CA2222511A1 - Multilayer polymer film with additional coatings or layers - Google Patents
Multilayer polymer film with additional coatings or layers Download PDFInfo
- Publication number
- CA2222511A1 CA2222511A1 CA002222511A CA2222511A CA2222511A1 CA 2222511 A1 CA2222511 A1 CA 2222511A1 CA 002222511 A CA002222511 A CA 002222511A CA 2222511 A CA2222511 A CA 2222511A CA 2222511 A1 CA2222511 A1 CA 2222511A1
- Authority
- CA
- Canada
- Prior art keywords
- layers
- film
- percent
- multilayer
- optical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 229920006254 polymer film Polymers 0.000 title abstract description 5
- 238000000576 coating method Methods 0.000 title description 6
- 230000003287 optical effect Effects 0.000 claims abstract description 76
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 103
- 239000000463 material Substances 0.000 claims description 42
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 39
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 35
- -1 polyethylene naphthalate Polymers 0.000 claims description 24
- 239000012788 optical film Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 7
- 229920001634 Copolyester Polymers 0.000 claims 1
- 125000005487 naphthalate group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 139
- 238000000034 method Methods 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 12
- 229920000728 polyester Polymers 0.000 description 12
- 238000002310 reflectometry Methods 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 8
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 7
- 230000008033 biological extinction Effects 0.000 description 7
- 229940117389 dichlorobenzene Drugs 0.000 description 7
- 238000001429 visible spectrum Methods 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000012748 slip agent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- SKTKMAWOMQFTNS-UHFFFAOYSA-N 6-methoxycarbonylnaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)OC)=CC=C21 SKTKMAWOMQFTNS-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 101100345589 Mus musculus Mical1 gene Proteins 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002178 crystalline material Substances 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 102000003800 Selectins Human genes 0.000 description 1
- 108090000184 Selectins Proteins 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920009441 perflouroethylene propylene Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- AAEVYOVXGOFMJO-UHFFFAOYSA-N prometryn Chemical compound CSC1=NC(NC(C)C)=NC(NC(C)C)=N1 AAEVYOVXGOFMJO-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
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- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/08—Mirrors
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/28—Interference filters
- G02B5/285—Interference filters comprising deposited thin solid films
- G02B5/287—Interference filters comprising deposited thin solid films comprising at least one layer of organic material
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
- G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
- G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
-
- 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
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
- B32B2551/00—Optical elements
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- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/91—Product with molecular orientation
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- 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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
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- 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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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- 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.]
Abstract
A multilayer polymer film has an optical stack including a plurality of alternating polymer layers with skin layers having mechanical, optical, or chemical properties differing from those of the layers in the optical stack.
Description
CA 02222~11 1997-11-26 WO 97/01440 PCT/US96t10691 MULTILAYER POLYMER FILM
WIT~ ADDITIONAL COATINGS OR LAYERS
Background of the Invention Multilayer optical stacks are well-known for providing a wide variety of optical properties. Such multilayer stacks may act as reflective polarizers or mirrors, reflecting light of all polarizations. They may also function as wavelength selective reflectors such as "cold mirrors" that reflect visible light but l,~r,smi~ infrared or "hot mirrors" that transmit visible and reflect infrared.
Examples of a wide variety of multilayer stacks that may be constructed are inçluded in United States Patent Application 08/402,041 filed March 10, 1995.
A problem with multilayer stacks as known in the art is that the stacks themselves may not have all of the physical, chemical, or optical properties desired. Some way of otherwise supplying these desirable properties would therefore be useful.
Summary of the Invention According to one embodiment of the invention a multilayer film has adhered to one or both of its major surfaces at least one additional layer selected for mPçh~nical, chemical, or optical properties that differ from the properties of the materials of the layers of the optical stack.
According to another embodiment of the invention a multilayer film has adhered to one or both of its surfaces an additional layer that will protect the multilayer optical stack.
Brief Description of the Drawings Figures IA, IB, and 2 show the preferred multilayer optical film;
Figures 3 through 8 show trancmis~ion spectra for the multilayer optical films of Examples I through 6;
CA 02222~11 1997-11-26 Figure 9 shows a multilayer film of the invention having an ~dition~l layer adhered to one of its major surfaces, Figure 10 shows a multilayer film acco,di-,g to the invention having additional layers adhered to both of its major surfaces; and Figure 11 shows a multilayer film having one additional layer adhered to one of its major surfaces and two additional layers adhered to its other ma~or surface.
Detailed Description Multilayer Optical Film The advantages, characteristics and m~nllf~ctllring of multilayer optical films are most completely described in the above-mentioned copending andcommonly-~csigned US Patent Application 08/402,041, filed March 10, 1995, titledOPTICAL FILM, which is incorporated herein by reference. The multilayer optical film is useful, for example, as highly efficient mirrors and/or polarizers. A relatively brief description of the properties and characteristics of the multilayer optical film is presented below followed by a description of illustrative embodiments of bac~light systems using the multilayer optical film according to the present invention.
Multilayer optical films as used in conjunction with the present invention exhibit relatively low absorption of incident light, as well as high reflectivity for off-axis as well as normal light rays. These properties generally hold whether the films are used for pure reflection or reflective polarization of light. The unique properties and advantages of the multilayer optical film provides an opportunity to design highly-efficient backlight systems which exhibit low absorption losses when compared to known b~cl~light systems.
An exemplary multilayer optical film of the present invention as illustrated in Figures lA and lB includes a multilayer stack 10 having alternating layers of at least two materials 12 and 14. At least one of the materials has the property of stress induced birefringence, such that the index of refraction (n) of the material is affected by the stretching process. Figure IA shows an exemplary CA 02222~11 1997-11-26 multilayer stack before the stretching process in which both materials have the same index of refraction. Light ray 13 experiences relatively little change in index of refraction and passes through the stack. In Figure IB, the same stack has been stretched, thus h~c,easil.g the index of refraction of material 12. The di~lence in 5 refractive index at each boundary between layers will cause part of ray lS to be reflected By stretching the multilayer stack over a range of uniaxial to biaxialorientation, a film is created with a range of reflectivities for di~lelllly oriented plane-polarized inciclent light. The multilayer stack can thus be made useful asreflective polarizers or mirrors.
