WO2004048089A1 - Articles of manufacture incorporating polyester/polycarbonate blends - Google Patents
Articles of manufacture incorporating polyester/polycarbonate blends Download PDFInfo
- Publication number
- WO2004048089A1 WO2004048089A1 PCT/US2003/037032 US0337032W WO2004048089A1 WO 2004048089 A1 WO2004048089 A1 WO 2004048089A1 US 0337032 W US0337032 W US 0337032W WO 2004048089 A1 WO2004048089 A1 WO 2004048089A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyester
- thermoplastic article
- bis
- hydroxyphenyl
- mole
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 77
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 74
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 69
- 239000000203 mixture Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title description 7
- 239000000463 material Substances 0.000 claims abstract description 69
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 65
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 65
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 60
- -1 alicyclic dicarboxylic acids Chemical class 0.000 claims description 59
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 34
- 239000004744 fabric Substances 0.000 claims description 22
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 21
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- 238000005299 abrasion Methods 0.000 claims description 15
- 239000006085 branching agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 229920001634 Copolyester Polymers 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- 150000002989 phenols Chemical class 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002009 diols Chemical group 0.000 claims description 7
- 229920002635 polyurethane Polymers 0.000 claims description 7
- 239000004814 polyurethane Substances 0.000 claims description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- 150000007513 acids Chemical class 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 5
- 239000000123 paper Substances 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical class C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000003086 colorant Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 3
- 239000002557 mineral fiber Substances 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical class OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 claims description 2
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims description 2
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical class OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 claims description 2
- BLDLRWQLBOJPEB-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfanylphenol Chemical class OC1=CC=CC=C1SC1=CC=CC=C1O BLDLRWQLBOJPEB-UHFFFAOYSA-N 0.000 claims description 2
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical class OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 claims description 2
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 claims description 2
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 claims description 2
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 claims description 2
- YNWRQXYZKFAPSH-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfinyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 YNWRQXYZKFAPSH-UHFFFAOYSA-N 0.000 claims description 2
- SUCTVKDVODFXFX-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfonyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(S(=O)(=O)C=2C=C(C)C(O)=C(C)C=2)=C1 SUCTVKDVODFXFX-UHFFFAOYSA-N 0.000 claims description 2
- AZZWZMUXHALBCQ-UHFFFAOYSA-N 4-[(4-hydroxy-3,5-dimethylphenyl)methyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(CC=2C=C(C)C(O)=C(C)C=2)=C1 AZZWZMUXHALBCQ-UHFFFAOYSA-N 0.000 claims description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 claims description 2
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 claims description 2
- UTHNVIIBUGSBMJ-UHFFFAOYSA-N 4-[3-(4-hydroxy-3,5-dimethylphenyl)cyclohexyl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C2CC(CCC2)C=2C=C(C)C(O)=C(C)C=2)=C1 UTHNVIIBUGSBMJ-UHFFFAOYSA-N 0.000 claims description 2
- NIRYBKWMEWFDPM-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-methylbutyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CCC1=CC=C(O)C=C1 NIRYBKWMEWFDPM-UHFFFAOYSA-N 0.000 claims description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- 239000004609 Impact Modifier Substances 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002216 antistatic agent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 125000005586 carbonic acid group Chemical group 0.000 claims description 2
- 150000004653 carbonic acids Chemical class 0.000 claims description 2
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical compound BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- QPJDMGCKMHUXFD-UHFFFAOYSA-N cyanogen chloride Chemical compound ClC#N QPJDMGCKMHUXFD-UHFFFAOYSA-N 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical group C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002667 nucleating agent Substances 0.000 claims description 2
- SJDACOMXKWHBOW-UHFFFAOYSA-N oxyphenisatine Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2NC1=O SJDACOMXKWHBOW-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 239000012744 reinforcing agent Substances 0.000 claims description 2
- 239000003340 retarding agent Substances 0.000 claims description 2
- 239000012748 slip agent Substances 0.000 claims description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical class [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical class OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- JPSMTGONABILTP-UHFFFAOYSA-N 4-(4-hydroxy-3,5-dimethylphenyl)sulfanyl-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(SC=2C=C(C)C(O)=C(C)C=2)=C1 JPSMTGONABILTP-UHFFFAOYSA-N 0.000 description 1
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 description 1
- GIXXQTYGFOHYPT-UHFFFAOYSA-N Bisphenol P Chemical compound C=1C=C(C(C)(C)C=2C=CC(O)=CC=2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 GIXXQTYGFOHYPT-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009734 composite fabrication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- CJOJIAKIRLKBOO-UHFFFAOYSA-N dimethyl 2-hydroxybenzene-1,4-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C(O)=C1 CJOJIAKIRLKBOO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920006334 epoxy coating Polymers 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1716—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- 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
-
- 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
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31786—Of polyester [e.g., alkyd, etc.]
Definitions
- This invention pertains to a novel thermoplastic article having decorative materials on the surface thereof. More specifically, this invention pertains to an article produced by applying heat and pressure to a laminate comprising: at least one decorative material, for example, a fabric, metallic wire, paper, or printed layer, and an upper or lower sheet material, to produce a thermoplastic article having the decorative materials on the surface thereof.
- the novel thermoplastic articles provided by the present invention may be used in the construction industry as glazing for windows, in partitions and as decorative panels.
- the sheet material may be textured during or after formation of the articles.
- Glass both transparent and translucent, has been used as glazing material for windows and partitions and, for certain uses, it is painted or stained to provide specific decorative effects. Glass is high in density and weight, is difficult to fabricate at the work site, is generally brittle, and can constitute a safety hazard.
- Glass substitutes such as polyvinyl chloride sheeting, acrylic, e.g., poly(methyl methacrylate), sheeting and polycarbonate sheeting have been used as substitutes for glass in certain glazing applications. Generally, these substitutes are made for clear (transparent), non-decorative applications.
- the sheet material provided by this invention may be used primarily for producing or obtaining decorative applications with varying degrees of transparency and various levels of enhanced security.
- United States Patent 5,413,870 describes a sturdy wall covering especially useful in a bathroom or shower area, the wall covering being comprised of a laminate that includes a clear or transparent acrylic cast in the first layer, a clear polyester thermoset resin in the second layer, and a thin fabric sheet as the third layer and a pigmented polyester thermoset coating over the fabric layer.
- the polyester thermosetting resins in this case are applied as a liquid and subsequently cured as a solid.
- There are several difficulties when using polyester thermosetting resins Removing air bubbles from the liquid thermosetting resins can be difficult. Thermosetting resins can undergo significant shrinkage during curing.
