die orifice.
(12) as the manufacture method of (11) described foamed polyester sheet, wherein, the material of described injection is a gaseous state under normal temperature, normal pressure.
(13) as the manufacture method of (11) or (12) described foamed polyester sheet, wherein, after described melts extruded from the die orifice of slit-shaped, this melts is cast in metal roller or is with, then this melts is put into water, carry out cooling curing.
(14) a kind of manufacture method of foamed polyester sheet, wherein, behind the amorphousness sheet that 0.01 weight %～3 weight % normal temperature and pressures are made of the resin combination of the Poly(Trimethylene Terephthalate) that contains 50 weight %～100 weight % for the injection of gasiform material down, this amorphousness sheet is heated to 60 ℃～200 ℃, makes the material foaming of described injection.
(15) as the manufacture method of each the described foamed polyester sheet in (11)～(14), wherein, the material of described injection is a nitrogen.
The foamed polyester sheet that the present invention relates to has excellent light reflective, flexibility, heat insulating ability, lightweight.Therefore, be used under the situation of light reflecting board, have excellent light reflective, diffuse, and having the punching press or the bendability that easily are processed into to corrugationless the shape that is fit to light source, is useful as the light reflecting board of lighting fixturess such as the lamp box of liquid crystal indicator, luminescent lamp etc.In addition, foam piece of the present invention is useful in various uses such as food product containers, packing timber, building materials.
Description of drawings
Fig. 1 is the synoptic diagram of one of embodiment of the light reflecting board that the present invention relates to of expression.
Embodiment
Below the present invention is specifically described.
Foamed polyester sheet of the present invention is the foam piece that contains Poly(Trimethylene Terephthalate) (PTT) resin of 50 weight %～100 weight %.
At this, Poly(Trimethylene Terephthalate) (PTT) is meant with terephthalic acid and is sour composition, is the polyester of the PTT repeating unit formation of diol component with propylene glycol (also claim 1, ammediol is designated hereinafter simply as " TMG ").
50 weight % of foamed polyester sheet of the present invention～100 weight % are made of the PTT resin, so can realize having excellent flexibility, the sheet material of formability.It is believed that this is because of following 3 points, the first, the crystallization speed of PTT inherent appropriateness; The second, the chemical stability that PTT (PTT is the low saturated polyester of a kind of chemical reactivity) molecular structure brings; The 3rd, the crystalline flexibility that jagged molecular structure brings.
From the flexibility of sheet material, the easiness and the stable on heating viewpoint of manufacturing, the ratio of PTT resin is preferably 70 weight %～100 weight %, more preferably 80 weight %～100 weight %, more preferably 90 weight %～100 weight %.This PTT can also contain other copolymer composition.
As copolymer composition, can enumerate for example ethylene glycol, 1, the 1-propylene glycol, 1, the 2-propylene glycol, 2, the 2-propylene glycol, 1, the 2-butyleneglycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, decamethylene-glycol, 1, the 12-dodecanediol, 1, the 2-cyclohexanediol, 1, the 3-cyclohexanediol, 1, the 4-cyclohexanediol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 5-sodium sulfo isophthalate, 3,5-dicarboxylic acid Phenylsulfonic acid tetramethyl-phosphonium salt, m-phthalic acid, oxalic acid, succsinic acid, hexanodioic acid, dodecanedioic acid, fumaric acid, toxilic acid, 1,4-cyclohexane dicarboxylic acid etc. can form the monomer of ester; Polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol and these multipolymer etc.
Thermostability, the flexibility of sheet material, light reflective, thermotolerance when making sheet material in order to improve, the composition that preferably makes above-mentioned random copolymerization are 30 moles below the %, more preferably 20 moles below the %, and more preferably 10 moles below the %.
As for the polymerization degree of PTT of the present invention, preferred intrinsic viscosity [η] is 0.5dl/g～4dl/g.Intrinsic viscosity is that the manufacturing of sheet material becomes easily under the above situation of 0.5dl/g, makes bubble size trickle easily simultaneously, forms easily to have excellent intensity, the foam piece and the formed body of flexibility.Intrinsic viscosity [η] is under the following situation of 4.0dl/g, can easily form sheet material.Intrinsic viscosity [η] is 0.7dl/g～3dl/g more preferably, and more preferably 0.9dl/g～2.5dl/g is preferably 1.0dl/g～2dl/g especially.
Preferred its C-terminal base concentration of PTT of the present invention is 0eq/ ton～80eq/ ton.Whereby, can easily improve weathering resistance, reagent resistance, hydrolytic resistance and the thermotolerance of sheet material and formed body.C-terminal base concentration is 0eq/ ton～50eq/ ton more preferably, and more preferably 0eq/ ton～30eq/ ton is preferably 0meq/kg～20meq/kg especially, and this concentration is low more good more.
Based on identical reason, as the TMG of the diol component of PTT through i.e. two (3-hydroxypropyl) ether composition (structural formula :-OCH of ehter bond bonded glycol dipolymer composition
2CH
2CH
2OCH
2CH
2CH
2O-is designated hereinafter simply as " BPE ") containing ratio be preferably 0 weight %～2 weight %.Containing ratio is 0.1 weight %～1.5 weight % more preferably, more preferably 0.15 weight %～1.2 weight %.
Foamed polyester sheet of the present invention can also contain various organic substances, inorganic substance, various additives etc. except PTT.In this case, the ratio of PTT must be in above-mentioned scope.In addition, the ratio of PTT can be by using
1H NMR (Nuclear Magnetic Resonance) spectrum (being designated hereinafter simply as " NMR ") is with HFIP:CDCl
3=1:1 obtains as solvent analysis.At this moment, comprised in the ratio of the PTT that is calculated with various PTT oligopolymer, BPE headed by the cyclic dimer.
As the organic substance beyond the PTT, can enumerate the monomer of ring-type, catenate PTT oligopolymer, the sour composition that constitutes PTT or diol component and the lower molecular weight reactant that these materials form, resin and the various additive beyond the PTT.As the resin beyond the PTT, can enumerate thermoplastic polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN, poly-naphthalic acid propylene glycol ester; Heat cured polyester; Polyamide thermoplastics such as nylon 6, nylon 66, Ni Long11, nylon 12; Polyolefine such as polyethylene, polypropylene; Polycarbonate; Urethane; Fluorine-type resin; Silicone based resin; Polyphenylene sulfide; Resins, epoxy; Acrylic resin; Mierocrystalline cellulose etc. and these copolymer resins etc.
As the inorganic substance beyond the PTT, can enumerate inorganic filler, inorganic lubricant, polymerizing catalyst residues etc. such as glass fibre, carbon fiber, talcum, mica, wollastonite, kaolin, lime carbonate, two acidifying titaniums, silicon-dioxide.
As additive, can enumerate the pigment, matting agent, thermo-stabilizer, fire retardant, static inhibitor, defoamer, positive toner, antioxidant, UV light absorber, nucleator, whitening agent, impurity trapping agent, thickening material, surface conditioner of dyestuff, the organic or inorganic of organic or inorganic etc.
As thermo-stabilizer, the phosphorus compound of preferred 5 valencys and/or 3 valencys, hindered phenol based compound.In the part by weight of phosphoric in the powder, the addition of phosphorus compound is preferably 2ppm～500ppm, more preferably 10ppm～200ppm.As concrete compound, preferred trimethyl phosphite, phosphoric acid, phosphorous acid, three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (Irgafos168 that Ciba Co., Ltd. makes etc.).
At this, the hindered phenol based compound be phenol be the adjoining position of hydroxyl to have sterically hindered big substituent phenol be derivative, it has ester bond more than 1 at intramolecularly.As the addition of hindered phenol based compound, in the part by weight with respect to powder, it is preferably 0.001 weight %～1 weight %, more preferably 0.01 weight %～0.2 weight %.
