WO1994013482A1 - A biaxially oriented two-layer copolyester film for capacitor dielectric use - Google Patents
A biaxially oriented two-layer copolyester film for capacitor dielectric use Download PDFInfo
- Publication number
- WO1994013482A1 WO1994013482A1 PCT/US1992/010709 US9210709W WO9413482A1 WO 1994013482 A1 WO1994013482 A1 WO 1994013482A1 US 9210709 W US9210709 W US 9210709W WO 9413482 A1 WO9413482 A1 WO 9413482A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- biaxially oriented
- film
- layer
- copolyester film
- bibenzoate
- Prior art date
Links
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 75
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 238000004804 winding Methods 0.000 claims abstract description 17
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000003989 dielectric material Substances 0.000 claims abstract description 7
- 230000003746 surface roughness Effects 0.000 claims abstract description 3
- 238000007669 thermal treatment Methods 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 57
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- -1 polyethylene terephthalate Polymers 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 239000010419 fine particle Substances 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002902 bimodal effect Effects 0.000 claims description 6
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 5
- 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Chemical class 0.000 claims description 3
- 239000011572 manganese Chemical class 0.000 claims description 3
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 238000010023 transfer printing Methods 0.000 claims description 3
- 239000011701 zinc Chemical class 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- UHPJWJRERDJHOJ-UHFFFAOYSA-N ethene;naphthalene-1-carboxylic acid Chemical compound C=C.C1=CC=C2C(C(=O)O)=CC=CC2=C1 UHPJWJRERDJHOJ-UHFFFAOYSA-N 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 230000000063 preceeding effect Effects 0.000 claims 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims 1
- 239000011236 particulate material Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 25
- 238000006068 polycondensation reaction Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 150000002009 diols Chemical class 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 3
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 239000002355 dual-layer Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- YSTSBXDVNKYPTR-UHFFFAOYSA-N CC(c(cc1)ccc1-c(cc1)ccc1C(C)=O)=O Chemical compound CC(c(cc1)ccc1-c(cc1)ccc1C(C)=O)=O YSTSBXDVNKYPTR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002987 primer (paints) Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/14—Organic dielectrics
- H01G4/18—Organic dielectrics of synthetic material, e.g. derivatives of cellulose
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
- H01G4/206—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06 inorganic and synthetic material
-
- 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
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/16—Capacitors
Definitions
- This invention relates to a two-layer biaxially oriented copolyester film having low shrinkage properties and good thermal properties for use as a capacitor dielectric film.
- the film of the present invention must have good winding characteristics as well as slipperiness to permit the film to slide over a previously wound section (i.e., to be non-blocking) while also having minimum layer-to-layer distance.
- the film of the present invention has good mechanical strength, especially stiffness (tensile modulus) and thus thickness reduction can be achieved, making the film of the present invention exceptionally useful as a capacitor dielectric.
- thermal stability is important because with surface mounting assembly a capacitor incorporating the dielectric film must be dipped in a solder bath at approximately 260°C to solder the leads of the capacitor to a circuit board.
- the majority of the prior art films fail due to melting and/or shrinking during or shortly after exposure to a solder bath. Because the yield in such a process is particularly low, the cost of the circuits using these film capacitors is so high as to be prohibitive.
- the circuit manufacturer must make do with ceramic capacitors, which have inferior dielectric properties. Similar properties with respect to thermal stability and mechanical strength
- capacitor dielectric films Another desired characteristic of capacitor dielectric films is a low water pickup.
- Low water pickup is important because this retards the degradation of the capacitor due to corrosion of the metallized layer.
- a film water pickup at 23°C and 50 % r.h. of less than 0.1 weight-% and preferably less than 0.06 weight-% are possible.
- European Patent Application No. 423,402 filed October 17, 1989 by Katoh et al discloses a thermal plastic polymeric film said to have usefulness as a material for capacitors and for thermal transfer ribbons.
- the polymeric substrate can be polyester, polyphenylene sulfide, polyamides, polysulfones, and polyvinylidene fluoride. While some of these polymers have good thermal characteristics, they are either very expensive to produce, have relatively poor mechanical properties or relatively high moisture pick-up that make their usefulness for capacitor films or thermal transfer ribbons impractical.