- crosslinked polyester resins are known to be brittle. This invention alleviates many of these difficulties. Advantages of this invention over the prior art include higher heat deflection temperature (HDT), increased stiffness and increased creep resistance with time.
- HDT heat deflection temperature
- the present invention provides a thermoplastic article, typically in the form of sheet material, having a decorative material on the surface thereof.
- the thermoplastic article is obtained by applying heat and pressure to a laminate comprising, (1) at least one decorative material, and (2) at least one lower sheet material or upper sheet material.
- an adhesive layer may be used between (1) and (2).
- the upper or lower sheet materials are produced from miscible polyester/polycarbonate blends.
- the polyester component as described below, preferably comprises a minimum level of 1 ,4 cyclohexanedimethanol as a comonomer in order to effect miscibility with polycarbonate.
- thermoplastic article having a decorative material on the surface thereof obtained by applying heat and pressure to a laminate comprising, (1) at least one decorative material comprising metallic wire, rods or bars; natural fibers; glass fibers, mineral fibers, fabric, paper, and/or printed layer; and (2) at least one lower sheet or upper sheet material; wherein the upper or lower sheet materials are formed from a miscible polyester/aromatic polycarbonate blend comprising:
- a preferred blend composition is 50-90 weight% by weight of the polyester and 50-10 weight% by weight of the aromatic polycarbonate.
- An even more preferred composition is 60-80 weight% polyester and 40-20 weight% by weight aromatic polycarbonate.
- Polyesters suitable in the context of the present invention are polyesters having repeating unit of the Formula I:
- R is the residue of 1 ,4 cyclohexanedimethanol or a mixture of 1 ,4 cyclohexanedimethanol and at least one aryl, alkane or cycloalkane containing diol having 2 to 20 carbon atoms or chemical equivalent thereof; and wherein R 1 is the decarboxylated residue derived from an aryl, aliphatic, or cycloalkane containing diacid of 3 to 20 carbon atoms or chemical equivalent thereof.
- diol portion, R examples are ethylene glycol, 1 ,2 -propylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,5- pentanediol, 1 ,6-hexanediol, 1 ,2- or 1 ,3- cyclohexanedimethanol, neopentyl glycol, and 2,2,4,4 tetramethyl-1,3-cyclobutanediol.
- the preferred second glycol is ethylene glycol.
- Examples of the diacid portion, R 1 are malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, dodecanedioic, 1 ,4-, 1 ,5-, and 2,6-decahydronaphthalenedicarboxylic acid, and cis- or trans-1 ,4-cyclohexanedicarboxylic acid.
- Examples of useful aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, 4,4'- biphenyldicarboxylic, trans 3,3'-and trans 4,4 stilbenedicarboxylic acid, 4,4'- dibenzyldicarboxylic acid, 1 ,4-, 1 ,5'-, 2,3-, 2,6, and 2,7- naphthalenedicarboxylic acid.
- Chemical equivalents of these diacids include esters, alkyl esters, dialkyl esters, diaryl esters, anhydrides, salts, acid chlorides, acid bromides, and the like and are included within the scope of this invention.
- the preferred dicarboxylic acids are terephthalic and isophthalic acid or mixtures thereof.
- the preferred chemical equivalent comprises dialkyl esters of terephthalic and isophthalic acid. Mixtures of any of these acids or equivalents may be used.
- a preferred polyester useful within the scope of this invention is a polyester having from 40 to 100 mole %, more preferably 60 to 80 mole % of 1 ,4-cyclohexanedimethanol wherein the total mole percentages of the glycol component in the polyester equal 100 mole %.
- the remainder of the glycol component may be any of the other glycols described herein but preferably is ethylene glycol in the amount of 0 to 60 mole %, more preferably, 20 to 40 mole %.
- any diacid as described herein may be used, 80 to 100 mole % terephthalic acid, is preferred for this embodiment.
- polyester useful within the scope of this invention is a polyester having from 100 mole% 1 ,4-cyclohexanedimethanol wherein the total mole percentages of the glycol component in the polyester equal 100 mole %. Also, in this particular embodiment, it is preferred that isophthalic acid is present in the amount of 5 to 50 mole%, more preferably, 20 to 40 mole%. Although any diacid as described herein may be used, it is preferred that terephthalic acid is present in the amount of 95 to 50 mole %.
- polyesters of the present invention Conventional polycondensation processes, well known in the art, are used to prepare the polyesters of the present invention. These include direct condensation of the acid(s) with the diol(s) or by ester interchange using lower alkyl esters.
- the inherent viscosity of the polyesters of the present invention may range from about 0.4 to 1.0 dl/g at 25°C in a solvent consisting of 60% by weight phenol and 40% by weight tetrachlorethane.
- the polymerization reaction may be carried out in the presence of one or more conventional polymerization catalysts. Typical catalysts or catalyst systems for polyester condensation are well known in the art. Suitable catalysts are disclosed, for example, in U.S. Patent Nos.
- catalyst systems include Ti, Ti/P, Mn/Ti/Co/P, Mn/Ti/P, Zn/Ti/Co/P, Zn/AI, and Li/AI.
- cobalt is not used in the polycondensation, copolymerizable toners may be incorporated into the copolyesters to control the color of these copolyesters so that they are suitable for the intended applications where color may be an important property.
- branching agents may also be useful in making the polyesters formed within the context of the invention.
- the branching agent can be one which provides branching in the acid unit portion of the polyester, or in the glycol unit portion, or it can be a hybrid. Some of these branching agents have already been described herein. However, illustrative of such branching agents are polyfunctional acids, polyfunctional glycols and acid/glycol hybrids.
- Examples include tri or tetracarboxylic acids, such as trimesic acid, pyromellitic acid and lower alkyl esters thereof and the like, and tetrols such as pentaerythritol. Also triols such as trimethylopropane or dihydroxy carboxylic acids and hydroxydicarboxylic acids and derivatives, such as dimethyl hydroxy terephthalate, and the like are useful within the context of this invention. Trimellitic anhydride is a preferred branching agent. The branching agents may be used either to branch the polyester itself or to branch the polyester/polycarbonate blend of the invention. Polycarbonates useful in this invention comprise the divalent residue of dihydric phenols bonded through a carbonate linkage and are represented by structural formulae II and III.
- A denotes an alkylene group with 1 to 8 carbon atoms; an alkylidene group with 2 to 8 carbon atoms; a cycloalkylene group with 5 to 15 carbon atoms; a cycloalkylidene group with 5 to 15 carbon atoms; a carbonyl group; an oxygen atom; a sulfur atom; -SO- or -SO 2; or a radical conforming to e and g both denote the number 0 to 1 ; Z denotes F, CI, Br or C- .alkyl; and if several Z radicals are substituents in one aryl radical, they may be identical or different from one another; d denotes an integer of from 0 to 4; and f denotes an integer of from 0 to 3.