Multilayer optical films constructed according to the present invention exhibit a Brewster angle (the angle at which reflectance goes to zero for light inridrnt at any of the layer interfaces) which is very large or is nonexistent for the polymer layer interfaces. In contrast, known multilayer polymer films exhibit relatively small Brewster angles at layer interfaces, resulting in tr~ncmicsion of light 15 and/or undesirable iridesc~nce. The multilayer optical films according to the present invention, however, allow for the construction of mirrors and polarizers whose reflectivity for p polarized light decrease slowly with angle of incidence, are independent of angle of incidenre, or increase with angle of inridence away fromthe normal. As a result, multilayer stacks having high reflectivity for both s and p 20 polarized light over a wide bandwidth, and over a wide range of angles can be achieved.
Figure 2 shows two layers of a multilayer stack, and indicates the three dimensional indices of refraction for each layer. The indices of refraction for each layer are nlx, nly, and nlz for layer 102, and n2x, n2y, and n2z for layer 104.
25 The relationships between the indices of refraction in each film layer to each other and to those of the other layers in the film stack determine the reflectance behavior of the multilayer stack at any angle of incidence, from any ~7imllth~1 direction. The principles and design considerations described in US Patent Application 08/402,041 can be applied to create multilayer stacks having the desired optical effects for a 30 wide variety of circllmct~nces and applications. The indices of refraction of the CA 02222~11 1997-11-26 layers in the multilayer stack can be manipulated and tailored to produce the desired optical properties.
Referring again to Figure lB, the multilayer stack 10 can include tens, hundreds or thous~nrlc of layers, and each layer can be made from any of a5 number of di~~ materials. The characteristics which deterrnine the choice of materials for a particular stack depend upon the desired optical pe~rollllance of the stack. The stack can contain as many materials as there are layers in the stack. For ease of m~nllf~ct~lre, preferred optical thin film stacks contain only a few different materials.
The boundaries between the materials, or chemically identical materials with dirreren~ physical properties, can be abrupt or gradual. Except for some simple cases with analytical solutions, analysis of the latter type of stratified media with continlloucly varying index is usually treated as a much larger number of thinner uniform layers having abrupt boundaries but with only a small change in 15 properties between adjacent layers.
The p~efe~ed multilayer stack is comprised of low/high index pairs of film layers, wherein each low/high index pair of layers has a col..bined optical th;~n~ss of 1/2 the center wavelength of the band it ls designed to reflect. Stacks of such films are commonly referred to as quarterwave stacks. For multilayer 20 optical films concerned with the visible and the near infrared wavelengths, aquarterwave stack design results in each of the layers in the multilayer stack having an average thickness of not more than 0.5 microns.
In those applications where reflective films (e.g. mirrors) are desired, the desired average tr~ncmission for light of each polarization and plane of 25 inr.idence generally depends upon the intended use of the reflective film. One way to produce a multilayer mirror film is to biaxially stretch a multilayer stack. For a high efficiency reflective film, average tr~ncmiccion along each stretch direction at normal incidence over the visible spectrum (380-750 nm) is desirably less than 10 percent (reflectance greater than 90 percent), preferably less than 5 percent 30 (reflect~nce greater than 95 percent), more preferably less than 2 percent (reflectance greater than 98 percent), and even more preferably less than l percent CA 02222~11 1997-11-26 (reflect~nce greater than 99 percent). The average tr~ncmiccion at 60 degrees from the normal from 380-750 nm is desirably less than 20 percent (reflectance greater than 80 percent), preferably less than 10 percent (reflectance greater than 90 percent), more preferably less than 5 percent (reflectance greater than 95 percent), 5 and even more preferably less than 2 percent (reflectance greater than 98 percent), and even more preferably less than 1 percent (reflectance greater than 99 percent).
In addition, asymmetric reflective films may be desirable for certain applications. In that case, average trancmiCcion along one stretch direction may be desirably less than~ for example, 50 percent, while the average trancmicsion along 10 the other stretch direction may be desirably less than, for example 20 percent, over a bandwidth of, for example, the visible spectrum (380-750 nm), or over the visible spectrum and into the near infrared (e.g., 380-850 nm).
Multilayer optical films can also be designed to operate as reflective polarizers. One way to produce a multilayer reflective polarizer is to uniaxially 15 stretch a multilayer stack. The resulting reflective polarizers have high reflectivity for light with its plane of polarization parallel to one axis (in the stretch direction) for a broad range of angles of incidence, and cimnlt~neously have low reflectivity and high tr~ncmiccivity for light with its plane of polarization parallel to the other axxis (in the non-stretch direction) for a broad range of angles of incidence. By 20 controlling the three indices of refraction of each film, nx, ny and nz, the desired polarizer behavior can be obtained.
For many applications, the ideal reflecting polarizer has high reflectance along one axis (the so-called extinction axis) and zero reflectance along the other (the so-called trAnsmicsion axis), at all angles of incidence. For the25 tr~ncmiccion axis of a polarizer, it generally desirable to nlaxil--i~e trancmiccion of light polarized in the direction of the tr~ncmiccion axis over the bandwidth of interest and also over the range of angles of interest.
The average tr~ncmicsion at normal incidence for a polarizer in the tr~ncmiCcion axis across the visible spectrum (380-750 nm for a bandwidth of 30030 nm) is desirably at least 50 percent, preferably at least 70 percent, more preferably at least 80 percent, and even more preferably at least 90 percent. The average CA 02222~11 1997-11-26 l,~h~,..;ccion at 60 degrees from the normal (measured along the tr~ncmicsion axis for p-polarized light) for a polarizer from 380-750 nm is desirably at least 50 percent, preferably at least 70 percent, more preferably at least 80 percent, and even more preferably at least 90 percent.