- U.S. Patent No. 3,008,934 discloses copolyesters containing as acid derived units 4,4'-bibenzoate and a host of other dicarboxylates including 2,6- naphthalic dicarboxylate. It also discloses oriented fibers and films prepared from these copolyesters, however, biaxially oriented PENBB films are not disclosed or envisioned. In particular, those films with improved stiffness (tensile modulus) and tensile strength in both MD and TD as well as thermostability, UV stability, hydrophobicity, dimensional stability and impermeability toward gases in comparison to PET film are not disclosed in U.S. Patent No. 3,008,934. Japanese Patent No. 50.
- thermoplastic polymer having excellent thermal stability characteristics and having the requisite mechanical strengths, especially improved stiffness (tensile modulus) sufficient to permit those skilled in the art to produce a film capable of being employed as a capacitor film.
- the present invention relates to a biaxially oriented PENBB copolyester film having at least about 25 mole-% of the diacid or diester content in the copolymer of 4,4'-bibenzoic acid or of 4,4'-dimethyl bibenzoate with the remainder of the copolyester being produced from a different diacid or diester.
- the copolyester must have a melting point sufficient to permit the copolymer to withstand a solder bath such as those known in the capacitor dielectric manufacturing industry, i.e. , the copolyester film must not melt or shrink. With the present invention, shrinkages of less than 0.5 % at 1 50°C are possible, preferably films having a shrinkage of equal to or less than 0.3 % are possible.
- a copolyester film useful for capacitor dielectrics must also have good winding characteristics, slipperiness, as well as the mechanical strength, especially stiffness to form an ultrathin film.
- the reason thickness reduction of polymeric films employed for dielectric material in a capacitor is ad ⁇ vantageous because the electrostatic capacitance of the capacitor is proportional to the dielectric constant of the dielectric material and inversely proportional to the square of the thickness of the film. If the dielectric material is constant, reducing the thickness of the film makes the production of capacitors of a smaller size and a larger capacity possible.
- a bimodal particle distribution of filler material can be employed to provide sufficient slip and good winding characteristics.
- These particles may also be in the form of agglomerated fine particles which, upon blending with the polymer resin and subsequent film processing, break up into finely divided particles.
- the particles may be added in a range from 0.01 to 5 parts by weight, based on the weight of the copolyester, and have an average particle diameter of about 0.01 to about 5 ⁇ m.
- the R a value of layer A should be _ ⁇ 1 0 nm and the R a value of layer B should be > 10 nm.
- the present invention comprises a biaxially oriented PENBB copoiyester film useful for capacitor dielectrics or thermal transfer printing ribbon base, wherein the biaxially oriented copolyester film has at least 25 mole-
- Figure 1 is a graph showing the dependence of the melting point tempera ⁇ ture of the preferred PENBB copolyester, based on 2,6-naphthalate and 4,4'- bibenzoate on its molar diacid ratio.
- the PENBB copolyesters of the present invention are made by reacting at least two dicarboxylic acids, or their ester equivalents with suitable glycols or diols, as is well known in the art. Such a reaction produces monomers or oligomers of the copolyester. The monomers or oligomers are then subject to a polycondensation reaction, as known in the art, to produce a copolyester.
- the PENBB copolyester of the present invention is derived primarily from dicarooxylic acids or their ester equivalents with at least 25 mole-% of the dicar- boxylic acid being 4,4'-bibenzoic acid (or the ester equivalent) having the following formula:
- the remainder of the copolyester may be formed from other dicarboxylic acids or their ester equivalents, such as terephthalic acid, isophthalic acid, phthalic acid, naphthaiene-2, 6-dicarboxylic acid, 1 ,4-cyclohexane dicarboxylic acid, di-(4-phenyl)-acetylene dicarboxylic acid, 1 ,2-di-(4-phenyl)-ethylene dicarboxylic acids, sebacic acid, malonic acid, adipic acid, azelaic acid, glutaric acid, suberic acid, succinic acid, and the like, or mixtures of these can be employed in the present invention.
- Naphthalene-2, 6-dicarboxylic acid is the preferred remainder diacid.
- Suitable diols employed in the present invention include ethylene glycol, diethylene glycol, propylene glycol, butanediol, 1 ,5-pentaediol, 1 ,6-hexanediol, neopentyl glycol, 1 , 10-decanediol, cyclohexane dimethanol, and the like.
- Ethylene glycol is the preferred glycol.