- alkylene is meant a bivalent saturated aliphatic radical wherein the two valences are on different carbon atoms, e.g., ethylene,; 1 ,3-propyIene; 1 ,2-propylene; 1 , 4-butylene; 1 ,3-butylene; 1 ,2- butylene, amylene, isoamylene, etc.
- alkylidene is meant a bivalent radical wherein the two valences are on the same carbon atoms, e.g., ethylidene, propylidene, isopropylidine, butylidene, isobutylidene, amylidene, isoamylidene, 3,5,5,-trimethylhexylidene.
- cycloalkylene are cyclopropylene, cyclobutylene, and cyclohexylene.
- Examples of “cycloalkylidene” are cyclopropylidene, cyclobutylidene, and cyclohexylidene.
- C ⁇ _ 4 .alkyl are methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.
- the dihydric phenols employed are known, and the reactive groups are thought to be the phenolic hydroxyl groups.
- Typical of some of the dihydric phenols employed are bis-phenols such as 2,2-bis-(4- hydroxyphenyl)-propane (bisphenol A), 3,3,5-trimethyl-1 ,1-bis(4- hydroxyphenyl)-cyclohexane, 2,4-bis-(4-hydroxyphenyl)-2-methyl-butane, 1 ,1-bis-(4-hydroxyphenyl)-cyclohexane, alpha, alpha'-bis-(4- hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl4-hydroxyphenyl)- propane, 2,2-bis-(3-chloro-4-hydroxyphenyl)propane, bis-(3,5-dimethyl4- hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxypheny
- dihydric phenols might include hydroquinone, resorcinol, bis-(hydroxyphenyl)-alkanes, bis- (hydroxyphenyl)ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)- sulfoxides, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-sulfones, and .alpha.,. alpha.
- dihydric phenols are described, for example, in U.S. Pat. Nos. 2,991 ,273; 2,999,835; 2,999,846; 3,028,365; 3,148,172; 3,153,008; 3,271 ,367; 4,982,014; 5,010,162 all incorporated herein by reference.
- the polycarbonates of the invention may entail in their structure, units de ⁇ ved from one or more of the suitable bisphenols.
- the most preferred dihydric phenol is 2,2-bis-(4- hydroxyphenyl)-propane (bisphenol A).
- the carbonate precursors are typically a carbonyl halide, a diarylcarbonate, or a bishaloformate.
- the carbonyl halides include, for example, carbonyl bromide, carbonyl chloride, and mixtures thereof.
- the bishaloformates include the bishaloformates of dihydric phenols such as bischloroformates of 2,2-bis(4-hydroxyphenyl)-propane, hydroquinone, and the like, or bishaloformates of glycol, and the like. While all of the above carbonate precursors are useful, carbonyl chloride, also known as phosgene, and diphenyl carbonate are preferred.
- the aromatic polycarbonates can be manufactured by any processes such as by reacting a dihydric phenol with a carbonate precursor, such as phosgene, a haloformate or carbonate ester in melt or solution. Suitable processes are disclosed in U.S. Pat. Nos. 2,991 ,273; 2,999,846; 3,028,365; 3,153,008; 4,123,436; all of which are incorporated herein by reference.
- the polycarbonates of this invention have a weight average molecular weight, as determined by gel permeation chromatography, of about 10,000 to 200,000, preferably 15,000 to 80,000 and their melt flow index, per ASTM D-1238 at 300°C is about 1 to 65 g/10 min, preferably about 2 to 30 g/10 min.
- the polycarbonates may be branched or unbranched. It is contemplated that the polycarbonate may have various known end groups. These resins are known and are readily available in commerce.
- Branching agents such as tri- and tetrafunctional phenols and carbonic acids, as well as bisphenols with carbonic acid side chains are typically used.
- An example might include 1 ,4- bis(4',4"-dihydroxytriphenylmethyl)benzene,and trisphenol TC.
- Nitrogen- containing branching agents are also used. Examples might include: cyanic chlorid and 3,3-bis(4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
- Polymer miscibillity is defined herein as a polymer forming a single phase.
- the preferred miscible blends of this invention were first disclosed in
- thermoplastic article can comprise the laminate of the invention having multiple upper or multiple lower layers, i.e., decorative layer, upper or lower sheet material, upper or lower sheet material, upper or lower sheet material, etc. or any combination of decorative layer and upper or lower sheet material so long as one decorative layer remains on the surface of the thermoplastic article.
- an adhesive layer may be used between any of the layers described in the invention.
- the adhesive layer can comprise any adhesive known in the art.
- Specific examples within the scope of this invention are polyurethane, modified polyethylenes, sulfopolyesters, epoxy coatings all of which are known in the art.
- Sulfopolyesters useful as adhesives in the practice of this invention can be either linear or branched.
- Preferred sulfopolyesters have a glass transition temperature (denoted as Tg) between -25°C and +90°C. More preferred sulfopolyesters have a Tg between 0°C and +65°C. Even more preferred sulfopolyesters have a Tg between +5°C and +55°C.
- useful sulfopolyesters have an inherent viscosity (a measure of molecular weight) of a least 0.1 and preferably at least 0.2 and more preferably at least 0.3 as measured in a 60/40 parts by weight solution of phenol/tetrachloroethane at 25°C and a concentration of about 0.25 grams of polymer in 100 mL of solvent.
- preferred compositions have a number-average-molecular weight (Mn) of at least 4000 daltons.
- polyester/polycarbonate blends of this invention maybe made by conventional melt processing techniques.
- pellets of the polyester may be mixed with pellets of the polycarbonate and subsequently melt blended on either a single or twin screw extruder to form a homogenous mixture.
- the miscible blend compositions of the invention may contain impact modifiers, UV stabilizers, stabilizers, nucleating agents, extenders, flame retarding agents, reinforcing agents, fillers, antistatic agents, mold release agents, colorants, antioxidants, extrusion aids, slip agents, release agents, carbon black, and other pigments, and the like all and mixtures thereof which are known in the art for their utility in polyester/polycarbonate blends.
- impact modifiers UV stabilizers, stabilizers, nucleating agents, extenders, flame retarding agents, reinforcing agents, fillers, antistatic agents, mold release agents, colorants, antioxidants, extrusion aids, slip agents, release agents, carbon black, and other pigments, and the like all and mixtures thereof which are known in the art for their utility in polyester/polycarbonate blends.
- phosphorous based stabilizers for further color reductions, if needed, is well known in the art.
- thermoplastic articles of the present invention comprises a decorative material.