The average tr~ncmicsion for a multilayer reflective polarizer at normal in~idçnce for light polarized in the direction of the extinction axis across the visible spectrum (380-750 nm for a bandwidth of 300 nm) is desirably at less than 50 percent, preferably less than 30 percent, more preferably less than 15 percent, and even more plefe-ably less than 5 percent. The average tr~ncmiccion at 60 degrees from the normal (measured along the trancmicsion axis for p-polarized light) for a polarizer for light polarized in the direction of the extinction axis from 380-750 nm is desirably less than 50 percent, preferably less than 30 percent, more preferably less than 15 percent, and even more preferably less than 5 percent.
For certain applications, high reflectivity for p-polarized light with its plane of polarization parallel to the tr~ncmicsion axis at off-normal angles arepre~,.ed. The average reflectivity for light polarized along the tr~ncmission axis should be more than 20 percent at an angle of at least 20 degrees from the normal.
In addition, although reflective polarizing films and asymmetric reflective films are dicc~csed separately herein, it should be understood that two or more of such films could be provided to reflect substantially all light incident on them (provided they are properly oriented with respect to each other to do so).
This construction is typically desired when the multilayer optical film is used as a reflector in a bacL light system according to the present invention.
If some reflectivity occurs along the tr~ncmission axis, the efficiency of the polarizer at off-normal angles may be reduced. If the reflectivity along the trancmicsion axis is different for various wavelengths, color may be introduced into the l.~nsl,lilled light. One way to measure the color is to determine the root mean square (RMS) value of the tr~ncmicsivity at a selected angle or angles over the wavelength range of interest. The percent RMS color, CR~S, can be determined according to the equation:
CA 02222~11 1997-11-26 ¦((T- T) ) d,l r _ 1l ~'RMS - -- -where the range 11 to 12 is the wavelength range, or bandwidth, of interest, T is the tr~ncmicsivity along the tr~ncmicsion axis, and T is the average tr~ncmiccivity along the tr~ncmission axis in the wavelength range of interest. For applications where a low color polarizer is desirable, the percent RMS color should be less than 10 percent, preferably less than 8 percent, more preferably less than 3.5 percent, and even more plefel~bly less than 2 percent at an angle of at least 30 degrees from the normal, preferably at least 45 degrees from the normal, and even more preferably at least 60 degrees from the normal.
Preferably, a reflective polarizer combines the desired percent RMS
color along the tr~ncmission axis for the particular application with the desired amount of reflectivity along the extinction axis across the bandwidth of interest.
For polarizers having a bandwidth in the visible range (400-700 nm, or a bandwidth of 300 nm), average tr~ncmic.cion along the extinction axis at normal incidence is desirably less than 40 percent, more desirably less than 25 percent, preferably less than 15 percent, more preferably less than 5 percent and even more preferably less than 3 percent.
Materials Selection and Processin~
With the design considerations described in the above mentioned US
Patent Application 08/402,041, one of ordinary skill will readily appreciate that a wide variety of materials can be used to form multilayer reflective films or polarizers according to the invention when processed under conditions selected to yield thedesired refractive index relationships. The desired refractive index relationships can be achieved in a variety of ways, incl-lding stretching during or after film formation (e.g., in the case of organic polymers), extruding (e.g., in the case of liquid crystalline materials), or coating. In addition, it is pre~e,-ed that the two materials have similar rheological properties (e.g., melt viscosities) such that they can be co-extruded.
CA 02222~11 1997-11-26 In general, appropriate cor"binalions may be achieved by selecting, as the first material, a crystalline or semi-crystalline, or liquid crystalline material, preferably a polymer. The second material, in turn, may be crystalline, semi-crystalline, or amorphous. The second material may have a bil~flingel1ce opposite 5 to or the same as that of the first material. Or, the second material may have no birefringence. It should be understood that in the polymer art it is generally recognized that polymers are typically not entirely crystalline, and thelt;Çore in the context of the present invention, crystalline or semi-crystalline polymers refer to those polymers that are not amorphous and includ~s any of those materials 10 commonly referred to as crystalline, partially crystalline, semi-crystalline, etc. The second material may have a birefringence opposite to or the same as that of the first material. Or, the second material may have no birefringence.
Specific examples of suitable materials include polyethylene naphth~l~te (PEN) and isomers thereof (e.g., 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-PEN), 15 polyalkylene terephth~l~tes (e.g., polyethylene terephthalate, polybutylene terephth~l~te, and poly-1,4-cyclohex~nerlimethylene terephthalate), polyimides (e.g., polyacrylic imides), polyetherimides, atactic polystyrene, polycarbonates, polymethacrylates (e.g., polyisobutyl methacrylate, polypropylmethacrylate, polyethylmeth~crylate, and polymethylmethacrylate), polyacrylates (e.g., 20 polybutylacrylate and polymethylacrylate), syndiotactic polystyrene (sPS), syndiotactic poly-alpha-methyl styrene, syndiotactic polydichlorostyrene, copolymers and blends of any of these polystyrenes, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, and cellulose nitrate), polyalkylene polymers (e.g., polyethylene, polypropylene, 25 polybutylene, polyisobutylene, and poly(4-methyl)pentene), fluorinated polymers (e.g., perfluoroalkoxy resins, polytetrafluoroethylene, fluorinated ethylene-propylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene), chlorinated polymers (e.g., polyvinylidene chloride and polyvinylchloride), polysulfones, polyethersulfones, polyacrylonitrile, 30 polyamides, silicone resins, epoxy resins, polyvinylacetate, polyether-amides, ionomeric resins, elastomers (e.g., polybutadiene, polyisoprene, and neoprene), and CA 02222~11 1997-11-26 WO 97/01440 PCTtUS96/10691 polyurethanes. Also suitable are copolymers, e.g., copolymers of PEN (e.g., copolymers of 2,6-, 1,4-, 1,5-, 2,7-, and/or 2,3-naphthalene dicarboxylic acid, or esters thereof, with (a) terephthalic acid, or esters thereof; (b) isophthalic acid, or esters thereof; (c) phthalic acid, or esters thereof; (d) alkane glycols; (e) cycloalkane glycols (e.g., cyclohexane ~imPth~ne diol); (f) alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxylic acids (e.g., cyclohexane dicarboxylic acid)), copolymers of polyalkylene terephth~l~tec (e.g., copolymers of terephthalic acid, or esters thereof, with (a) n~phth~l~ne dicarboxylic acid, or esters thereof; (b) isophthalic acid, or esters thereof; (c) phthalic acid, or esters thereof; (d) alkane glycols; (e) cycloalkane glycols (e.g., cyclohexane tlimeth~nel diol); (f) alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxylic acids (e.g., cyclohexane dicarboxylic acid)), and styrene copolymers (e.g., styrene-butadiene copolymers and styrene-acrylonitrile copolymers), 4,4'-bibenzoic acid and ethylene glycol. In addition, each individual layer may include blends of two or more of the above-described polymers or copolymers (e.g., blends of sPS and atactic polystyrene). The coPEN desc,;bed may also be a blend of pellets where at least one component is a polymer based on n~rhth~ltone dicarboxylic acid and other components are other polyesters or polycarbonates, such as a PET, a PEN or a coPEN.