As concrete compound, [3-(3 can to enumerate tetramethylolmethane-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Irganox1010 that Ciba Co., Ltd. makes etc.), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester (Irganox1076 that Ciba Co., Ltd. makes etc.), N, N '-hexa-methylene two (3,5-tertiary butyl-4-hydroxy-hydroxyl cinnamide), Triethylene glycol two [3-(a 5-tertiary butyl-4-hydroxy-tolyl) propionic ester] (Irganox245 that Ciba Co., Ltd. makes etc.), N, N ' hexane-1, two [the 3-(3,5-di-tert-butyl-hydroxy phenyl propionic acid amide) (Irganox1098 that Ciba Co., Ltd. makes etc.) etc. of 6-two bases.Certainly, the stablizer that share these also is one of preferable methods.
Preferably in foam piece of the present invention, add the trapping agent of lower molecular weight volatile impunty.As trapping agent, the polymkeric substance of preferred polyamide, polyesteramide or oligopolymer have the low-molecular weight compound of amide group, amido etc.As addition, in part by weight, be preferably 0.001 weight %～1 weight %, more preferably 0.01 weight %～0.2 weight % with respect to powder.
As concrete compound, polymkeric substance such as polymeric amide, polymine such as preferred nylon 6.6, nylon 6, nylon 4.6; And N-phenylaniline and 2,4, the resultant of reaction of 4-2,4,4-Trimethyl-1-pentene (Irganox 5057 that Ciba Co., Ltd. makes etc.), N, N ' hexane-1, the two [3-(3,5 di-tert-butyl-hydroxy phenyl propionic acid amide) (Irganox1098 that Ciba Co., Ltd. makes etc.), 2 of 6-two bases, 6-di-t-butyl-4-(4,6-two (hot sulfenyl)-1,3,5-triazines-2-base is amino) phenol (Irganox565 that Ciba Co., Ltd. makes etc.) etc.Certainly, these to share also be one of preferable methods.
These materials comprise situation and the compatible situation about existing with polymer molecule that exists with particle form, and among the present invention, the median size that preferably contains is that the particle of 0.01 μ m～100 μ m is 0.1 weight %～30 weight % of PTT.Owing to have such particle, so can easily have a large amount of trickle bubbles.Particle more preferably median size is 0.1 μ m～50 μ m, and more preferably 0.3 μ m～20 μ m are preferably 0.5 μ m～10 μ m especially.
When the particulate median size was big more, the content of preferred particulates was also big, and the particulate median size more hour, reducing particulate content also can, but be preferably about 0.5 weight %～20 weight %, more preferably 1 weight %～15 weight % are preferably 2 weight %～10 weight % especially.Compare with positive globular particle, flat tabular or acicular particle is better, and preferably has projection.In addition, the particle of preferably using the consistency material low and that cohesiveness is also low with PTT to obtain.
Specifically, can enumerate with talcum, tetrafluoroethylene (being designated hereinafter simply as " PTFE ") is the fluorine-type resin of representative; The powder that forms by fluorine mica, plate-like aluminum oxide, layered silicate etc.Wherein, fluorine-type resin and fluorine mica can make the size of bubble become tiny, improve flexibility, heat insulating ability, the light reflective of sheet material, so it is preferred, and, the stable on heating viewpoint during from the manufacturing sheet material, most preferably PTFE.
The thickness of foamed polyester sheet of the present invention is preferably 1 μ m～10mm.By making thickness is more than the 1 μ m, and the processing of sheet material becomes easily, is below the 10mm by making thickness, and it is easy that hot briquetting becomes.The thickness of foamed polyester sheet is 10 μ m～5mm more preferably, and more preferably 50 μ m～3mm are preferably 100 μ m～2mm especially.
It is 0.05g/cm that foamed polyester sheet of the present invention needs apparent density
3～1.25g/cm
3And average bubble size is 0.01 μ m～50 μ m.By density, the bubble size of realizing this scope, can obtain having excellent light reflective, flexibility, bubble is difficult for breaking and has kept the foam piece of lightweight.
At this, mean sizes about bubble, use scanning electron microscope (being designated hereinafter simply as " SEM (Scanning Electron Microscope) ") to observe the cross section of sheet material, use image analysis software to calculate it and be equivalent to circular diameter, obtain the mean sizes of bubble with the form of this diameter according to observed cross-sectional image.The apparent density of foamed polyester sheet is preferably 0.1g/cm
3～1g/cm
3, 0.15g/cm more preferably
3～0.8g/cm
3, 0.2g/cm more preferably
3～0.7g/cm
3
The average bubble size of foamed polyester sheet is preferably 0.01 μ m～30 μ m, more preferably 0.01 μ m～20 μ m, more preferably 0.01 μ m～10 μ m.From the light reflective of giving the sheet material excellence, the viewpoint of flexibility, average bubble size is preferably below 1/5 of sheet thickness, more preferably below 1/10, more preferably below 1/50, is preferably below 1/100 especially.
Bubble in the foamed polyester sheet of the present invention must not be flat.As it is not flat index, can use the ratio (S/T) of mean sizes (T) of mean sizes (S) and thickness direction of the face direction of bubble, should (S/T) be necessary for 0.05～10, more preferably 0.1～10, more preferably 0.5～5, more preferably 0.7～3, be preferably 1～2 especially.S/T is when above-mentioned scope, and the bubble of foam piece is difficult for breaking, and in addition, is principal constituent in conjunction with foam piece of the present invention with the Poly(Trimethylene Terephthalate), is difficult for occurring in foam piece folding line or scar.
Preferably adjust the crystallinity of foamed polyester sheet of the present invention according to applied purposes, purpose.Make under the situation that the former sheet material of the formed body of desired shape uses by hot briquetting as being used for, the crystalline attitude of preferred polyester foam piece right and wrong, on the other hand, as requiring under the situation of stable on heating container, light reflecting board, the preferred polyester foam piece is a crystalline state.
The index of crystalline state can use with power compensation differential scanning calorimeter (being designated hereinafter simply as " DSC (Differential Scanning Calorimetry) ") with sheet material 0 ℃ keep 3 minutes after with the size of the setting heat-up rate of 10 ℃/min viewed exothermic peak when 0 ℃ is warmed up to 260 ℃.Observe exothermic peak and show that the leeway that crystallization is arranged is that degree of crystallinity is low, and represent easy hot briquetting, do not observe exothermic peak or exothermic peak and show that for a short time the leeway that does not have crystallization is the degree of crystallinity height.
Make under the situation of the former sheet material that is used for hot briquetting, preferred view is to exothermic peak, and preferred heat is more than the 10J/g, more preferably more than the 20J/g, require under the stable on heating situation, heat is preferably below the 5J/g, more preferably below the 3J/g, more preferably below the 1J/g, most preferably do not observe exothermic peak.The upper limit of exothermic peak is generally below the 90J/g.
After carrying out moulding, give thermotolerance in order to make it add thermal crystallization, the appearance time of the isothermal crystalization of preferred polyester foam piece is that the temperature under 1 second～60 seconds the situation is present in 100 ℃～150 ℃ scope.It is the index of the crystallization speed of the expression resin that constitutes sheet material, can realize These parameters when the resin of the PTT of containing of the present invention has specific structure.By making such sheet material, when can heating excipient, can easily carry out crystallization in the short period of time relatively, give thermotolerance.
At this, the appearance time of so-called isothermal crystalization is meant, with foamed polyester sheet after 280 ℃ of fusions, this melts chilling in liquid nitrogen is made its curing, with the composition that obtains thus with power compensation differential scanning calorimeter (DSC) 0 ℃ keep 3 minutes after, be warmed up to X ℃ with the setting heat-up rate of 500 ℃/min from 0 ℃, the observed shown appearance time of heat absorption that is produced by crystallization is the appearance time of isothermal crystalization when keeping for X ℃.The said temperature scope is preferred continuous more than 5 ℃, and more preferably 10 ℃, further preferred more than 20 ℃, particularly preferably in 100 ℃～150 ℃ whole temperature range, appearance time is 1 second～60 seconds.