- the decorative material may comprise metallic wire, rods or bars; natural fibers, glass fibers, mineral fibers, fabric, papers; and printed layers.
- fabric may be used as a decorative material to be encapsulated.
- the fabric may display images or decorative designs that have been produced, e.g., by weaving or knitting techniques, in the fabric.
- the fabrics which may be used in producing the articles of the present invention, comprise textile fibers, i.e., fibers of natural-occurring, semisynthetic or synthetic polymeric materials.
- the fabrics may be prepared from cotton, wool, silk, rayon (regenerated cellulose), polyester such as poly(ethylene terephthalate), synthetic polyamides such as nylon 66 and nylon 6, synthetic polyolefins such as polyethylene and polypropylene, acrylic, modacrylic and cellulose acetate fibers.
- the melting point of the textile fibers should be sufficiently high to avoid any degradation or distortion of the fabric during the manufacture or processing of the articles of this invention.
- the fabric may be woven, spun-bonded, knitted, or prepared by other processes well known in the textile trade and may be uncolored, e.g., white, or colored by conventional dyeing and printing techniques.
- the fabrics may be produced from dyed yarn or from filaments and yarn derived from mass colored polymers.
- the fabrics present within the thermoplastic articles of the present invention are substantially continuous and constitute a distinct layer.
- One embodiment of our invention is a novel laminate article comprising, (1 ) a fabric layer composed or made of textile fibers, and (2) an upper or lower layer of a miscible polyester/polycarbonate blend as described hereinabove.
- the second component (decorative component) of the thermoplastic articles of the present invention may comprise metallic wire, rod or bar.
- the metal wire may be formed by a variety of techniques to produce metal mesh fabric, screens, or open mesh having high transparency.
- the metal wire, rod or bar may be woven, welded, knitted, or fabricated by means of other processes well known in the metal wire fabrication trade.
- the metallic wire, rod and bar may be of various colors such as black, gray, green, blue, etc.
- the metallic element can be composed of different metallic materials such copper, aluminum, stainless steel, steel, galvanized steel, titanium, etc. or combinations thereof.
- the metallic component of the thermoplastic articles may be prepared from wire filaments, rods and bars having various cross-sectional areas and geometries, e.g., generally circular, oval or relatively flat.
- the thickness or diameter of the wire, rod and bar may range from about 0.001 to 19 mm (0.00004 to 0.75 inch) depending upon the end use of the thermoplastic article. However, for most of the articles of the present invention the thickness or diameter the wire, rod and bar will be in the range of about 0.0254 to 5.08 mm (0.001 to 0.20 inch).
- One embodiment of our invention is a novel laminate article comprising, (1 ) a metal wire mesh, and (2) an upper or lower layer of a miscible polyester/polycarbonate blend as described hereinabove.
- the decorative component may be decorative or printed papers, colored films, films printed with an image or picture, and the like.
- the thermoplastic articles of our invention can be used in the manufacture of decorative walls, partitions, and glazing applications.
- the thermoplastic articles are thermoformable according to methods known in the art of thermoforming.
- the upper and lower sheet materials used in the manufacture of the thermoplastic articles of the present invention may be the same or different.
- the upper and lower sheet materials may be produced from different miscible polyester/polycarbonate blends (as defined herein) or miscible compositions that contain different additives, e.g., pigment additives that alter the transparency of the miscible polyester/polycarbonate sheeting.
- the sheet material used in the preparation of the thermoplastic articles of our invention may be transparent, translucent, or one layer may be opaque, depending on the particular aesthetic effect desired.
- the upper and lower sheet materials may differ in degree of transparency or translucency and also in color.
- the miscible polyester/polycarbonate blends must be thermally compatible.
- thermal compatibility means that when layers of the sheet materials are bonded together under conditions of elevated temperature and pressure, the layers undergo approximately equal thermal expansion or contraction such that the solid surface is substantially planar.
- the thickness of the sheet materials used in the preparation of the thermoplastic articles is not an important feature of the present invention and depends upon a number of factors such as functionality, weight, cost and the like.
- the sheet material from which the upper (or outer) layer or surface is formed generally has a thickness in the range of about 0.76 to 6.4 mm (0.03-0.25 inch), preferably in the range of about 1.6 to 3.2 mm (0.063-0.126 inch).
- the sheet material from which the lower (or backing) layer or surface is formed typically has a thickness in the range of about 0.76 to 6.4 mm (0.03-0.25 inch), preferably about 3.2 mm (0.126 inch).
- thermoplastic article of the present invention may be produced by subjecting the laminate to temperatures and pressures sufficient to cause the upper or lower sheet materials to bond (or fuse) to the decorative layer.
- temperatures which cause decomposition, distortion, or other undesirable effects in the finished article or sheet material should be avoided. Avoidance of such extreme temperatures is an advantage of the miscible polyester/polycarbonate sheet materials of the present invention compared to the use of neat polycarbonate sheet.
- the bonding temperatures are in the range of about 90 to 300° C. (194 to 572° F.), preferably in the range of about 129 to 260° C. (265 to 500°F.).
- the pressures utilized in the bonding or laminating of the thermoplastic article of the invention preferably are in the range of about 0.65 to 3.45 MPa (about 95 to 500 pounds per square inch-psi).
- the optimal temperature for bonding the thermoplastic articles will vary depending, for example, on the particular miscible copolyester/polycarbonate blend employed and the thickness of the sheet materials used, and may be determined by those skilled in the art.
- the laminate is held at the appropriate temperature and pressure for about 4 to 24 minutes, or until such time as a bond is formed between the upper and lower sheet materials.
- the bonded/fused thermoplastic article is allowed to cool under pressures from about 0.69 to 2.4 MPa (about 100 to 350 psi), preferably about 1.4 MPa (200 psi), until it cools below the glass transition temperature of the miscible polyester/polycarbonate blend sheet material.
- the miscible polyester/polycarbonate blend sheet material may be bonded or fused to the decorative material without the use of an adhesive.
- the lamination process may utilize adhesives or coupling agents on the fabric to enhance the adhesion of the thermoplastic sheet materials to the decorative material.
- the miscible polyester/polycarbonate blends constituting the sheet materials used in the manufacture of the articles and sheeting of the present invention may not be as hard or scratch resistant as may be necessary or desired for certain end uses.
- an end use in which the exterior surface of the thermoplastic article may be subjected to scratching or abrasion, i.e., in a privacy partition may require the application of an abrasion-resistant coating to the exterior surface.
- films consisting of fluorinated hydrocarbons, poly(perfluoroethylene) such as TEDLAR from duPont Chemical Company or oriented poly(ethylene terephthalate) such as MYLAR from duPont Chemical Company may be used to improve both chemical and abrasion resistance.