Particularly prefe~,ed combinations of layers in the case of polarizers include PEN/coPEN, polyethylene terephth~l~te (PET)/coPEN, PEN/sPS, PET/sPS, PEN/Estar, and PET/Estar, where "coPEN" refers to a copolymer or blend based upon naphthalene dicarboxylic acid (as described above) and Estar ispolycyclohexanedimethylene terephthalate commercially available from F~ctm~n Chemical Co.
Particularly preferred combinations of layers in the case of reflective films include PET/Ecdel, PEN/Ecdel, PEN/sPS, PEN/THV, PEN/co-PET, and PET/sPS, where "co-PET" refers to a copolymer or blend based upon terephthalic acid (as described above), Ecdel is a thermoplastic polyester commercially available from F~ctm~n Chemical Co., and THV is a fluoropolymer co~-l...elcially available30 from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota.
CA 02222~11 1997-11-26 WO 97/01440 PCTrUS96/1069 The number of layers in the film is selected to achieve the desired optical properties using the minimllm number of layers for reasons of film thickness, flexibility and economy. In the case of both polarizers and reflective films, the number of layers is preferably less than 10,000, more preferably less than 5,000, and 5even more preferably less than 2,000.
As tliccucsed above, the ability to achieve the desired relationships among the various indices of refraction (and thus the optical propellies of the multilayer film) is influenced by the processing conditions used to prepare the multilayer film. In the case of organic polymers which can be oriented by 10stretching, the films are generally prepared by co-extruding the individual polymers to form a multilayer film and then orienting the film by stretching at a selected temperature, optionally followed by heat-setting at a selected temperature.
Alternatively, the extrusion and orientation steps may be performed simult~neously.
In the case of polarizers, the film is stretched substantially in one direction (uniaxial 15orientation), while in the case of reflective films the film is stretched subslalllially in two directions (biaxial orientation).
The film may be allowed to dimensionally relax in the cross-stretch direction from the natural reduction in cross-stretch (equal to the square root of the stretch ratio); it may simply be constrained to limit any substantial change in cross-20stretch dimension; or it may be actively stretched in the cross-stretch dimension.
The film may be stretched in the machine direction, as with a length orienter, or in width using a tenter.
The pre-stretch temperature, stretch temperature, stretch rate, stretch ratio, heat set temperature, heat set time, heat set relaxation, and cross-25stretch relaxation are selected to yield a multilayer film having the desired refractive index relationship. These variables are interdependent; thus, for example, a relatively low stretch rate could be used if coupled with, e.g., a relatively low stretch temperature. It will be apparent to one of ordinary skill how to select the appiopliate combination of these variables to achieve the desired multilayer film. In 30general, however, a stretch ratio in the range from 1:2 to 1:10 (more preferably 1:3 CA 02222~11 1997-11-26 to 1:7) in the stretch direction and from 1:0.2 to 1:10 (more ple~,~bly from 1:0.2 to 1:7) orthogonal to the stretch direction is ple~.,ed.
Suitable multilayer films may also be prepared using techniques such as spin coating (e.g., as described in Boese et al., J. Polym. Sci.: Part B, 30:1321 5 (1992) for birefringent polyimides, and vacuum deposition (e.g., as described by Zang et. al., Appl. Phys. Letters, 59:823 (1991) for crystalline organic compounds;
the latter technique is particularly useful for certain combinations of crystalline organic compounds and inorganic materials.
Exemplary multilayer reflective mirror films and multilayer reflective 10 polarizers will now be described in the following examples.
Example I
PEN:THV 500~ 449. Mirror) A coextruded film co~ inil-Sg 449 layers was made by extruding the 15 cast web in one operation and later orienting the film in a laboratory film-sl~e~cl~h~g appa,al~s. A Polyethylene naphth~l~te (PEN) with an Intrinsic Viscosity of 0.53 dVg (60 weight percent phenoW0 weight percent dichlorobenzene) was delivered by one extruder at a rate of 56 pounds per hour and THV 500 (a fluoropolymer available from Minnesota Mining and M~nuf~ctlJring Company) was 20 delivered by another extruder at a rate of 11 pounds per hour. The PEN was on the skin layers and 50 percent of the PEN was present in the two skin layers. The feedblock method was used to generate 57 layers which was passed through three multipliers producing an extrudate of 449 layers. The cast web was 20 mils thickand 12 inches wide. The web was later biaxially oriented using a laboratory 25 stretching device that uses a pantograph to grip a square section of film andsimultaneously stretch it in both directions at a uniform rate. A 7.46 cm square of web was loaded into the stretcher at about 100 degrees C and heated to 140 degrees C in 60 seconds. Stretching then commenced at 10 percent/sec (based on original dimloncinns) until the sample was stretched to about 3.5x3.5. Tmme~i~tely 30 after the stretching the sample was cooled by blowing room temperature air at it.
CA 02222~11 1997-11-26 Figure 3 shows the tr~ncmiscion of this multilayer film. Curve (a) shows the response at normal incidence for light polarized in the tr~ncmicsion direction, while curve (b) shows the response at 60 degrees for p-polarized light polarized in the tr~ncmiCcion direction.