That is, when the foamed polyester sheet that the present invention relates to being carried out the heat analysis, between 0 ℃～150 ℃, can observe the exothermic peak that produces by crystallization with power compensation differential scanning calorimeter (DSC).
From the angle of thermotolerance and post-treatment, longitudinal direction of preferred foamed polyester sheet of the present invention (MD) and transverse direction (TD) are-2%～5% at 150 ℃ percent thermal shrinkage.Percent thermal shrinkage is the index that expression constitutes the loose distortion of polymer molecule of sheet material, and it is 0% o'clock, and expression is distortion not.Be in by the degree that makes distortion among a small circle above-mentioned, under the situation that hot environment is used, the dimensional change in the time of can suppressing temperature variation or the distortion of sheet material.When making sheet material, longitudinal direction (MD) expression collects direction, transverse direction (TD) expression direction orthogonal with it.Little distortion like this can be by not applying that over-drastic stretches or tension force is realized making the sheet material operation, and it is to use the PTT can be in the feature of not carrying out generating under the tensile situation sheet material of the present invention of bubble as raw material.
Percent thermal shrinkage more preferably-1%～3% more preferably-0.5%～2%, is preferably-0.3%～1% especially.Direction beyond preferred longitudinal and transverse also is such shrinking percentage.Foamed polyester sheet of the present invention so realize so low percent thermal shrinkage easily, also reduces in length and breadth the shrinking percentage of direction in addition owing to initiatively not stretching easily.
The foamed polyester sheet of the present invention preferably average light reflectivity under the wavelength of 400nm～700nm is more than 80%.By making such reflectivity, foamed polyester sheet of the present invention is suitable as light reflecting board.More preferably making the average light reflectivity is more than 85%, more preferably more than 90%.At this, luminous reflectance factor is meant that the reflectivity with barium sulfate white plate is made as 100% relative value.Such reflection of light rate can followingly realize: with the few PTT of absorption to the light of above-mentioned scope is raw material, does not add the pigment that absorbs such light, has a large amount of trickle bubbles.
Sheet material preferred hue of the present invention is good.Do not using pigment or dyestuff to carry out under the painted state, tone is preferably represented the index L of brightness
*Be more than 80, more preferably more than 85, be preferably more than 90 especially.To L
*The upper limit be not particularly limited, be generally below 100.And, preferably represent the index b of yellow chromaticity
*Be-5～10, more preferably-3～8, more preferably-2～5.
In addition, the value that obtains divided by density of the preferred modulus in tension of sheet material of the present invention is 50MPacm
3/ g～1500MPacm
3/ g.In addition, modulus in tension herein uses the mean value of MD direction and TD direction.By making sheet material, can make it have excellent flexibility and make the property handled become easy with such value.The value that modulus in tension obtains divided by density is 100MPacm more preferably
3/ g～1200MPacm
3/ g, more preferably 200MPacm
3/ g～1100MPacm
3/ g is preferably 300MPacm especially
3/ g～1000MPacm
3/ g.
Then, the manufacture method to foamed polyester sheet of the present invention describes.
Foamed polyester sheet of the present invention can obtain by " special melt extrude foaming ", in described " special melt extrude foaming ", at 50 weight %～100 weight % is to inject in the melts of Poly(Trimethylene Terephthalate) (PTT) that the melt temperature at this melts is the specific material of gasiform under the normal pressure of specified quantitative, behind the mixed dissolution, extrude from die orifice under given conditions, when carrying out moulding, make the material foaming of described injection, promptly carry out cooling curing then.
Before the concrete manufacture method of explanation, at first above-mentioned " special melt extrude foaming " described.
Normal pressure can be deposited so that interior concentration is molten with saturation concentration in the melts of resin for the gasiform material down.The pressure of system is low more, and saturation concentration is low more.Therefore, utilize that high pressure makes that its this material of high density dissolved reduces at pressure, saturation concentration is lower than under its molten situation of depositing concentration and resin isolation, forms bubble.At this moment, after the hypersaturated state of short period of time, at first, produce the very small nuclei of bubbles as bubble, nuclei of bubbles is grown up then, produces the bubble of supersaturation concentration part.
In " special melt extrude foaming ", produce in a large number as the nuclei of bubbles on the basis of bubble and this nuclei of bubbles is grown up trickle bubbles are not important for producing in a large number.
In order to produce a large amount of nuclei of bubbles, need make supersaturation concentration is more than the certain value, so need be in the dissolving of the high pressure conditions more than the predetermined pressure, reach more than the predetermined concentration so that will become the material of gas, and do not form relief pressure in short period of time of bubble as yet at the molten material of depositing, saturation concentration is sharply descended.
For nuclei of bubbles is grown up, importantly exceedingly do not improve the concentration of the material that will become gas.This is because bubble can sharply be grown up when supersaturation concentration was too high.In addition, also need pressure to reduce to non-pressurized melts cooling curing and suppress the growth of bubble as far as possible promptly.
In addition, according to the inventor's research,, easily bubble is reduced to the known degree when in the past utilizing PET, PBT that is not less than by using the melts as principal constituent with PTT.Its reason it be unclear that, and it is believed that it is because the spination molecular structure of PTT, the polar group concentration of appropriateness and lower melt temperature.
In addition, other purpose of the present invention is to make bubble reach the S/T of pre-determined range, promptly forms non-flat bubble, for this reason, does not importantly stretch when making sheet material or compresses.Usually be karyogenesis bubble by the solidified sheet material is stretched with the impurity that contains as the trickle foam piece of the PET of light-reflecting sheet, so it can only obtain flat bubble.In " special melt extrude foaming " of the present invention, such stretching process is dispensable, so can access non-flat bubble.But, should be noted that equally among the present invention and in the process of collecting, do not wanting stretched sheet by extruding the generation bubble.
Specify manufacture method of the present invention below.
The PTT composition can obtain by known method.For example, the PTT composition is a raw material with dimethyl terephthalate (DMT) and propylene glycol and other copolymer compositions in case of necessity, with four titanium butoxide is catalyzer, pass through usual method, after normal pressure, 180 ℃～260 ℃ temperature are carried out transesterification reaction, under reduced pressure, 220 ℃～270 ℃ carry out polycondensation, can obtain the PTT composition thus.
The method that the additive of necessity can be by adding when the polymerization when making foamed polyester sheet, polymerization be after the method for method that melting mixing etc. add or these combination waits adds, and can suitably select described additive in conjunction with the kind of additive, amount, desired performance etc.Add through melting mixing under the situation of various additives, the PTT composition that polymerization obtains is through dropping into them in single screw extrusion machine or the twin screw extruder etc. with various additives in molten state behind the cooling curing or directly.
Above-mentionedly specially melt extrude in the foaming, for the melts that forms by PTT, use forcing machine, the PTT composition is supplied to supply unit, by the rotation of screw rod, make the said composition fusion, and send from forcing machine, the melts sent by the stream through heating, is extruded from the die orifice of slit-shaped etc.
As forcing machine, can use single screw rod or twin screw extruder, placed in-line series connection forcing machine of these forcing machines etc. more than 2.The screw rod of forcing machine preferably uses optimal screw rod according to the character of the material gas of the character of applied PTT composition, injection.Forcing machine preferably sets in not residual not melts and pyrolysated temperature that can composite inhibiting, and preferably set in the fusing point that is approximately the PTT composition+0 ℃～30 ℃, more preferably be set in fusing point+0 ℃ of PTT composition～20 ℃, further preferably set in fusing point+0 of PTT composition ℃～15 ℃.