- the abrasion resistant film typically has a thickness in the range of about 0.025 to 0.254 mm (0.001-0.01 inch), preferably about 0.051 to 0.178 mm (0.002-0.007 inch), and most preferably about 0.076 mm (0.003 inch).
- abrasion resistant film thinner or thicker than these ranges may be used since the thickness of such film is limited only by the equipment available cost and functionality considerations.
- An adhesive optionally may be used between the miscible copolyester/polycarbonate blend and the abrasion resistant film.
- an abrasion resistant coating may be applied to a plastic film and then the film bearing the abrasion resistant coating may be laminated to one or both sides of the article of the present invention.
- the film may be selected from a number of thermoplastic materials compatible with the lamination process such as poly(vinyl chloride), PETG copolyester, poly(ethylene terephthalate), poly(methyl methacrylate), polycarbonate, miscible polyester/polycarbonate blends, and the like.
- PETG is defined herein as a polyester comprising, terephthalic acid, ethylene glycol and 1 ,4- cyclohexanedimethanol.
- PETG comprises from 80 to 100 mole % terephthalic acid, 20 to 60 mole % 1 ,4-cyclohexanedimethanol and 80 to 40 mole % ethylene glycol based on the mole percentages for diacids totaling 100 mole % and the mole percentages for diols totaling 100 mole %.
- the film thickness may range from 0.0025-0.381 mm (0.001-0.015 inch) with a thickness of 0.0762-0.203 mm (0.003-0.008) being most preferred.
- the coating may be selected from a number of commercially- available materials such as polyurethanes, fluorinated polyurethanes and silicones which are cured by heat or they may be selected from materials that are cured by ultraviolet (UV) or electron beam (EB) radiation. Such UV/EB cured materials fall under the general class of acrylates and modified acrylates that contain fluorine, silicone, epoxy, polyester, polyether or caprolactone residues or functional groups. The particular coating material selected will depend primarily on the degree of abrasion resistance required.
- liquid, heat- or UV/EB-curable precursor of the abrasion resistant coating may be carried out according to conventional procedures and usually is accomplished on a roll coating machine.
- the thickness of the coating applied to a film generally is 0.0076-0.051 mm (0.0003-0.002 inch) with thickness of about 0.0127 mm (0.0005 inch) being most preferred.
- coatings may be applied in a manner similar to the application of paints.
- the coatings exist either as predominantly undiluted material with very little volatile content or as solvent- or water-based materials.
- they may be applied directly to the finished product. Application may be carried out by a variety of techniques such as roll, paint, spray, mist, dip and the like.
- thermoplastic article or laminate based on the miscible polyester/polycarbonate blend
- the thermoplastic article can be thermoformed or otherwise shaped into sliding glass doors, shower doors, entrance doors, privacy partitions, multi- paned windows, and tabletops and other furniture pieces.
- the thermoplastic articles of this invention may be formed, heat draped, or molded.
- the articles of the present invention have an appealing appearance with low density to facilitate transport and installation of building materials produced there from.
- This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
- the starting materials are commercially available unless otherwise indicated.
- Laminate A is comprised of a polyethylene based fabric placed on the top of one of the surfaces of a 1/4" sheet of a miscible copolyester/polycarbonate blend (75 wt% PCTG/25 wt% PC). The total laminate thickness is approximately 1/4".
- Laminate B is comprised of a polyethylene based fabric placed on the top of one of the surfaces of a 1/4" sheet of a neat copolyester (PETG). The laminate sheet, which measures 2' x 2', is then placed in a clamped frame and subjected to a uniform load (10 psi) at 60 C. After 10 hours, the center (maximum) deflection of the two laminates, still under load, was measured.
- Laminate A had a deflection of 3.5", while laminate B had a deflection of 4.5".
- PETG in this example is poly(ethylene terephthalate) modified with 31 mole % 1 ,4- cyclohexanedimethanol.
- PCTG in this example is poly(cyclohexylenedimethylene terephthalate) modified with 34 mole % ethylene glycol.
- PC in this example refers to polycarbonate, namely, bisphenol A.
- Laminate A is comprised of a polyethylene based fabric placed on the top of one of the surfaces of a 1/8" sheet of a miscible copolyester/polycarbonate blend (75 wt% PCTG/25 wt% PC). The total laminate thickness is 1/8".
- Laminate B is comprised of a polyethylene based fabric placed on the top of one of the surfaces of a 1/8" sheet of a neat (PC). The two laminate sheets, A and B, prepared measures 2' x 2'. The two laminates are allowed to equilibrate to the lab environment, in particular moisture level, for two months.
- PCTG in this example is poly(cyclohexylenedimethylene terephthalate) modified with 34 mole % ethylene glycol.