Example 2 (PEN.PMMA. 601. Mirror) A coextruded film cont~ining 601 layers was made on a sequential flat-film-making line via a coextrusion process. Polyethylene Naphth~l~te (PEN) with an Intrinsic Viscosity of 0.57 dUg (60 weight percent phenoU40 weight percent dichlorobenzene) was delivered by extruder A at a rate of 114 pounds per hour with 64 pounds per hour going to the feedblock and the rest going to skin layers described below. PMM:A (CP-82 from ICI of Americas) was delivered by extruder B at a rate of 61 pounds per hour with all of it going to the feedblock. PEN was on the skin layers of the ,feedblock. The feedblock method was used to generate 151layers using the feedblock such as those described in US Patent 3,801,429, after the feedblock two symmetric skin layers were coextruded using extruder C metering about 30 pounds per hour of the same type of PEN delivered by extruder A. This extrudate passed through two multipliers producing an extrudate of about 601 layers. US Patent 3,565,985 describes similar coextrusion multipliers.- The extrudate passed through another device that coextruded skin layers at a total rate of 50 pounds per hour of PEN from extruder A. The web was length oriented to a draw ratio of about 3.2 with the web temperature at about 280 degrees F. The film was subsequently preheated to about 310 degrees F in about 38 seconds and drawn in the transverse direction to a draw ratio of about 4.5 at a rate of about 11 percent per second. The film was then heat-set at 440 degrees F with no relaxation allowed. The finished film thickness was about 3 mil.
As seen in Figure 4, curve (a), the bandwidth at normal incidence is about 350 nm with an average in-band extinction of greater than 99 percent. The amount of optical absorption is difficult to measure because of its low value, but is less than I percent. At an incidence angle of 50 percent from the normal both s CA 02222~11 1997-11-26 (curve (b)) and p-polarized (curve (c)) light showed similar extinctions, and the bands were shifted to shorter wavelengths as expected. The red band-edge for s-polarized light is not shifted to the blue as much as for p-polarized light due to the expected larger bandwidth for s-polarized light, and due to the lower index seen by the p-polarized light in the PEN layers.
(PEN:PCTG, 449~ Polarizer) A coextruded film cont~ining 481 layers was made by extruding the cast web in one operation and later orienting the film in a laboratory film-stretching appa~alLIs. The feedblock method was used with a 61 layer feedblock and three (2x) multipliers. Thick skin layers were added between the final multiplier and the die. Polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.47 dl/g (60weight percent phenol/40 weight percent dichlorobenzene) was delivered to the feedblock by one ext~ruder at a rate of 25.0 pounds per hour. Glycol modified polyethylene dimethyl cyclohexane terephthalate (PCTG 5445 from F~ctm~n) was delivered by another extruder at a rate of 25.0 pounds per hour. Another stream of PEN from the above extruder was added as skin layers after the multipliers at a rate of 25.0 pounds per hour. The cast web was 0.007 inches thick and 12 inches wide.The web was layer uniaxially oriented using a laboratory stretching device that uses a pantograph to grip a section of film and stretch it in one direction at a uniform rate while it is allowed to freely relax in the other direction. The sample of web loaded was about 5.40 cm wide (the unconstrained direction) and 7.45 cm long between the g-ippe,~ of the pantograph. The web was loaded into the stretcher atabout 100 degrees C and heated to 135 degrees C for 45 seconds. Stretching was then comm~nced at 20 percent/second (based on original dimensions) until the sample was stretched to about 6:1 (based on gripper to gripper measurements).
Tmme(ii~tely after stretching, the sample was cooled by blowing room temperatureair at it. In the center, the sample was found to relax by a factor of 2Ø
Figure 5 shows the tr~ncmicsion of this multilayer film where curve a shows tr~ncmiscion of light polarized in the non-stretch direction at normal CA 02222~11 1997-11-26 incidçnce, curve b shows tr~ncmission of p-polarized light polarized in the non-stretched direction at 60 degree incidence, and curve c shows the tr~ncmicsion of light polarized in the stretch direction at normal incidence. Average tr~ncmiccion for curve a from 400-700 nm is 89.7 percent, average tr~ncmiCcion for curve b from 400-700 nm is 96.9 percent, and average trancmission for curve c from 400-700 nmis 4.0 percent. Percent RMS color for curve a is 1.05 percent, and percent RMS
color for curve b is 1.44 percent.
(PEN:CoPEN. 601. Polarizer) A coextruded film cont~ining 601 layers was made on a sequential flat-film-making line via a coextrusion process. A Polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.54 dltg (60 weight percent Phenol plus 40 weight percent dichlorobenzene) was delivered by on extruder at a rate of 75 pounds perhour and the coPEN ~was delivered by another extruder at 65 pounds per hour. ThecoPEN was a copolymer of 70 mole percent 2,6 naphthalene dicarboxylate methyl ester, 15 percent dimethyl isophthalate and 15 percent dimethyl terephth~l~te with ethylene glycol. The feedblock method was used to generate 151 layers. The feedblock was dçsigned to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. The PEN skin layers were coextruded on the outside of the optical stack with a total thickness of 8 percent of the coextruded layers. The optical stack was multiplied by two sequçnti~l multipliers. The nominal multiplication ratio of the multipliers were 1.2 and 1.27, respectively. The film was subsequently preheated to 310 degree F in about 40 seconds and drawn in the transverse direction to a drawratio of about 5.0 at a rate of 6 percent per second. The finished film thickness was about 2 mils.
Figure 6 shows the tr~ncmicsion for this multilayer film. Curve a shows trancmiccion of light polarized in the non-stretch direction at normal incirl~nce, curve b shows tr~ncmiscion of p-polarized light at 60 degree incidence, and curve c shows trancrnicsion of light polarized in the stretch direction at normal CA 02222~11 1997-11-26 incidence. Note the very high tr~ncmission of p-polarized light in the non-stretch direction at both normal and 60 degree incidence (80-100 percent). Also note thevery high reflectance of light polarized in the stretched direction in the visible range (400-700 nm) shown by curve c. Reflect~nce is nearly 100 percent between 500 5 and 650 nm.