Preferably strainer is being set removing impurity etc. as required between forcing machine and die orifice, or toothed gear pump etc. is being set, static mixer perhaps is being set, perhaps heat exchange unit is being set so that homo(io)thermism to improve the dispersiveness of injected material to improve weight feed.Under such situation, preferred suitably selective pressure and temperature be not so that near the material that injects this machine class becomes big bubble.Be provided with under the situation of these machines, also preferably set, and preferably set in the fusing point that is approximately the PTT composition+0 ℃～30 ℃ in not residual not melts and pyrolysated temperature that can composite inhibiting.
Specially melt extrude in the foaming, the normal pressure that is infused in melt temperature to melts is the gasiform material down.Consider that from the difficulty aspect of handling the preferred material that injects also is a gaseous state at normal temperature, normal pressure.As concrete example, can enumerate inert compound whipping agents such as nitrogen, carbonic acid gas, helium, argon, water; Aliphatic hydrocarbon whipping agents such as ethane, propane, butane, ethene, propylene, sherwood oil, pentane class, hexane class, iieptanes, toluene, trichloromethane, tetrachloromethane, trichlorofluoromethane, methyl alcohol, 2-propyl alcohol, isopropyl ether, butanone; Methyl chloride, ethylene dichloride, trichloromethane, fluoromethane, methylene fluoride, Halothane, chlorotrifluoromethane, Refrigerant 12, chlorofluoroethane, dichloro tetrafluoro ethane etc.
As the concrete example of fluorine carbon, can enumerate freonll-11 (R-11, R-12), substitute CFC series freonll-11 (Fleon) halogenated hydrocarbons whipping agents such as freonll-11 (R-134a), CFC-11, CFC-12, CFC-113, CFC-114 etc.Among these, the aspect consideration that never promotes the crystallization of sheet material and reduce bubble size, preferred nitrogen, helium, argon, water, special preferred nitrogen.
As the amount of the injection of such material,, need this amount is set at 0.01 weight %～3 weight % from making the bubble granular and making the viewpoint in apparent good order and condition of sheet material.Injection rate is 0.02 weight %～1 weight % more preferably, more preferably 0.05 weight %～0.5 weight %.
As the method for injecting, if at forcing machine between the die orifice, can inject period arbitrarily, but preferably utilize forcing machine to inject, because can equably material be injected melts like this.
Then, melts is extruded from die orifice, is shaped to flaky shape, the while relief pressure, and the material of injection becomes bubble.As die orifice, can suitably select according to the purpose shape of sheet material, but in order to obtain the sheet material of homogeneous thickness, the preferred linearity slit that is known as T mould, I mould, the circle-shaped slit that is known as round mould of using.The structure of preferred suitably design die orifice is not so that foam in the die orifice., the pressure of the melts of die orifice inlet need be set at more than the 5MPa for this reason, be preferably set to more than the 10MPa, 12MPa more preferably is more preferably more than the 15MPa.The upper limit is not particularly limited, and the structure of slave unit is considered, is preferably set to the following extrusion pressure of 100MPa, more preferably is set at below the 50MPa.
Die temperature when extruding is not preferably set than the lowland in the solidified scope does not take place melts, specifically, preferred settings in fusing point+0 of composition ℃～30 ℃, more preferably be set in fusing point+0 ℃～20 ℃, further preferably set in fusing point+0 ℃～15 ℃, preferably in the scope that melts evenly can be extruded, set than the lowland as far as possible.
Specially melt extrude in the foaming, the melts that is shaped to sheet and foaming curings that then is cooled among the present invention, need promptly be cooled off it is solidified, with the maximization of inhibition bubble.Consequently can reduce the bubble footpath of foam piece of the present invention.At this, be meant that promptly cooling the time will make its thermal property with above-mentioned sheet material, specifically, preferably from be expressed into by die orifice with sheet cools to the time below the crystallized temperature be in 60 seconds, in more preferably 40 seconds, be preferably especially in 20 seconds.Obtain under the situation of amorphousness sheet, importantly will especially promptly make its cooling curing.
As the method that realizes such cooling curing, can enumerate method that melts is contacted with solids such as cooling roller below the crystallized temperature that is controlled at the PTT composition or cooling zones, make method that liquid such as sheet material and water contact and the method that makes up these methods etc.Among these, most preferably the melts cast (configuration) that will be extruded by the slit-shaped die orifice is put into the method that water promptly carries out cooling curing then to roller or be with.
Solid such as cooling roller, band is thermal conduction good metal system solid preferably.More preferably 0 ℃～50 ℃ of the solid that is contacted, the temperature of liquid, are preferably 0 ℃～20 ℃ especially by more preferably 0 ℃～30 ℃.From be expressed into by die orifice make its time that contacts with solid, liquid be preferably 0.05 second～10 seconds, more preferably 0.1 second～5 seconds, be preferably 0.2 second especially～2 seconds.
In addition, among the present invention, should be noted that until rolling by the process of extruding the sheet material that has produced bubble in stretched sheet not.Therefore, preferably will collect speed setting is below 10 times of linear velocity that come from the melts of die head, more preferably below 8 times, more preferably below 5 times.On the other hand, lower limit is to guarantee the smooth velocity ratio of sheet material, specifically, is preferably more than 0.9 times, more preferably more than 0.95 times, more preferably more than 1.0 times.By being set at such velocity ratio, can easily S/T be controlled at pre-determined range.
Foamed polyester sheet of the present invention can be made by " special solid foamed method ", wherein, after in the amorphousness sheet that the resin combination that by 50 weight %～100 weight % is Poly(Trimethylene Terephthalate) forms, being the gasiform material under the normal temperature and pressure of injection specified quantitative, promptly this this sheet material is heated to specific temperature, makes the material foaming of above-mentioned injection.But in this case, resulting only is the sheet material of crystallization.
Before describing concrete manufacture method, at first above-mentioned " special solid foamed method " described.
Normal pressure can the concentration with corresponding gaseous tension be deposited so that interior concentration is molten in the amorphousness sheet for the gasiform material down.System pressure is low more, and the then molten concentration of depositing is low more.In " special melt foaming method ", saturation concentration is lower than under the molten situation of depositing concentration, and this material forms bubble after resin isolation, but for solid, it slowly discharges on the surface, does not form bubble.But identical with the situation of melts when sheet material being heated under the situation of the temperature more than the glass transition point, this material will form bubble.
In " special solid foamed method ", produce in a large number as the nuclei of bubbles on the basis of bubble and this nuclei of bubbles is grown up trickle bubbles are not important for producing in a large number.
In order to produce a large amount of nuclei of bubbles, need to inject and under the high pressure conditions more than the predetermined pressure, to form the material of bubble in a large number, and the temperature that needs promptly sheet material is heated to more than the glass transition point is overflowed on the surface to avoid injected material so that become the material of gas and reach more than the predetermined concentration.
For nuclei of bubbles is grown up, the concentration that does not exceedingly improve the material that will become gas also is important.This is because bubble can sharply be grown up during excessive concentration.
In addition, compare with PET, the crystallization speed of PTT is fast, so, importantly to improve the temperature of sheet material fast.Need to prove,, can not obtain foam piece with identical method because the crystallization speed of PBT is exceedingly fast and can not obtains the amorphousness sheet.
In addition, other purpose of the present invention is to make bubble reach the S/T of pre-determined range, promptly forms non-flat bubble, for this reason, does not importantly stretch when making sheet material or compresses.In " special solid foamed method " of the present invention, stretching or compression section are dispensable, so can access non-flat bubble.But, should be noted that equally among the present invention and after sheet material is added the thermogenesis bubble, do not want stretched sheet.
Below " special solid foamed method " of the present invention specifically described.
Be the concrete example of gasiform material down as the normal temperature and pressure that is injected in the special solid foamed method in the sheet material, can enumerate inert compound whipping agents such as nitrogen, helium, argon; Ethane, propane, butane, ethene, propylene, sherwood oil, pentane class, hexane class, iieptanes, toluene, trichloromethane, tetrachloromethane, trichlorofluoromethane, methyl chloride, ethylene dichloride, fluoromethane, methylene fluoride, Halothane, chlorotrifluoromethane, Refrigerant 12, chlorofluoroethane, dichloro tetrafluoro ethane etc.Among these, consider preferred nitrogen, helium, argon, special preferred nitrogen from the aspect that reduces bubble size.