- Suitable copolyesters of the present invention can comprise, for example, polyethylene terephthalate/4,4'-bibenzoate, polybutylene terephthalate/4,4'- bibenzoate, polypropylene terephthalate/4,4'-bibenzoate, polyethylene napht- halate/4,4-bibenzoate, polyethylene terephthalate/isophthalate/4,4'-bibenzoate, polyethylene terepntna ⁇ ate/adipate/4,4'-bibenzoate, polyethylene terepthalate/- sulphoisophthalate/4,4-bibenzoate, and the like.
- the IV value inherent viscosity, as measured in a 1 : 1 weight-ratio mixture of pentafluorophenol and hexafluoroi- sopropanol at a concentration of 0.2 g/dl and a temperature of 25 ° C
- PENBB polymer after extrusion be > 0.5 dl/g and preferably > 0.55 dl/g.
- a polyethylene naphthalate bibenzoate copolyester comprises roughly equimolar portions of the esters ethylene naphthalate and 4,4'-bibenzoate, or the acids of naphthalene-2,6-dicarboxylic acid and bibenzoic acid .
- the copolyester is obtained by polycondensation of the diacids or diesters with a diol. It may be advantageous, however, to employ an excessive amount of the diol in order to influence the reaction kinetics.
- a mixture of two or more dicarboxylic acids or esters are mixed with at least of two or 100 mole-% of the corresponding diol.
- the diacids or their ester equivalents and the diols are mixed uniformly and heated to approximately 200°C in the presence of a transesterification catalyst, as is well known in the art.
- the reaction yields monomer or low molecular weight polyester which is subsequently subjected to the polycondensation reaction in the presence of a polycondensation catalyst.
- stabilizers, antioxi- dants, delustrants, pigments, fillers, antistatic agents, etc. may be uniformly mixed with the copolyester.
- the addition of particuiate matter is - insofar as it is inert - preferably performed in an ethylene glycol slurry before, during or immediately following the ester formation or transesterification and at all events before the polycondensation. This addition in a less viscous state enables improved dispersion of the particuiate matter.
- Suitable catalysts are antimony, manganese, cobalt, magnesium, zinc, calcium, etc., as are well known in the art.
- the preferred transesterification catalyst, where employed, would be manganese and/or cobalt.
- the perferred polycondensation catalyst would be antimony compounds. Such catalysts are well known and conventional in the prior art.
- the two-layer biaxially oriented copolyester film of the present invention can be manufactured by a coextrusion process, where the copolyester resin composition A containing no or only very fine particulates and copolyester resin composition B containing larger particles are heated to a molten state in separate extruder and then combined in a combining block or dual manifold die and extruded in the form of a two-layer amorphous sheet onto a polished, revolving casting drum.
- the amorphous sheet is rapidly cooled or "quenched” to form a cast sheet of polyester.
- the cast polyester sheet is removed from the casting drum and then axially stretched in one direction, either in the direction of the film travel (machine direction, MD) or perpendicular to the machine direction
- the copolyester film of this invention is biaxially oriented, i.e. stretched in both the machine direction and the transverse direction.
- the total stretch ratios in the machine direction and the transverse direction lie between 1 :2 and 1 : 10, perferably between 1 :2.5 and 1 :5.
- the product of the total stretch ratios should be between 1 to 30, and preferably between 5 to 20.
- Biaxial drawing is performed such that the birefringeance is ⁇ 0.2, preferably ⁇ 0.1 to ensure adequately isotropic properties.
- Birefringeance is the absolute value of the difference between the maximum and minimum refractive indices in the plane of the film, as measured on common instruments such as Abbe refractometer, optical bench or compensators.
- a heat setting step takes place to lock in the properties of the film.
- the heat setting occurs at a temperature between the cold-crystallization temperature and the melt temperature of the copolymer composition.
- the film may be wound on a roll, or in some cases surface treatment of the film such as corona treatment, plasma or flame treatment may be employed before winding the film on the roll, particularly where the film will be further coated with a primer coating or a metallic coating, for example.
- the film it is desirable for the film to have a final total thickness of between 0.1 and 1 2 ⁇ m, preferably between 0.3 and 6 ⁇ m. No matter what copolyester composition is employed, it must be able to withstand a solder bath which is typically in the range of about 260°C for about 10 seconds. Copolyesters which can survive this conditioning are thermally stable for the present invention. Copolyesters of the present invention typically have a melting point dependent upon the composition. Figure 1 illustrates a melting point curve based on a preferred composition of PENBB. Similar curves are also expected for other copolyesters of the present invention.