- PC in this example is polycarbonate, namely, bisphenol A.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20030786890 EP1575774B1 (en) | 2002-11-22 | 2003-11-18 | Articles of manufacture incorporating polyester/polycarbonate blends |
JP2004555502A JP2006507162A (en) | 2002-11-22 | 2003-11-18 | Articles of manufacture comprising polyester / polycarbonate blends |
AU2003295689A AU2003295689A1 (en) | 2002-11-22 | 2003-11-18 | Articles of manufacture incorporating polyester/polycarbonate blends |
DE60322951T DE60322951D1 (en) | 2002-11-22 | 2003-11-18 | OBJECTS CONTAINING POLYESTER / POLYCARBONATE MIXTURES |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/302,001 US6896966B2 (en) | 2002-11-22 | 2002-11-22 | Articles of manufacture incorporating polyester/polycarbonate blends |
US10/302,001 | 2002-11-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004048089A1 true WO2004048089A1 (en) | 2004-06-10 |
Family
ID=32324649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2003/037032 WO2004048089A1 (en) | 2002-11-22 | 2003-11-18 | Articles of manufacture incorporating polyester/polycarbonate blends |
Country Status (7)
Country | Link |
---|---|
US (1) | US6896966B2 (en) |
EP (1) | EP1575774B1 (en) |
JP (1) | JP2006507162A (en) |
AT (1) | ATE404364T1 (en) |
AU (1) | AU2003295689A1 (en) |
DE (1) | DE60322951D1 (en) |
WO (1) | WO2004048089A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007045067A (en) * | 2005-08-11 | 2007-02-22 | Mitsubishi Plastics Ind Ltd | Laminated sheet for designed coating and metal sheet coated with laminated sheet |
JP2008544033A (en) * | 2005-06-17 | 2008-12-04 | イーストマン ケミカル カンパニー | Films and / or sheets produced from polyester compositions containing cyclobutanediol and articles made therefrom |
Families Citing this family (68)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7118799B2 (en) * | 2002-11-22 | 2006-10-10 | Eastman Chemical Company | Thermoplastic article having a decorative material embedded therein |
DE10261196A1 (en) * | 2002-12-20 | 2004-07-01 | Basf Ag | laminating adhesive |
US8518457B2 (en) * | 2004-05-11 | 2013-08-27 | Pulmonox Technologies Corporation | Use of inhaled gaseous nitric oxide as a mucolytic agent or expectorant |
JP4929585B2 (en) * | 2004-11-10 | 2012-05-09 | 大日本印刷株式会社 | Molded sheet |
US7959836B2 (en) | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Process for the preparation of transparent, shaped articles containing polyesters comprising a cyclobutanediol |
US7955533B2 (en) * | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Process for the preparation of transparent shaped articles |
US7959998B2 (en) * | 2005-03-02 | 2011-06-14 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US20060199871A1 (en) * | 2005-03-02 | 2006-09-07 | Hale Wesley R | Multilayered, transparent articles and a process for their preparation |
US7786252B2 (en) * | 2005-03-02 | 2010-08-31 | Eastman Chemical Company | Preparation of transparent multilayered articles |
US7955674B2 (en) * | 2005-03-02 | 2011-06-07 | Eastman Chemical Company | Transparent polymer blends containing polyesters comprising a cyclobutanediol and articles prepared therefrom |
US7968164B2 (en) * | 2005-03-02 | 2011-06-28 | Eastman Chemical Company | Transparent polymer blends and articles prepared therefrom |
US7462684B2 (en) | 2005-03-02 | 2008-12-09 | Eastman Chemical Company | Preparation of transparent, multilayered articles containing polyesters comprising a cyclobutanediol and homogeneous polyamide blends |
US7964258B2 (en) * | 2005-03-02 | 2011-06-21 | Eastman Chemical Company | Transparent, oxygen-scavenging compositions and articles prepared therefrom |
US20100184940A1 (en) * | 2005-03-02 | 2010-07-22 | Eastman Chemical Company | Polyester Compositions Which Comprise Cyclobutanediol and Certain Thermal Stabilizers, and/or Reaction Products Thereof |
US20060270773A1 (en) * | 2005-05-26 | 2006-11-30 | Hale Wesley R | Polyester-polycarbonate blends for diffuser sheets with improved luminance |
US20060270806A1 (en) * | 2005-05-26 | 2006-11-30 | Hale Wesley R | Miscible high Tg polyester/polymer blend compositions and films formed therefrom |
US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
US7704605B2 (en) | 2006-03-28 | 2010-04-27 | Eastman Chemical Company | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
US20100298523A1 (en) * | 2005-06-17 | 2010-11-25 | Eastman Chemical Company | Polyester Compositions Which Comprise Cyclobutanediol and at Least One Phosphorus Compound |
US8431202B2 (en) * | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
US7655746B2 (en) | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
US9267007B2 (en) * | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
US7838596B2 (en) * | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
US20070100125A1 (en) * | 2005-10-28 | 2007-05-03 | Crawford Emmett D | Polyester compositions comprising minimal amounts of cyclobutanediol |
US8193302B2 (en) | 2005-10-28 | 2012-06-05 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain phosphate thermal stabilizers, and/or reaction products thereof |
US20070100122A1 (en) * | 2005-10-28 | 2007-05-03 | Crawford Emmett D | Polyester compositions containing cyclobutanediol and articles made therefrom |
US20100096589A1 (en) * | 2005-10-28 | 2010-04-22 | Emmett Dudley Crawford | Polyester compositions containing low amounts of cyclobutanediol and articles made therefrom |
ATE505500T1 (en) * | 2005-10-28 | 2011-04-15 | Eastman Chem Co | HIGH GLASS TRANSITION TEMPERATURE POLYESTER COMPOSITIONS CONTAINING CYCLOBUTANEDIOL AND ARTICLES MADE THEREFROM |
US20100087574A1 (en) * | 2005-10-28 | 2010-04-08 | Emmett Dudley Crawford | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US8586701B2 (en) | 2005-10-28 | 2013-11-19 | Eastman Chemical Company | Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
US20070142511A1 (en) * | 2005-12-15 | 2007-06-21 | Crawford Emmett D | Polyester compositions which comprise cyclobutanediol ethylene glycol, titanium, and phosphorus with improved color and manufacturing processes therefor |
US7737246B2 (en) | 2005-12-15 | 2010-06-15 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor |
US7704592B2 (en) * | 2006-03-09 | 2010-04-27 | Politec Polimeri Tecnici S.A. | Multilayer polymeric product based on polyethylene terephthalate and polycarbonate and its use as a building material |
US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
US20070232778A1 (en) * | 2006-03-28 | 2007-10-04 | Leslie Shane Moody | Certain polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and high trans-cyclohexanedicarboxylic acid |