(PEN:sPS, 481, Polarizer) A 481 layer multilayer film was made from a polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.56 dVg measured in 60 weight percent phenol and 40 weight percent dichlorobenzene purchased from F.actm~n ChPmic~lc and a syndiotactic polystyrene (sPS) homopolymer (weight average molecular weight = 200,000 Daltons, sampled from Dow Corporation). The PEN
was on the outer layers and was extruded at 26 pounds per hour and the sPS at 23pounds per hour. The~ feedblock used produced 61 layers with each of the 61 being approximately the same thickness. After the feedblock three (2x) multipliers were used. Equal thickness skin layers cont~ining the same PEN fed to the feedblock were added after the final multiplier at a total rate of 22 pounds per hour. The web was extruded through a 12 inch wide die to a thickness of about 0.011 inches (0.276 mm). The extrusion temperature was 290 degrees C.
This web was stored at ambient conditions for nine days and then uniaxially oriented on a tenter. The film was preheated to about 320 degrees F (160 degrees C) in about 25 seconds and drawn in the transverse direction to a draw ratio of about 6:1 at a rate of about 28 percent per second. No relaxation was allowed in the stretched direction. The finished film thickness was about 0.0018inches (0.046 mm).
Figure 7 shows the optical performance of this PEN:sPS reflective polarizer containing 481 layers. Curve a shows transmission of light polarized in the non-stretch direction at normal incidence, curve b shows transmission of p-polarized light at 60 degree incidence,.and curve c shows tr~ncmicsion of light polarized in the stretch direction at normal incidence. Note the very high -CA 02222~11 1997-11-26 tr~n~micsion of p-polarized light at both normal and 60 degree inci~ence Averagetr~ncmicsion for curve a over 400-700 nm is 86.2 percent, the average tr~ncmicsion for curve b over 400-700 nm is 79.7 percent. Also note the very high reflect~nce of light polarized in the stretched direction in the visible range (400-700 nm) shown by 5 curve c. The film has an average transmicsion of 1.6 percent for curve c between 400 and 700 nm. The percent RMS color for curve a is 3.2 percent, while the percent RMS color for curve b is 18.2 percent.
(PEN:CoPEN~ 603, Polarizer) A reflecting polarizer comprising 603 layers was made on a sequçnti~l flat-film making line via a coextrusion process. A polyethylene naphth~l~te (PEN) with an intrinsic viscosity of 0.47 dl/g (in 60 weight percent15 phenol plus 40 weight percent dichlorobenzene) was delivered by an extruder at a rate of 83 pounds (38 kg) per hour and the CoPEN was delivered by another extruder at 75 pounds (34 kg) per hour. The CoPEN was a copolymer of 70 mole percent, 2,6 naphthalene dicarboxylate methyl ester, 15 mole percent dimethyl terephthalate, and 15 mole percent dimethyl isophthalate with ethylene glycol. The 20 feedblock method was used to generate 151 layers. The feedblock was designed to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. This optical stack was multiplied by two sequential multipliers. The nominal multiplication ratio of the multipliers was 1.2 and I .4, respectively. Between the final multiplier and the 25 die, skin layers were added composed of the same CoPEN described above, delivered by a third extruder at a total rate of 106 pounds (48 kg) per hour. The film was subsequently preheated to 300 degrees F (150 degrees C) in about 30 seconds and drawn in the transverse direction to a draw ratio of approximately 6 at an initial rate of about 20 percent per second. The finished film thickness was 30app,oxil"ately 0.0035 inch (0.089 mm).
Figure 8 shows the optical performance of the polarizer of Example 6. Curve a shows transmission of light polarized in the non-stretch direction at CA 02222~11 1997-11-26 normal incidçnce, curve b shows tr~ncmicsion of p-polarized light in the nonstretch direction at 50 degree angle of incidence, and curve c shows trancmiCcion of light polarized in the stretch direction at normal incidence. Note the very high tr~ncmiccion of light polarized in the non-stretch direction. Average ~li.nc,n;cs;on for curve a over 400-700 nm is 87 percent. Also note the very high reflectance of light polarized in the stretched direction in the visible range (400-700 nm) shown by curve b. The film has an average tr~ncmiccion of 2.5 percent for curve b between400 and 700 nm. In addition, the percent RMS color of this polarizer is very low.
The percent RMS color for curve b is 5 percent.
While the multilayer optical stacks, as described above, can provide significant and desirable optical properties, other properties, which may be mloc.h~nical, optical, or chemical, are difficult to provide in the optical stack itself without degrading the performance of the optical stack. Such properties may be provided by inclurling,one or more layers with the optical stack that provide these properties while not contributing to the primary optical function of the optical stack itself. Since these layers are typically provided on the major surfaces of the optical stack, they are often known as "skin layers."