- the film composi ⁇ tion must be such that one surface is rough. This is achieved by incorporating inert insoluble particles into one or both layers of the film.
- Layer A which is essentially smooth, contains no or only very fine particles.
- Layer B which is rough, contains particles. In the case that layer A also contains particles, those in layer B are larger.
- Layer B may also contain particles with a bimodal particle size distribution in which case it is possible that the finer particles are the same size as the opiional fine particles layer A.
- the fine inert insoluble particles can be in the form of an agglomerate which disperses or breaks up upon orientation of the film to form fine inert insoluble particles.
- these particles may be added to the raw materials or more preferably to the monomers before or during polycondensation or to the polymer before extrusion.
- inert particles either in agglomerated form or finely dispersed powders can be kaolin, talc, silica, carbonates of magnesium, calcium, or barium; sulfates of calcium, or barium; phosphates of lithium, calcium, or magnesium; oxides of aluminum, silicon, titanium, zirconium, or mixtures thereof, lithium fluoride, carbon black, or the organic acid salts of calcium, barium, zinc, and manganese.
- fine particles made of crosslinked polymers such as polystyrene, polyacrylate, or polymethacrylate, for example, which are inert with respect to the reactions described herein to make the copolyester.
- the particles may be of one type or mixtures of several types.
- the shapes of the particles can be irregular, flaky, spherical, or elongated.
- spherical particles are employed particularly for the large particles.
- the hardness, density and color of the particles is generally immaterial.
- the average size of the particle should be less than 10 ⁇ m, and generally preferably less than 3 ⁇ m as will be discussed later.
- the amount of particles incorporated into the film should generally be in a range of from 0.01 % to 5 % by weight and preferably between 0.5 % and 2.0 % by weight.
- the bimodal particle distribution for the present invention comprises from about 0.01 to about 3 % by weight of inert particles having an average particle diameter of 3 to 50 nm which optionally may be aggregates of the fine particles, said aggregates having an average particle diameter of 0.05 to 5 ⁇ m.
- the other modal particle distribution consists of 0.005 to 1 % by weight having an average particle diameter of 0.05 to 4 ⁇ m and are preferably spherical with an aspect ratio of from 1 .0 to 1 .2.
- the content of the fine inert panicles should be in a range from 0.01 to 3 % by weight based on the weight of the copolyester. If the content is less than 0.01 % by weight, the excess air is trapped between the layers upon winding.
- the larger particles are more spherical in shape and differ from the ultra fine lumpy particles.
- the larger particles have a particle size of about 0.5 ⁇ m to 4 ⁇ m and employed in a range of 0.005 to 1 % by weight, based on the weight of the copolyester.
- the average particle diameter of the large particles is not larger than the thickness of the film.
- the large particle diameters size is between about 0.2 and 3 ⁇ m. If the large particle size is less than 0.05 ⁇ m, the resulting film has insufficient slipperiness and cannot be handled easily. If it exceeds 4 ⁇ m in size, the surface of the film is excessively rough and the dielectric breakdown voltage is decreased and insulation defects increase.
- the bimodal particle distribution described in the present invention is generally similar to that described in European Patent Application No. 423,402, as previously described. With the present invention, however, it is contemplated that a broader range (types) of inert particles can be employed for both the fine particle size and the large particle size.
- the tensile properties of the film were determined in a tensile tester produced by Zwick (Ulm, Germany). The test parameters were testing length 100 mm sample size 200x1 5 mm draw rate (modulus) 10 %/min draw rate (other values) 100 %/min
- the aspect ratio of a non-spherical particle is determined by dividing the length of the longest axis through the particle A e by the length of the shortest axis perpendicular to Ariz A s
- the values A, and A s can be determined by microscopy, such as SEM. Water Pick-Up at 50 % r.h.
- the film sample is conditioned at 50 % relative humidity and 25 °C for ⁇ 2 days. It is then quickly placed in a commercial coulometric water tester manufactured by Du Pont. The sample is heated under a dry stream of N 2 until no more water is desorbed by the sample. The desorbed water in the N 2 stream is absorbed onto P 2 O 5 and the amount is determined coulometrically, using the calibration constant of the instrument determined daily with a known sample.
- the R a value gives the surface roughness in the form of the arithmetic average of all displacements of the roughness R from the center line.