As the amount of the injection of such material,, need to inject 0.01 weight %～3 weight % from making the viewpoint of bubble granular.Injection rate is 0.02 weight %～1 weight % more preferably, more preferably 0.05 weight %～0.5 weight %.
As method for implanting, can by the amorphousness sheet is put into pressure be more than the 0.5MPa above-mentioned gas atmosphere 10 minutes with on realize.Pressure is preferably more than the 10MPa, more preferably more than the 15MPa.In addition, the time was preferably more than 30 minutes, more preferably more than 60 minutes, was preferably especially more than 120 minutes.For crystallization not taking place when the injecting gas, preferably the temperature with sheet material is controlled at (preferred below 20 ℃, more preferably below 10 ℃) below 40 ℃.
The sheet material that has injected such gas promptly is heated to 60 ℃～200 ℃, makes the material foaming of injection.At this, promptly be meant the meaning of gas in the scope that is not less than above-mentioned amount of injection.More preferably 100 ℃～200 ℃ of the temperature of heating, more preferably 120 ℃～200 ℃.At this moment, in order to make its foaming, importantly rapid heating makes its foaming before carrying out crystallization.Such heating can be by being immersed in it in the inert liq of heating or its contact being realized through the roller of heating.
Among the foamed polyester sheet of the present invention, the amorphousness sheet can be made expanded moldings by moulding.
Expanded moldings preferably makes its crystallization when moulding.So can improve thermotolerance.As the degree of crystallization, when preferably using power compensation differential scanning calorimeter (DSC) that foamed polyester sheet is carried out the heat analysis, between 0 ℃～150 ℃, do not observe the exothermic peak that produces by crystallization.
In addition, the apparent density of preferred polyester foam piece is 0.05g/cm
3～1.25g/cm
3, 0.1g/cm more preferably
3～1g/cm
3, 0.15g/cm more preferably
3～0.8g/cm
3, be preferably 0.2g/cm especially
3～0.7g/cm
3
The shape of formed body can suitably be selected according to purposes.It is tabular etc. for example can to enumerate case shape, cup-shaped, ripple.As the method that molds such formed body, can enumerate compression moulding, linear moulding, drape forming, the moulding of plunger pressing aid, vacuum forming, vacuum pressure moulding, air-pressure forming etc., among these, more preferably vacuum pressure moulding.
When carrying out moulding, preferably at first sheet material is heated to 30 ℃～80 ℃ temperature by modes such as well heater irradiation or hot-plates.By operation like this, can easily make sheet material softening and do not make its crystallization, thereby improve formability, transfer printing.More preferably 40 ℃～70 ℃ of temperature, are preferably 50 ℃～60 ℃ especially by more preferably 45 ℃～65 ℃.
Then, sheet material is contacted with mould carry out moulding, the die temperature of this moment preferably sets at 60 ℃～180 ℃.Among the present invention, in order to ensure formability, importantly foamed polyester sheet is roughly noncrystalline state when excipient, in order to guarantee thermotolerance behind the excipient, importantly makes the formed body crystallization.Therefore, when preferably making the formed body crystallization, die temperature is controlled at a certain temperature range.In order to give this formed body enough thermotolerances, die temperature is preferably more than 65 ℃, in order to suppress to break from mold releasability or bubble after the moulding, preferably die temperature is arranged on below 180 ℃.Die temperature more preferably is set at 80 ℃～160 ℃, is preferably 100 ℃～150 ℃ especially.After carrying out moulding, improve the temperature of mould or heat from the outside so that sheet material reaches the temperature of above-mentioned scope also is one of preferable methods.
Among the present invention, hot briquetting can be carried out under the situation of stacked 2 above foamed polyester sheets.This moment preferred when moulding the sheet material of one side of increased pressure aspirating hole is set so that the air between sheet material is easy to spill.
The light reflecting board that foamed polyester sheet of the present invention is used etc. as lighting fixturess such as the lamp box of liquid crystal indicator, luminescent lamps is extremely to be fit to.
As the desired function of these light reflecting boards, first can enumerate have high reflectivity, high diffuse particularly.Because foamed polyester sheet of the present invention has a large amount of average bubble size in inside is that 0.01 μ m～trickle like this bubble of 50 μ m is so that apparent density is 0.05g/cm
3～1.25g/cm
3, simultaneously not have painted be that the absorption of light is few to sheet material, thereby realized high reflectivity, particularly high diffuse.
The second, the shape that can be processed into corresponding light source can be enumerated, and this shape can be kept.Can process easily preferably that (can process with less external force) and work range are wide promptly can be processed into different shape.
Light reflecting board of the present invention has the ideal flexibility.If only in order to show flexibility, then the thickness of attenuate sheet material get final product, but do like this rigidity is excessively disappeared, and the strength of maintenance shape dies down, and light reflecting board can deform because of the variation of environment or the external force of a little sometimes.After deforming, can not reflect light to desired direction, it can occur the light and shade inequality as under the situation of liquid crystal display plate on picture.50 weight % of light reflecting board of the present invention～100 weight % are made of the Poly(Trimethylene Terephthalate) with crystalline flexibility (being derived from the spination molecular structure), and as described above, it contains a large amount of trickle bubbles, so formed the honeycomb structure that the thin-walled by ultra-fine micropore forms, even thickness thinning not, it also is a softish.It is processibility and rigidity that the result can take into account flexibility.
In addition, 50 weight % of light reflecting board of the present invention～100 weight % are made of the Poly(Trimethylene Terephthalate) with crystalline elastic recovery (being derived from the spination molecular structure), and S/T is 0.05～10, containing a large amount of average bubble size is the non-flat trickle bubble of 0.01 μ m～50 μ m, be difficult to the disruptive honeycomb structure thereby formed, therefore, it has the snappiness recovery, is processed into shapes such as curved surface easily and can bend or occur fold.In addition, even some failures are arranged in the processing, can return to original shape and carry out the possibility of reworking also higher.
Such characteristic is to expect from the light reflecting board that is made of the common trickle foam piece of PTT sheet material, PET.
Light source comprises the light source of small-sized point-like thing that the such thread of luminescent lamp, incandescent light such large-scale point-like thing, LED are such and so on, comprise one or more situations about being used in combination of using, so it is extremely preferred can easily forming multiple shape as described above.When bending or generation fold, not only can not reflect light to desired direction, and the reflectivity step-down of the part of fold, as under the situation of liquid crystal display plate, the light and shade inequality of striated can appear.
The light reflecting board of the present invention preferably average light reflectivity under the wavelength of 400nm～700nm is more than 80%, and is more preferably more than 85%, preferred especially more than 90%.
Consider that from the property handled, the rigidity when being provided with, the opacifying property aspect of light thickness is preferably 100 μ m～2mm, more preferably 200 μ m～1.5mm are preferably 500 μ m～1.2mm especially.
Because the light source heat release, so the preferred light reflector has thermotolerance, therefore, light reflecting board is preferably crystalline.As crystalline index, when utilizing power compensation differential scanning calorimeter to carry out the heat analysis, whether observing the exothermic peak that is produced by crystallization between 0 ℃～150 ℃ is this index, preferred exothermic peak area is below the 5J/g, more preferably below the 3J/g, more preferably below the 1J/g, certainly, most preferably do not observe this exothermic peak fully.
The shape of light reflecting board is selected according to light source, can enumerate that tabular, ripple are tabular, case shape etc.In addition, cover light source around, can reflect light to a direction coniform, pyramid-shaped, bowl-shape also be preferred shape.