US20070232779A1 (en) * | 2006-03-28 | 2007-10-04 | Leslie Shane Moody | Certain polyester compositions which comprise cyclohexanedimethanol, moderate cyclobutanediol, cyclohexanedimethanol, and high trans cyclohexanedicarboxylic acid |
US8114929B2 (en) * | 2006-07-03 | 2012-02-14 | Sabic Innovative Plastics Ip B.V. | Transparent polycarbonate-polyester blends with improved performance under caustic aqueous environments |
US20080027207A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents |
US7709595B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
US7709593B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
US7745368B2 (en) * | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
US20080053752A1 (en) * | 2006-09-06 | 2008-03-06 | Peter Miller | System and method for securing a window in a panel |
US8287991B2 (en) * | 2006-10-04 | 2012-10-16 | Eastman Chemical Company | Using branched polymers to control the dimensional stability of articles in the lamination process |
US20080085390A1 (en) | 2006-10-04 | 2008-04-10 | Ryan Thomas Neill | Encapsulation of electrically energized articles |
ATE468968T1 (en) * | 2006-10-16 | 2010-06-15 | Valspar Sourcing Inc | MULTI-LAYER THERMOPLASTIC FILM |
US7655737B2 (en) * | 2006-11-16 | 2010-02-02 | Sabic Innovative Plastics Ip B.V. | Polycarbonate-polyester blends, methods of manufacture, and methods of use |
US20080149165A1 (en) * | 2006-12-22 | 2008-06-26 | General Electric Company | Luminescent solar collector |
US8901272B2 (en) * | 2007-02-02 | 2014-12-02 | Grupo Petrotemex, S.A. De C.V. | Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration |
JP4968459B2 (en) * | 2007-04-12 | 2012-07-04 | 住友ベークライト株式会社 | HARD COAT FILM FOR INJECTION MOLDING AND METHOD FOR PRODUCING INJECTION MOLDING USING THE FILM |
EP2150407A4 (en) | 2007-05-08 | 2013-03-06 | Hunter Douglas Ind Switzerland | Multivariate color system with texture application |
US20090105380A1 (en) * | 2007-10-22 | 2009-04-23 | Eastman Chemical Company | Uv absorbing additives suitable for thermoplastic articles made from processes with extended heat histories |
US8501287B2 (en) | 2007-11-21 | 2013-08-06 | Eastman Chemical Company | Plastic baby bottles, other blow molded articles, and processes for their manufacture |
CN101868340B (en) | 2007-11-21 | 2016-04-20 | 伊士曼化工公司 | Plastic baby bottles, other blow molded articles and preparation method thereof |
US8198371B2 (en) | 2008-06-27 | 2012-06-12 | Eastman Chemical Company | Blends of polyesters and ABS copolymers |
US20100099828A1 (en) * | 2008-10-21 | 2010-04-22 | Eastman Chemical Company | Clear Binary Blends of Aliphatic Polyesters and Aliphatic-Aromatic Polyesters |
US8895654B2 (en) | 2008-12-18 | 2014-11-25 | Eastman Chemical Company | Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid |
KR101639631B1 (en) | 2009-12-28 | 2016-07-14 | 에스케이케미칼주식회사 | Thermoplastic article comprising decorative materials |
JP5549423B2 (en) * | 2010-06-09 | 2014-07-16 | 住友ベークライト株式会社 | Structure and resin plate |
US8420868B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
US8394997B2 (en) | 2010-12-09 | 2013-03-12 | Eastman Chemical Company | Process for the isomerization of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
US8420869B2 (en) | 2010-12-09 | 2013-04-16 | Eastman Chemical Company | Process for the preparation of 2,2,4,4-tetraalkylcyclobutane-1,3-diols |
US9150006B2 (en) | 2011-06-23 | 2015-10-06 | Eastman Chemical Company | Lamination process optimization utilizing neopentyl glycol-modified polyesters |
US10065404B2 (en) | 2011-07-29 | 2018-09-04 | Eastman Chemical Company | In-line lamination of heavy-gauge polymer sheet with a pre-formed polymer film |
US20130217830A1 (en) | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
TWI495680B (en) | 2013-11-07 | 2015-08-11 | Ind Tech Res Inst | Polyester composition, electronic device, and method of forming film |
US20170066873A1 (en) * | 2015-09-09 | 2017-03-09 | Eastman Chemical Company | Compositions for the production of objects using additive manufacturing |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5643666A (en) * | 1995-12-20 | 1997-07-01 | Eastman Chemical Company | Solid surfaces which are prepared from copolyesters laminated onto a high resolution image |
US5958539A (en) * | 1997-08-26 | 1999-09-28 | Eastman Chemical Company | Thermoplastic article having textile fiber fabric embedded therein |
US5998028A (en) * | 1997-08-26 | 1999-12-07 | Eastman Chemical Company | Thermoplastic article having metallic wire, rod or bar embedded therein |
US6025069A (en) * | 1998-06-19 | 2000-02-15 | Eastman Chemical Company | Thermoplastic article having high-relief surface |
WO2002040590A2 (en) * | 2000-11-03 | 2002-05-23 | Eastman Chemical Company | Blends of polycarbonate and polyester and sheets and films formed therefrom |
WO2003066330A2 (en) * | 2002-02-08 | 2003-08-14 | Eastman Chemical Company | Ultraviolet protected multi-layer structures of copolyester/polycarbonate blends |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL104015C (en) | 1953-10-16 | |||
DE1007996B (en) | 1955-03-26 | 1957-05-09 | Bayer Ag | Process for the production of thermoplastics |
US3153008A (en) | 1955-07-05 | 1964-10-13 | Gen Electric | Aromatic carbonate resins and preparation thereof |
US2991273A (en) | 1956-07-07 | 1961-07-04 | Bayer Ag | Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates |
US3148172A (en) | 1956-07-19 | 1964-09-08 | Gen Electric | Polycarbonates of dihydroxyaryl ethers |
US2999846A (en) | 1956-11-30 | 1961-09-12 | Schnell Hermann | High molecular weight thermoplastic aromatic sulfoxy polycarbonates |
US2999835A (en) | 1959-01-02 | 1961-09-12 | Gen Electric | Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same |
US3094508A (en) * | 1959-04-16 | 1963-06-18 | Armstrong Cork Co | Branched polycarbonate and process for preparing same |
US3546008A (en) | 1968-01-03 | 1970-12-08 | Eastman Kodak Co | Sizing compositions and fibrous articles sized therewith |
US3734874A (en) | 1970-02-27 | 1973-05-22 | Eastman Kodak Co | Polyesters and polyesteramides containing ether groups and sulfonate groups in the form of a metallic salt |
DE2431072C3 (en) | 1974-06-28 | 1980-04-30 | Bayer Ag, 5090 Leverkusen | Thermoplastic copolyesters and processes for their manufacture |
US4136089A (en) | 1975-02-22 | 1979-01-23 | Bayer Aktiengesellschaft | Molded articles of crystalline poly (ethylene/alkylene) terephthalates which crystallize rapidly |
US4188314A (en) | 1976-12-14 | 1980-02-12 | General Electric Company | Shaped article obtained from a carbonate-polyester composition |
US4391954A (en) | 1976-12-14 | 1983-07-05 | General Electric Company | Thermoplastic molding composition |
US4123436A (en) | 1976-12-16 | 1978-10-31 | General Electric Company | Polycarbonate composition plasticized with esters |