- the measurement is performed according to DIN standard 4768 on a surface tester (Perthometer SPG made by Feinpr ⁇ f GmbH of Gottingen, Germany). The values given are based on 6 individual measurements, in which the highest value is discarded before averaging.
- the cut-off, i.e. individual length of the measure ⁇ ment sections, is 0.08 mm.
- the residual melt is granulated .
- the granules are white, opaque and crystalline.
- An IV value of 0.56 dl/g was determined for the granules (measured at a concentration of 0.1 g/ml in pentafluorophenol/hexafluoroisopropanol [weight ratio 1 :1 ] at 25°C).
- the granules are further condensed for 20 hours at 240°C under vacuum in the solid phase. After this treatment the IV value is 1 .1 dl/g. The melting point (T is 281 °C.
- EXAMPLE 2 (preparation of copolyester with particuiate filler) The same procedure as in Example 1 is followed, except that 23 parts of a slurry of BaSO 4 particles in ethylene glycol is added to the transesterified mixture just before adding the triphenyl phosphate and antimony trioxide. This slurry is prepared by dispersing 10 parts by weight of BaSO 4 with an average particle diameter of 0.6 ⁇ m in 30 parts by weight of ethylene glycol. The resulting copolyester contains 0.3 wt.-% BaS0 4 particles.
- copolyesters prepared according to examples 1 and 2 are each melted in separate extruders, sent to a multimanifold slot die via 2 gear pumps running at equal throughput, combined to form a two-layer film, cooled on a chill roll to 20 °C.
- the thus obtained amorphous film is heated to 1 25°C and drawn by a factor of 3.5 in MD, then TD.
- the film is then heat set under restraint at 260°C for 10 seconds to afford a two-layer biaxially oriented copolyester film 8 ⁇ m thick with a rough and a smooth side, which can be wound with no difficulty.
- the mechanical properties are:
- the shrinkage, measured after 1 5 min. treatment in a forced air oven at 1 50°C is 0.3% in both MD and TD.
- the water pickup of the film at 50 % r.h. and 25 °C is 0.04 %.
- EXAMPLE 4 (comparative) A monolayer film is prepared from the copolyester according to Example 1 in a manner similar to example 3, except that only one extruder is used. After drawing, it is not possible to wind this film due to wrinkles and blocking.
- the roughness R a of a portion of the film is:
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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EP93900179A EP0674586A4 (en) | 1992-12-09 | 1992-12-09 | A biaxially oriented two-layer copolyester film for capacitor dielectric use. |
PCT/US1992/010709 WO1994013482A1 (en) | 1992-12-09 | 1992-12-09 | A biaxially oriented two-layer copolyester film for capacitor dielectric use |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/US1992/010709 WO1994013482A1 (en) | 1992-12-09 | 1992-12-09 | A biaxially oriented two-layer copolyester film for capacitor dielectric use |
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WO1994013482A1 true WO1994013482A1 (en) | 1994-06-23 |
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PCT/US1992/010709 WO1994013482A1 (en) | 1992-12-09 | 1992-12-09 | A biaxially oriented two-layer copolyester film for capacitor dielectric use |
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WO (1) | WO1994013482A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0674580A1 (en) * | 1992-12-09 | 1995-10-04 | Hoechst Aktiengesellschaft | Improved biaxially oriented copolyester film for magnetic recording media |
EP0770473A1 (en) * | 1995-10-25 | 1997-05-02 | Hoechst Diafoil GmbH | Polyester compound and film made therefrom |
EP0924050A2 (en) * | 1997-12-18 | 1999-06-23 | Toray Industries, Inc. | A polyester film and a production method thereof |
EP0947982A2 (en) * | 1998-04-01 | 1999-10-06 | Mitsubishi Polyester Film GmbH | Multilayered biaxially oriented polyester film, method of preparation and its use as magnetic tape film |
WO2002070255A1 (en) * | 2001-03-05 | 2002-09-12 | Mitsubishi Polyester Film Gmbh | Amorphous, subduedly colored film made of a bibenzol-modified thermoplastic material, method for the production and use thereof |