When being processed into such shape, punch process that can be by utilizing slit, severing, mould etc., bending process, pressurization processing, thermoforming etc. are processed, wherein, requiring under the stable on heating situation or requiring preferably to carry out thermoforming under the situation of self retentivity of shape.This is because when carrying out thermoforming, variant part is by heat setting, so the dimensional precision excellence.
Embodiment
Below, based on embodiment embodiments of the present invention are elaborated, but the invention is not restricted to these embodiment.Main measured value among the present invention is to measure by following method.
(1) Poly(Trimethylene Terephthalate) (PTT) containing ratio, BPE containing ratio:
Following the obtaining of PTT containing ratio (weight %): the 100mg sheet material is dissolved into HFIP:CDCl
3Among=the 1:1, the use film filter (MEMBRANE FILTER, 1 μ m, the PTFE) solution behind the insoluble composition of filtration, by
1H-NMR measures and obtains.The mensuration machine uses FT-NMRDPX-400 (manufacturing of Bruker society).In addition, the weight to after the insoluble composition measurement vacuum-drying that removes by filter is used to calculate the PTT containing ratio.
(2) intrinsic viscosity [η]:
Following the obtaining of intrinsic viscosity [η]: use Ostwald viscosimeter,, calculate according to following formula 1 with being extrapolated to concentration than η sp/C and equaling 0 of specific viscosity η sp in 35 ℃, ortho chloro phenol and concentration C (g/100 milliliter).
[formula 1]
[η]＝lim(ηsp/C)
C→0
(3) C-terminal base concentration:
With 1g PTT composition dissolves in the 25ml phenylcarbinol, thereafter, after adding the 25ml chloroform, carry out titration with the potassium hydroxide benzyl alcohol solution of 1/50N, utilize following formula 2 by titration value VA (ml) and the blank value V0 when not having the PTT composition obtain C-terminal base concentration.
[formula 2]
C-terminal base concentration (eq/ ton)=(VA-V0) * 20
(4) apparent density:
50 ℃ of dryings, the weight when usefulness reaches the constant value is obtained the apparent density of foamed polyester sheet divided by volume with foamed polyester sheet.In addition, volume is obtained by sheet material is immersed in the water.
(5) exothermic peak that forms by crystallization:
Use the Perkin Elmer system Pyris 1 of society (having cooling unit) as power compensation differential scanning calorimeter (DSC), with sheet material or formed body 0 ℃ keep 3 minutes after, setting heat-up rate with 10 ℃/min, be warmed up to 260 ℃ from 0 ℃, carry out heat analysis, observe the exothermic peak and the exothermic peak area that have the crystallization of having no way of to form.
(6) appearance time of isothermal crystalization:
The appearance time of isothermal crystalization is following tries to achieve: with sheet material after 280 ℃ of fusions, with this melts chilling in liquid nitrogen, make its curing obtain composition, use the Perkin Elmer system Pyris1 of society (band cooling unit) as power compensation differential scanning calorimeter (DSC), with composition 0 ℃ keep 3 minutes after, setting heat-up rate with 500 ℃/min, be heated to X ℃ from 0 ℃, remain on X ℃, the heat absorption that mensuration is produced by crystallization measures the time at peak, obtains the appearance time of isothermal crystalization.
(7) the ratio S/T of the mean sizes (T) on mean sizes (S) on the average diameter of bubble and the face direction and the thickness direction:
Use scanning electron microscope (being designated hereinafter simply as " SEM ") to observe the sheet material cross section of MD direction (sheet length direction) and this two direction of TD direction (sheet width direction), utilize image analysis software to obtain the ratio S/T of the mean sizes (T) on the average diameter of bubble and mean sizes (S) on the face direction and the thickness direction by viewed cross-sectional image.Image analysis software use that Planetron company makes image-Pro Plus ver.4.0.The cross section of bubble is projected to the major axis of equivalent ellipsoidal of sub-elliptical and the mean value of the length on the minor axis and on all directions of MD direction and TD direction, average the average diameter of obtaining bubble.In addition, the height of the external tetragon (bubble integral body being surrounded and had the minimum rectangle on the limit parallel with sheet face direction fully) of bubble and the mean value of width are averaged on all directions of MD direction and TD direction, obtain S and T.
(8) percent thermal shrinkage:
Based on JIS K7133, film is implemented thermal treatments in 30 minutes but do not applied tension force at 150 ℃, measure the dimensional change of this moment, obtain percent thermal shrinkage.
(9) average light reflectivity:
The UV-2200 that uses Shimadzu Seisakusho Ltd. to make moves into 8 ° of firing angles, and it is the total reflectivity of 400nm～700nm that wavelength is measured on every 10nm ground, calculates its simple mean value, obtains the average light reflectivity.At this moment, be 100% with the barium sulfate powder, adjust determinator.
(10) tone (L value, b
*Value):
Use the color computer of suga trier (strain) to measure.
(11) flexibility-1:
Sheet material is folded into 180 ℃, observes the state of this moment.With take place being evaluated as of fracture " * ", with the surface occur being evaluated as of crackle " △ ", will be both not fracture be evaluated as " zero " of crackle will not appear yet.
(12) flexibility-2:
By tension test based on ASTM D882, obtain modulus in tension, divided by density, the quotient that usefulness obtains is as the index of flexibility, processing difficulty or ease with this Young's modulus.
(13) processibility:
Curvature is carried out in observation
Bending machining the time machining state.To not form desired curvature and bending or surface have taken place being evaluated as " * ", will not bending be evaluated as " zero " who fold also do not occur of fold occurred.
[embodiment 1]
In 98.8 weight part intrinsic viscosities [η] is 1.3dl/g, the C-terminal base concentration Irganox1098 that to be 10eq/ ton, the BPE containing ratio Irgafosl68 that to be the PTFE that adds 1 weight part median size, 5 μ m among the PTT of 0.5 weight %, 0.1 weight part make as Ciba Co., Ltd. of thermo-stabilizer, 0.1 weight part make as Ciba Co., Ltd. of the trapping agent of lower molecular weight volatile impunty, obtain fusing point and be 225 ℃ PTT composition, said composition is supplied to be set in 235 ℃
Single screw extrusion machine in, after the dissolving, make it by being heated to the stream with the forcing machine uniform temp, from as the wide 100mm of die orifice, the T mould of 0.5mm is extruded with 5m/ minute linear speed at interval, is shaped to sheet.
At this moment, the nitrogen of 0.1 weight % of composition is injected in the middle of this forcing machine, mix, dissolve with melts.In addition, the pressure of the melts of T mould inlet is 15MPa.After will being poured on the metal system of its 50mm rotation roller by the melts that the T mould is extruded, import in the water coolant, make its cooling curing, obtain foam piece.At this moment, controlling so that rotate roller and water coolant reaches 10 ℃, is 0.6 second from extrusion melt to the time that makes its contact rotation roller, and the time of crystallized temperature below 68 ℃ that is cooled to said composition is in 20 seconds.
The thickness of the foamed polyester sheet that obtains is 1mm, the wide 100mm of being, even bend 180 °, sheet material does not rupture yet.In addition, intrinsic viscosity [η] is 1.15dl/g, and C-terminal base concentration is the 15eq/ ton, and the BPE containing ratio is 0.5 weight %, and density is 0.6g/cm
3, average bubble directly is 20 μ m, is 1.3 (S/T), has trickle and non-flat bubble, and the luminous reflectance factor excellence is 85%, and percent thermal shrinkage is all little of 0.2% in MD/TD two directions.In addition, the crystallization heat be the appearance time of 15J/g, isothermal crystalization at 100 ℃～150 ℃ four corner all between 1 second～60 seconds, have good hot formability.
The foamed polyester sheet that obtains is carried out moulding with the vacuum pressure method of forming, obtain the cup-shaped moulding product of internal diameter 200mm, degree of depth 50mm.When carrying out moulding, at first with sheet material with after the well heater irradiated heat to 55 ℃, make the aluminium-making mould of its Contact Heating to 120 ℃ with the condition of vacuum tightness 720mmH, moulding pressure 0.2MPa, carry out excipient, kept 120 seconds at this state then, make its crystallization, carry out moulding thus.The apparent density of resulting expanded moldings is 0.6g/cm
3, be the light-weight formed body.The results are shown in following table 1 and table 2.