DE2715932A1 (en) | 1977-04-09 | 1978-10-19 | Bayer Ag | FAST CRYSTALLIZING POLY (AETHYLENE / ALKYLENE) TEREPHTHALATE |
US4111846A (en) | 1977-05-06 | 1978-09-05 | W. R. Grace & Co. | Hydrosol and catalyst preparation |
DE2811982A1 (en) | 1978-03-18 | 1979-09-27 | Huels Chemische Werke Ag | METHOD FOR PRODUCING HIGH MOLECULAR POLY (ETHYLENE TEREPHTHALATE) |
US4233196A (en) | 1979-04-30 | 1980-11-11 | Eastman Kodak Company | Polyester and polyesteramide compositions |
US4238593B1 (en) | 1979-06-12 | 1994-03-22 | Goodyear Tire & Rubber | Method for production of a high molecular weight polyester prepared from a prepolymer polyester having an optional carboxyl content |
US4260671A (en) * | 1979-11-09 | 1981-04-07 | Eastman Kodak Company | Polycarbonate overcoats and binders for photoconductive layers and elements |
US4786692A (en) | 1982-12-20 | 1988-11-22 | General Electric Company | High strength, reduced heat distortion temperature thermoplastic composition |
NO170326C (en) | 1988-08-12 | 1992-10-07 | Bayer Ag | DIHYDROKSYDIFENYLCYKLOALKANER |
US4946932A (en) | 1988-12-05 | 1990-08-07 | Eastman Kodak Company | Water-dispersible polyester blends |
DE3926719A1 (en) | 1988-12-23 | 1990-07-05 | Bayer Ag | POLYCARBONATES FROM ALKYLCYCLOHEXYLIDENBISPHENOLS |
FR2682956B1 (en) | 1991-10-29 | 1994-01-07 | Rhone Poulenc Chimie | PROCESS FOR THE PREPARATION OF WATER-SOLUBLE AND / OR HYDRODISPERSABLE POLYESTERS AND USE OF SUCH POLYESTERS FOR SIZING TEXTILE THREADS. |
EP0577849A4 (en) * | 1992-01-29 | 1995-03-01 | Daicel Chem | Polycarbonate and production thereof. |
WO1995018191A1 (en) | 1993-12-29 | 1995-07-06 | Eastman Chemical Company | Water-dispersible adhesive composition and process |
US5543488A (en) | 1994-07-29 | 1996-08-06 | Eastman Chemical Company | Water-dispersible adhesive composition and process |
US5413870A (en) | 1994-01-03 | 1995-05-09 | Flood; Christopher J. | Decorative bathroom panel including embedded fabric |
DE69532875T2 (en) | 1994-10-24 | 2004-08-19 | Eastman Chemical Co., Kingsport | Water-dispersible block copolyesters |
US6162890A (en) | 1994-10-24 | 2000-12-19 | Eastman Chemical Company | Water-dispersible block copolyesters useful as low-odor adhesive raw materials |
US5646237A (en) | 1995-08-15 | 1997-07-08 | Eastman Chemical Company | Water-dispersible copolyester-ether compositions |
US20030030172A1 (en) * | 2001-06-15 | 2003-02-13 | Gabrie Hoogland | Formed decorative film |
-
2002
- 2002-11-22 US US10/302,001 patent/US6896966B2/en not_active Expired - Lifetime
-
2003
- 2003-11-18 EP EP20030786890 patent/EP1575774B1/en not_active Expired - Lifetime
- 2003-11-18 DE DE60322951T patent/DE60322951D1/en not_active Expired - Lifetime
- 2003-11-18 AU AU2003295689A patent/AU2003295689A1/en not_active Abandoned
- 2003-11-18 AT AT03786890T patent/ATE404364T1/en not_active IP Right Cessation
- 2003-11-18 WO PCT/US2003/037032 patent/WO2004048089A1/en active Application Filing
- 2003-11-18 JP JP2004555502A patent/JP2006507162A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5643666A (en) * | 1995-12-20 | 1997-07-01 | Eastman Chemical Company | Solid surfaces which are prepared from copolyesters laminated onto a high resolution image |
US5958539A (en) * | 1997-08-26 | 1999-09-28 | Eastman Chemical Company | Thermoplastic article having textile fiber fabric embedded therein |
US5998028A (en) * | 1997-08-26 | 1999-12-07 | Eastman Chemical Company | Thermoplastic article having metallic wire, rod or bar embedded therein |
US6025069A (en) * | 1998-06-19 | 2000-02-15 | Eastman Chemical Company | Thermoplastic article having high-relief surface |
WO2002040590A2 (en) * | 2000-11-03 | 2002-05-23 | Eastman Chemical Company | Blends of polycarbonate and polyester and sheets and films formed therefrom |
WO2003066330A2 (en) * | 2002-02-08 | 2003-08-14 | Eastman Chemical Company | Ultraviolet protected multi-layer structures of copolyester/polycarbonate blends |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008544033A (en) * | 2005-06-17 | 2008-12-04 | イーストマン ケミカル カンパニー | Films and / or sheets produced from polyester compositions containing cyclobutanediol and articles made therefrom |
JP2008546561A (en) * | 2005-06-17 | 2008-12-25 | イーストマン ケミカル カンパニー | Thermoplastic article containing cyclobutanediol with a decorative material embedded inside |
JP2008546603A (en) * | 2005-06-17 | 2008-12-25 | イーストマン ケミカル カンパニー | Food storage container comprising a polyester composition formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
JP2008546560A (en) * | 2005-06-17 | 2008-12-25 | イーストマン ケミカル カンパニー | Glass laminate comprising a polyester composition formed from 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol |
JP2007045067A (en) * | 2005-08-11 | 2007-02-22 | Mitsubishi Plastics Ind Ltd | Laminated sheet for designed coating and metal sheet coated with laminated sheet |
JP4719529B2 (en) * | 2005-08-11 | 2011-07-06 | 三菱樹脂株式会社 | Laminated sheet for design coating and laminated sheet coated metal sheet |
Also Published As
Publication number | Publication date |
---|---|
DE60322951D1 (en) | 2008-09-25 |
EP1575774A1 (en) | 2005-09-21 |
US6896966B2 (en) | 2005-05-24 |
AU2003295689A1 (en) | 2004-06-18 |
EP1575774B1 (en) | 2008-08-13 |
JP2006507162A (en) | 2006-03-02 |
ATE404364T1 (en) | 2008-08-15 |
US20040101687A1 (en) | 2004-05-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1575774B1 (en) | Articles of manufacture incorporating polyester/polycarbonate blends | |
US8287991B2 (en) | Using branched polymers to control the dimensional stability of articles in the lamination process | |
JP5685240B2 (en) | Thermoplastic article containing cyclobutanediol with a decorative material embedded inside | |
EP1569795B1 (en) | Thermoplastic article having a decorative material embedded therein | |
EP1009630B1 (en) | Thermoplastic article having textile fiber fabric embedded therein | |
CN101203544B (en) | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein | |
EP1021297B1 (en) | Thermoplastic article having metallic wire, rod or bar embedded therein | |
US7906211B2 (en) | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein | |
US10882272B2 (en) | Tough shrinkable films | |
US20110144266A1 (en) | Thermoplastic Articles Comprising Cyclobutanediol Having a Decorative Material Embedded Therein | |
US20090105380A1 (en) | Uv absorbing additives suitable for thermoplastic articles made from processes with extended heat histories |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2003786890 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2004555502 Country of ref document: JP |
|
WWP | Wipo information: published in national office |
Ref document number: 2003786890 Country of ref document: EP |