A skin layer may be coextruded on one or both major surfaces of the multilayer stack during its rn~n~lf~cture to protect the multilayer stack from the high shear along the feedblock and die walls, and often an outer layer with the desired chemical or physical properties can be obtained by mixing an additive, such as, for example, a UV stabilizer, into the polymer melt that makes up the skin layer, and coextruding the skin layer with altered properties onto one or both sides of themultilayer optical stack during m~nllf~cture. Alternately, additional layers may be coextruded on the outside of the skin layers during m~nllf~cture of the multilayer film; they may be coated onto the multilayer film in a separate coating operation; or they may be laminated to the multilayer film as a separate film, foil, or rigid or semi-rigid reinforcing substrate such as polyester (PET), acrylic (PMMA), polycarbonate, metal, or glass. Adhesives useful for l~min~ting the multilayer polymer film to another surface include both optically clear and diffuse adhesives CA 02222~11 1997-11-26 and include both pressure sensitive and non-pressure sensitive adhesives. Pressure sensitive adhesives are normally tacky at room te"-pe,~ re and can be adhered to a surface by application of, at most, light finger pressure, while non-pressure sensitive adhesives include solvent, heat, or radiation activated adhesive systems. Examples 5 of adhesives useful in the present invention include those based on general compositions of polyacrylate; polyvinyl ether; diene-con~ -;ng rubber such as natural rubber, polyisoprene, and polyisobutylene; polychloropl~ne; butyl rubber;
but~diene-acrylonitrile polymer; thermoplastic elastomer;. block copolymers such as styrene-isoprene and styrene-isoprene-styrene block copolymers, ethylene-10 propylene-diene polymers, and styrene-butadiene polymer; poly-alpha-olefin;
amorphous polyolefin; silicone; ethylene-containing copolymer such as ethylene vinyl acetate, ethylacrylate, and ethyl methacrylate; polyurethane; polyamide; epoxy;
polyvinylpyrrolidone and vinylpyrrolidone copolymers; polyesters; and mixtures of the above. Additionally, the adhesives can contain additives such as t~ç~ifiPrs,15 plasticizers, fillers, an,tioxidants, stabilizers, pigments, difflsing particles, curatives, biocides, and solvents. Preferred adhesives useful in the present invention include VITEL 3300, a hot melt adhesive available from Shell Chemical Co. (Akron, OH), or an acrylic pressure sensitive adhesive such as a 90/10 IOA/AA acrylic adhesive from Minnesota Mining and M~nuf~ctllring Company, St. Paul, Minnesota. When a 20 l~..,;n~ling adhesive is used to adhere the multilayer film to another surface, the adhesive composition and thickness are preferably selected so as not to interfere with the optical properties of the multilayer stack. For example, when l~min~ting additional layers to a multilayer polymer polarizer or mirror wherein a high degree of tr~ncmiccion is desired, the i~min~ting adhesive should be optically clear in the 25 wavelength region that the polarizer or mirror is designed to be transparent.Figures 10 and 11 illustrate multilayer stacks having respectively one and two additional layers, respectively. Figures 10 and 11 will be used below todescribe a variety of additional layers that could be applied.
One area in which a skin layer having differing mechanical properties 30 is desirable relates particularly to uniaxially oriented multilayer optical stacks, such as reflective polarizers. Such stacks often tend to show a low tear recict~nce in the CA 02222~11 1997-11-26 principal draw direction. This can lead to reduced yields during the m~mlf~ct~lring process or to subsequent breakage of the film during h~n~ling In order to resistthis, tear resistant layers may be adhered to the outer major surfaces of the optical stack. These tough layers may be of any appro~l iate material and could even be the same as one of the materials used in the optical stack. Factors to be considered in selectin~ a material for a tear resistant layer include percent elongation to break, Young's modulus, tear strength, adhesion to interior layers, percent ~ nc~ Ance and absorbance in an ele.;l,o~ netic bandwidth of interest, optical clarity or haze, refractive indices as a function of frequency, texture and roughn~ss, melt thermal stability, molecular weight distribution, melt rheology and coextrudability, miscibility and rate of inter-diffusion between materials in the tough and optical layers, viscoelastic response, relaxation and crystallization behavior under draw conditions, thermal stability at use temperatures, weatherability, ability to adhere to coatings and permeability to various gases and solvents. Of course, as previously stated, it is importa,nt that the material chosen not have optical properties deleterious to those of the optical stack. They may be applied during the m~nnf~cturing process or later coated onto or laminated to the optical stack.
Adhering these layers to the optical stack during the manufacturing process, such as by a coextrusion process, provides the advantage that the optical stack is protected during the m~nuf~ctllring process.
Using Figure 10 to illustrate this aspect of the invention, a multilayer optical stack having tear resistant layers 400 is shown. Film 400 includes an optical stack 410. Optical stack 410 includes alternating layers 412 and 414 of two polymers having differing optical properties. Attached to the major surfaces of optical stack 410 are tear resistant layers 416 and 418. It should be noted that, although layers 416 and 418 are shown in Figure 10 as thicker than layers 412 and 414, Figure 10 is not to scale for a generally preferred embodiment. In general it is desirable that each of layers 416 and 418 have a thickness greater than 5 percent of the thickness of the optical stack. It is plerel,ed that each of layers 416 and 418 have a thickness in the range of 5 percent to 60 percent of the thickness of theoptical stack to provide tear resistance without unnecessarily increasing the amount _19_ CA 02222=,11 1997-11-26 WO 97/01440 PCTtUS96/10691 of material used. Thus, if the optical stack has 600 layers, in such a plefelledembodiment the thickness of each of tear resistant layers 416 and 418 would be equal to the thickness of 30 to 360 of the layers of the stack. In a more pl~r~ d embodiment each ofthe tear le~ Lanl layers 416 and 418 would have a thickness in5 the range of 30 percent to S0 percent of that of the optical stack.
In a particularly desirable embodiment, tear resistant outer layers may be of one of the same materials used in alternating layers 412 and 414. In particular, it has been discovered that in a reflective polarizer comprising alternating layers of PEN and coPEN, tear resistant outer layers of coPEN may be coextruded 10 during the manufacturing process.