In addition, " ME " in the table represents the special foaming that melt extrudes, and " S " represents special solid foamed method, " COOH " expression C-terminal base concentration.In addition, the value of record is represented the value of the value/TD direction of MD direction respectively in " percent thermal shrinkage " one.
[embodiment 2～4]
Except changing the condition shown in following table 1 and the table 2, similarly obtain foamed polyester sheet with the foregoing description 1.The results are shown in following table 1 and table 2.In any case, all within the scope of the invention, be to have excellent lightweight, the foamed polyester sheet of flexibility.
Among the embodiment 2,, add the little PTFE particle of a large amount of particle diameters, obtained having more tiny bubble and the high good foamed polyester sheet of luminous reflectance factor by improving extrusion pressure.
In addition, increased the gas injection rate among the embodiment 3, changed the thickness of sheet material among the embodiment 4, obtained and the foregoing description 1 same excellent foamed polyester sheet.
[embodiment 5]
Using intrinsic viscosity [η] is the PTT of 0.5 weight % as 0.9dl/g, C-terminal base concentration as 20eq/ ton, BPE containing ratio, and is 0.7mm with thickness setting, in addition, obtains foamed polyester sheet in the same manner with the foregoing description 1.At this moment, adjust the interval of T mould, so that the pressure of the melts of T mould inlet reaches more than the 20MPa.The results are shown in following table 1 and table 2.The resulting polyester foam piece has excellent lightweight, flexibility, luminous reflectance factor within the scope of the invention.
[embodiment 6]
The composition of fluorine mica (CO-OP CHEMICAL (strain) society makes SOMASIF MAE) the replacement PTFE of 3 weight part median sizes, 6 μ m has been added in use, in addition, obtains foamed polyester sheet in the same manner with the foregoing description 1.At this moment, adjust the interval of T mould, so that the pressure of the melts of T mould inlet reaches more than the 15MPa.The results are shown in following table 1 and table 2.The resulting polyester foam piece has excellent lightweight, flexibility, luminous reflectance factor within the scope of the invention.
[embodiment 7,8]
In 94.8 weight part intrinsic viscosities [η] is 1.15dl/g, C-terminal base concentration is the 15eq/ ton, the BPE containing ratio is the PTFE that adds 5 weight part median sizes, 2 μ m among the PTT of 0.5 weight %, 0.1 weight part is as the Irgafosl68 of Ciba Co., Ltd. manufacturing of thermo-stabilizer, 0.1 weight part is as the Irganox1098 of Ciba Co., Ltd. manufacturing of the trapping agent of lower molecular weight volatile impunty, obtain fusing point and be 225 ℃ PTT composition, utilize said composition to obtain the not sheet material of foaming of thickness 0.4mm, among the embodiment 7, under the state that temperature is remained on below 20 ℃, sheet material being put into the nitrogen atmosphere of 20MPa placed 120 minutes, inject 0.2 weight % nitrogen, among the embodiment 8, under the state that temperature is remained on below 20 ℃, sheet material is put into the 15MPa argon atmospher to be placed 100 minutes, inject 0.2 weight % argon, afterwards, 3 minutes after taking-up with the interior oil bath that puts it into 180 ℃, heat fast thus, make its foaming, obtain foamed polyester sheet.The results are shown in following table 1 and table 2.The resulting polyester foam piece has excellent lightweight, flexibility, luminous reflectance factor all within the scope of the invention.
[comparative example 1,2]
In the comparative example 1, use 95 weight % intrinsic viscosities [η] to replace 95 weight part PTT as the PET of 30eq/ ton and the talcum of 5 weight part median sizes, 5 μ m as 0.85dl/g, C-terminal base concentration, in the comparative example 2, use 95 weight part intrinsic viscosities [η] to replace 95 weight part PTT as the PBT of 50eq/ ton and the talcum of 5 weight part median sizes, 5 μ m as 1.0dl/g, C-terminal base concentration, in addition, obtain foamed polyester sheet in the same manner with the foregoing description 1.In addition, in the comparative example 2, the temperature of forcing machine, T mould etc. is set at than high 30 ℃ in the foregoing description 1.The results are shown in following table 1 and table 2.
The big luminous reflectance factor in bubble footpath of the sheet material of comparative example 1 is low.In addition, not only the big luminous reflectance factor in bubble footpath is low for the sheet material of comparative example 2, and is fractured into two halves when bending 180 °, and flexibility is poor.
[comparative example 3]
Adjust the interval of T mould, making extrusion pressure is 2MPa, in addition, obtains foam piece in the same manner with the foregoing description 1.The results are shown in following table 1 and table 2.The bubble footpath of resulting sheet material is big, and luminous reflectance factor is low.
[comparative example 4]
Use the carbonic acid gas of 4MPa to replace nitrogen, be pushed down into the carbonic acid gas of 0.8 weight %, in addition, obtain foam piece in the same manner with the foregoing description 7 at state below 20 ℃ that temperature is remained on.Even but the oil bath of putting into 180 ℃ is not foamed yet.The results are shown in following table 1 and table 2.
[comparative example 5]
Will by the nothing orientation amorphousness sheet of the thickness 250 μ m that constitute with identical PET that comparative example 1 uses and the polyethylene non-woven fabrics is overlapping roll, this spool is kept taking out after 48 hours in atmospheric acetone steam, in pressurized vessel, in the carbonic acid gas 2 hours of 20 ℃ of infiltration 5MPa.After this, put into the process furnace that is set in 200 ℃, make its foaming, obtain foam piece.Resulting foam piece is thick 1mm, apparent density 0.4g/cm
3, average bubble footpath 3 μ m, S/T be 1.2, the foam piece of luminous reflectance factor 90%.Similarly this sheet material is estimated flexibility and processibility with film of the present invention, the result is as follows: be difficult for carrying out bending machining, and be bent into
Curvature the time produced a large amount of folds.
[embodiment 9]
Use the sheet material of embodiment 1,2 and comparative example 1,3, make 26 inches LCD panel back light unit.Use 16 cold-cathode tubes as light source, the foam piece of embodiment 1,2 and comparative example 3 is used through the light reflecting board of vacuum forming as bellows-shaped shown in Figure 1.In addition, among Fig. 1, cold-cathode tube is configured in the central authorities, 5mm of recess below the foam piece.On the other hand, the sheet material processing difficulties of comparative example 2, so as flat light reflecting board, cold-cathode tube with above-mentioned same arranged spaced on sheet material 5mm.Pull on the diffusing panel (Asahi Chemical Industry's chemistry (strain) society makes DELAGLAS DS) of thickness 1.5mm on the above-mentioned light source, make back light unit.
Under the situation of the light reflecting board that use is made of the sheet material of embodiment 1,2, have high briliancy, and do not find the briliancy spot that cold-cathode tube produces.
On the other hand, use under the situation of the light reflecting board that the sheet material by comparative example 1,2 constitutes, compare with embodiment 1,2, not only briliancy is low, and is visually observed the briliancy spot of the striated that cold-cathode tube produces.Particularly under the situation of comparative example 2, the briliancy spot is obvious.
In addition, when the back light unit that has used the light reflecting board of comparative example 1 was lighted 10 hours, local temperature had been elevated to 80 ℃, but light reflecting board is not found distortion.
[table 1]
[table 2]
The specific embodiment of top reference has been described in detail the present invention, still, it will be evident to one skilled in the art that to apply various changes or modification under the condition that does not break away from the spirit and scope of the present invention.
The Japanese patent application that the application proposed based on January 19th, 2006 (special hope 2006-011194) is introduced this specification sheets with the form of reference with its content.