WO2002081208A1 (en) * | 2001-02-23 | 2002-10-17 | Mitsubishi Polyester Film Gmbh | Amorphous film consisting of a bibenzol-modified thermoplastic, method for the production thereof and use of the same |
WO2003059995A1 (en) * | 2002-01-10 | 2003-07-24 | Toray Industries, Inc. | Biaxially oriented thermoplastic resin film |
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US3008934A (en) * | 1958-07-28 | 1961-11-14 | American Viscose Corp | Filament and film forming interpolyesters of bibenzoic acid, certain aromatic acids and a dihydric alcohol |
JPS50135333A (en) * | 1974-04-16 | 1975-10-27 | ||
JPS57189823A (en) * | 1981-05-20 | 1982-11-22 | Toray Ind Inc | Production of polyester film |
EP0580093B1 (en) * | 1992-07-22 | 1998-07-29 | Hoechst Aktiengesellschaft | Biaxially oriented film comprising layers of polyethylennaphthalate bibenzoate (PENBB), process for preparing these films and application thereof |
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1992
- 1992-12-09 WO PCT/US1992/010709 patent/WO1994013482A1/en not_active Application Discontinuation
- 1992-12-09 EP EP93900179A patent/EP0674586A4/en not_active Withdrawn
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US4568599A (en) * | 1982-03-10 | 1986-02-04 | Toray Industries, Inc. | Laminated film and magnetic recording medium made therewith |
US4619869A (en) * | 1983-03-30 | 1986-10-28 | Teijin Limited | Biaxially oriented polyester film |
US4833024A (en) * | 1987-04-03 | 1989-05-23 | W. R. Grace & Co. | Low shrink energy films |
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Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0674580A4 (en) * | 1992-12-09 | 1995-11-22 | Hoechst Ag | Improved biaxially oriented copolyester film for magnetic recording media. |
EP0674580A1 (en) * | 1992-12-09 | 1995-10-04 | Hoechst Aktiengesellschaft | Improved biaxially oriented copolyester film for magnetic recording media |
US6106926A (en) * | 1995-10-25 | 2000-08-22 | Mitsubishi Polyester Film Gmbh | Thermoplastic raw material and film produced therefrom |
EP0770473A1 (en) * | 1995-10-25 | 1997-05-02 | Hoechst Diafoil GmbH | Polyester compound and film made therefrom |
EP0924050A3 (en) * | 1997-12-18 | 2000-05-03 | Toray Industries, Inc. | A polyester film and a production method thereof |
KR100550081B1 (en) * | 1997-12-18 | 2006-10-24 | 도레이 가부시끼가이샤 | Polyester film and manufacturing method |
EP0924050A2 (en) * | 1997-12-18 | 1999-06-23 | Toray Industries, Inc. | A polyester film and a production method thereof |
US6517762B1 (en) | 1997-12-18 | 2003-02-11 | Toray Industries, Inc. | Polyester film and production method thereof |
US7214339B2 (en) | 1997-12-18 | 2007-05-08 | Toray Industries, Inc. | Polyester film and a production method thereof |
EP0947982A3 (en) * | 1998-04-01 | 2000-02-23 | Mitsubishi Polyester Film GmbH | Multilayered biaxially oriented polyester film, method of preparation and its use as magnetic tape film |
EP0947982A2 (en) * | 1998-04-01 | 1999-10-06 | Mitsubishi Polyester Film GmbH | Multilayered biaxially oriented polyester film, method of preparation and its use as magnetic tape film |
US6551686B1 (en) | 1998-04-01 | 2003-04-22 | Mitsubishi Polyester Film Gmbh | Biaxially oriented polyester film having more than one layer, process for its production, and its use as magnetic tape film |
WO2002081208A1 (en) * | 2001-02-23 | 2002-10-17 | Mitsubishi Polyester Film Gmbh | Amorphous film consisting of a bibenzol-modified thermoplastic, method for the production thereof and use of the same |
WO2002070255A1 (en) * | 2001-03-05 | 2002-09-12 | Mitsubishi Polyester Film Gmbh | Amorphous, subduedly colored film made of a bibenzol-modified thermoplastic material, method for the production and use thereof |
WO2003059995A1 (en) * | 2002-01-10 | 2003-07-24 | Toray Industries, Inc. | Biaxially oriented thermoplastic resin film |
US7384690B2 (en) | 2002-01-10 | 2008-06-10 | Toray Industries, Inc. | Biaxially oriented thermoplastic resin film |
Also Published As
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EP0674586A1 (en) | 1995-10-04 |
EP0674586A4 (en) | 1996-02-28 |
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