Utilizability on the industry
Foamed polyester sheet of the present invention has excellent flexibility, thermal insulation, lightweight, light reflection The property. Therefore, as utilization of the present invention example, it is anti-at food containers, packing timber, building materials, light It is useful penetrating in the various uses such as plate. In addition, make in the situation of light reflecting board, because its tool Excellent light reflective, diffuse are arranged, and have easily be processed into to corrugationless suitable So the punching press of the shape of light source or bendability are its lamp box as liquid crystal indicator, glimmering The light reflecting board of the ligthing paraphernalias such as light modulation etc. is useful.
Claims (15)
1. foamed polyester sheet, it contains 50 weight %～100 weight % Poly(Trimethylene Terephthalate), and apparent density is 0.05g/cm
3～1.25g/cm
3, wherein, described foamed polyester sheet comprises the bubble that average bubble size is 0.01 μ m～50 μ m, and the ratio (S/T) of the mean sizes (T) of the mean sizes (S) of the face direction of described bubble and thickness direction is 0.05～10.
2. foamed polyester sheet as claimed in claim 1, wherein, the thickness of described foamed polyester sheet is 1 μ m～10mm.
3. foamed polyester sheet as claimed in claim 1 or 2, wherein, the average bubble size of described bubble is 0.01 μ m～30 μ m, and the mean sizes (S) of the face direction of described bubble is 0.7～3 with the ratio (S/T) of the mean sizes (T) of thickness direction.
4. as each the described foamed polyester sheet in the claim 1～3, wherein, described foamed polyester sheet is-2%～5% at 150 ℃ percent thermal shrinkage.
5. as each the described foamed polyester sheet in the claim 1～4, wherein, described foamed polyester sheet is more than 80% to the average light reflectivity of the light of wavelength with 400nm～700nm.
6. as each the described foamed polyester sheet in the claim 1～5, it is to utilize to melt extrude manufactured.
7. as each the described foamed polyester sheet in the claim 1～6, wherein, when utilizing power compensation differential scanning calorimeter to carry out the heat analysis, between 0 ℃～150 ℃, observed the exothermic peak that produces by crystallization.
8. as each the described foamed polyester sheet in the claim 1～7, wherein, the appearance time of the isothermal crystalization of described foamed polyester sheet is that 1～60 second temperature is present in 100 ℃～150 ℃ scope.
9. light reflecting board, it is made of each the described described foamed polyester sheet in the claim 1～8.
10. light reflecting board as claimed in claim 9, wherein, when utilizing power compensation differential scanning calorimeter to carry out the heat analysis, the observed exothermic peak that is produced by crystallization is 0J/g～3J/g between 0 ℃～150 ℃.
11. the manufacture method of a foamed polyester sheet, wherein, the melt temperature at this melts is the gasiform material under injection 0.01 weight %～3 weight % normal pressures in the melts that contains 50 weight %～100 weight % Poly(Trimethylene Terephthalate), after mixing, dissolving obtain melts, the described melts that obtains is extruded the material foaming that makes described injection when carrying out moulding, cooling curing then with the extrusion pressure of 5MPa～100MPa from die orifice.
12. the manufacture method of foamed polyester sheet as claimed in claim 11, wherein, the material of described injection is a gaseous state under normal temperature, normal pressure.
13., wherein, after described melts extruded from the die orifice of slit-shaped, this melts be cast in metal roller or be with as the manufacture method of claim 11 or 12 described foamed polyester sheets, then this melts is put into water, carry out cooling curing.
14. the manufacture method of a foamed polyester sheet, wherein, behind the amorphousness sheet that 0.01 weight %～3 weight % normal temperature and pressures are made of the resin combination of the Poly(Trimethylene Terephthalate) that contains 50 weight %～100 weight % for the injection of gasiform material down, this amorphousness sheet is heated to 60 ℃～200 ℃, makes the material foaming of described injection.
15. as the manufacture method of each the described foamed polyester sheet in the claim 11～14, wherein, the material of described injection is a nitrogen.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP011194/2006 | 2006-01-19 | ||
| JP2006011194 | 2006-01-19 |
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|---|---|
| CN101374893A true CN101374893A (en) | 2009-02-25 |
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| CNA2007800032301A Pending CN101374893A (en) | 2006-01-19 | 2007-01-18 | Polyester foam sheet and method for producing same |
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| JP (1) | JPWO2007083720A1 (en) |
| KR (1) | KR20080086903A (en) |
| CN (1) | CN101374893A (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111629895A (en) * | 2018-12-28 | 2020-09-04 | 株式会社Huvis | Foamed sheet including surface layer, method of preparing the same, and food container including the same |
| CN115003738A (en) * | 2020-01-27 | 2022-09-02 | 株式会社理光 | Foam sheet, product, and method for producing foam sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009086430A (en) * | 2007-10-01 | 2009-04-23 | Furukawa Electric Co Ltd:The | Light reflecting molded product |
| JP4873187B2 (en) * | 2008-06-09 | 2012-02-08 | 国立大学法人福井大学 | Method for foaming fiber material |
| JP2011215359A (en) * | 2010-03-31 | 2011-10-27 | Sekisui Plastics Co Ltd | Method of bending light reflection sheet, and light reflection plate |
| JP5667804B2 (en) * | 2010-07-13 | 2015-02-12 | 積水化成品工業株式会社 | Light reflector and manufacturing method thereof |
| CN103029391B (en) * | 2012-12-29 | 2015-02-25 | 四川东方绝缘材料股份有限公司 | Composite two-way stretch light reflex polyester film and fabrication method thereof |
| JP2014153496A (en) * | 2013-02-07 | 2014-08-25 | Fujifilm Corp | Film mirror and sunlight reflection plate using the same |
| JP6898109B2 (en) * | 2017-02-23 | 2021-07-07 | 積水化学工業株式会社 | Resin foam sheet and its manufacturing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2801483B2 (en) * | 1992-11-02 | 1998-09-21 | 積水化成品工業株式会社 | Method for producing thermoplastic polyester resin foam |
| JP3846024B2 (en) * | 1998-04-21 | 2006-11-15 | 東レ株式会社 | White film and method for producing white film |
| JP4522000B2 (en) * | 2001-02-01 | 2010-08-11 | 旭化成せんい株式会社 | Foam |
| JP2002300690A (en) * | 2001-03-30 | 2002-10-11 | Matsushita Electric Ind Co Ltd | Method of manufacturing diaphragm for speakers and diaphragm for speakers, using the same |
| JP2002309029A (en) * | 2001-04-10 | 2002-10-23 | Mitsui Chemicals Inc | Method for thermoplastic resin foam production |
| JP4369884B2 (en) * | 2005-03-09 | 2009-11-25 | 古河電気工業株式会社 | Thermoplastic resin foam |
-
2007
- 2007-01-18 JP JP2007554961A patent/JPWO2007083720A1/en active Pending
- 2007-01-18 CN CNA2007800032301A patent/CN101374893A/en active Pending
- 2007-01-18 KR KR1020087017729A patent/KR20080086903A/en not_active Application Discontinuation
- 2007-01-18 WO PCT/JP2007/050730 patent/WO2007083720A1/en active Application Filing
- 2007-01-19 TW TW096101998A patent/TW200730350A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111629895A (en) * | 2018-12-28 | 2020-09-04 | 株式会社Huvis | Foamed sheet including surface layer, method of preparing the same, and food container including the same |
| CN111629895B (en) * | 2018-12-28 | 2022-10-21 | 株式会社Huvis | Foamed sheet including surface layer, method of preparing the same, and food container including the same |
| CN115003738A (en) * | 2020-01-27 | 2022-09-02 | 株式会社理光 | Foam sheet, product, and method for producing foam sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007083720A1 (en) | 2007-07-26 |
| TW200730350A (en) | 2007-08-16 |
| KR20080086903A (en) | 2008-09-26 |
| JPWO2007083720A1 (en) | 2009-06-11 |
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