Example 7 A multilayered composite of alternating PEN and coPEN layers to form a reflective polarizer was coextruded with thick skin layers of coPEN to form 15 a tear resistant reflective polarizer. A coextruded film conl~inil-v 603 layers was made on a sequential flat-film extruder. A polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.47 dl/g (in 60 weight percent phenol plus 40 weight percent dichlorobenzene) was delivered by an extruder at a rate of 86 pounds per hour and the coPEN was delivered by another extruder at 78 pounds per hour. The coPEN
20 was a copolymer of 70 mole percent, 2,6 naphthalene dicarboxylate methyl ester and 30 percent dimethyl terephthalate with ethylene glycol. The feedblock extruded 151 layers. The feedblock was designed to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. This optical stack was multiplied by two25 sequential multipliers. The nominal multiplication ratio of the multipliers was 1.2 and 1.27, respectively. Between the final multipliers and the die, composed of coPEN as described above, layers were added. These layers were charged and delivered by a third extruder at a total rate of 187 pounds per hour. The film with the additional coPEN outer layers was preheated to 320 degrees F in about 40 30 seconds and drawn in the transverse direction to a draw ratio of applo~illlately 6 at an initial rate of about 20 percent per second. The finished film had a thickness of CA 02222~11 1997-11-26 WO 97/01440 PCT/US96t10691 app~ ely 100 ~lm inclutling an inner multilayered optical stack of about 50 ~m thickness and two exterior outer layers (one on each side of the film) of about 25 ~Lm thicL n-oss~ each. Tear resist~nce improved over the case without skins allowing the creation of wound rolls of tough reflective polarizer. Specifically, tear reCi~t~nce was measured on films made according to this example and on film madeunder similar conditions but without coPEN skin layers using a trouser tear testalong the principal draw direction, according to ASTM D-1938. Average film thir~nesses were 100 ~Lm and 48 llm, respectively. The average tear force valueswere 60.2 and 2.9 grams force, with standard deviations of 4.44 and 0.57 grams force, respectively. Analysis of the coPEN skin layers showed low orientation with indices of refraction of 1.63, 1.62, and 1.61 at 633 nm. Good interlayer adhesion was demonstrated by the difficulty of cleanly separating the construction. For further comparison a 48 ~Im optical stack having 3.8 ~lm outer layers of PEN wastested and found to have an average tear force of 2.8 grams with a standard deviation of 1.07.
The appearance and/or performance of a film may be altered by including a skin layer having a dye or pigment that absorbs in one or more selected regions of the spectrum. This can include portions or all of the visible spectrum as well as ultraviolet and infrared. Of course, if all of the visible spectrum is absorbed, the layer will be opaque. These can be selected in order to change the appare"l color of light transmitted or reflected by the film. They can also be used to compliment the properties of the film, particularly where the film transmits some frequencies while reflecting others. The use of an UV absorptive material in a cover layer is particularly desirable because it may be used to protect the inner layers that may be unstable when exposed to UV radiation. Thus, Figure 9 illustrates such a film with layer 316 representing a layer containing an electrom~gnetic absorbingmaterial.
Similar to the electrom~gnetic absorbing materials described above, a fluol esce." material could be incorporated in layer 316 of Figure 9 or one or both of layers 416 and 418 of Figure 9. Fluorescent materials absorb electrom~gnetic energy in the ultraviolet region of the spectrum and reemit in the visible. Desirable CA 02222~11 1997-11-26 fluorescelll materials include hindered amine light stabilizers (HALS) and are desc,;l)ed in more detail in United States Patent Application 08/34S,608, filed November 28, 1994, the disclosure of which is incorporated herein by reference.
Pressure sensitive adhesives form another desirable class of materials 5 that may be applied to a multilayer stack as layer 316 of Figure 9 or one of layers 416 or 418 of Figure 10. Generally pressure sensitive adhesives may be applied when the optical stack is inten~ed for later l~min~tion to another material, such as a glass or metal substrate.
Another material that could be incorporated in a skin layer such as layer 316 or one of layers 416 or 418 would be a slip agent. A slip agent will make the film easier to handle during the m~n~lf~cturing process. Typically a slip agent would be used with a mirror film rather than a film intended to ll~hSIIIil a portion of the light striking it. The side inclu~ling the slip agent would typically be the side inten-led to be l~min~ted to a supporting substrate in order to prevent the slip agent 15 from increasing haze associated with the reflection.
Another type of additional layer that could be used is a protective layer. Such a layer could be abrasion resistant or resistant to weathering and/or .hPmic~l action. Such coatingc would be particularly useful in situations where the multilayer film is to be exposed to a harsh or corrosive environment. Examples of 20 abrasion-resistant or hard coatings include acrylic hardcoats such as Acryloid A-l l and Paraloid K-120N, available from Rohm & Haas; urethane acrylates, such as described in US Patent No. 4,249,011 and those available from Sartomer Corp.;
and urethane hardcoats such as those obtained from reacting an aliphatic polyisocyanate such as Desmodur N-3300, available from Miles, Inc. with a 25 polyester such as Tone Polyol 0305, available from Union Carbide. Such layerscould also provide protection against trancmicsion of gases such as oxygen or carbon dioxide or water vapor through the film. Again this could be a single layer as shown in Figure 9 or layers on both sides as shown in Figure 10.
Other layers that could be added include layers cont~ining 30 holographic images, holographic diffusers, or other ~liffilcinsg layers. Such layers could be in a hard polymer or in an adhesive CA 02222~11 1997-11-26 Figure 11 shows alternative multilayer film 500 having alternating layers 512 and 514 with protective layers 516, 518, and 520. Thus, multiple additional layers could be provided adjacent a single major surface of the multilayer optical stack. An example of a use for a structure of the type shown in Figure 11 would be one in which protective layers 516 and 518 were tear resistant structures, as described above, and layer 520 was abrasion recict~nt The foregoing has been examples of various coatings that could be applied to the exterior of a multilayer stack to alter its properties. In general, any additional layers could be added that would have di~ren~ mechanical, chemical, or optical properties than those of the tayers of the stack itself.
WIT~ ADDITIONAL COATINGS OR LAYERS
Background of the Invention Multilayer optical stacks are well-known for providing a wide variety of optical properties. Such multilayer stacks may act as reflective polarizers or mirrors, reflecting light of all polarizations. They may also function as wavelength selective reflectors such as "cold mirrors" that reflect visible light but l,~r,smi~ infrared or "hot mirrors" that transmit visible and reflect infrared.
Examples of a wide variety of multilayer stacks that may be constructed are inçluded in United States Patent Application 08/402,041 filed March 10, 1995.
A problem with multilayer stacks as known in the art is that the stacks themselves may not have all of the physical, chemical, or optical properties desired. Some way of otherwise supplying these desirable properties would therefore be useful.
Summary of the Invention According to one embodiment of the invention a multilayer film has adhered to one or both of its major surfaces at least one additional layer selected for mPçh~nical, chemical, or optical properties that differ from the properties of the materials of the layers of the optical stack.
According to another embodiment of the invention a multilayer film has adhered to one or both of its surfaces an additional layer that will protect the multilayer optical stack.
Brief Description of the Drawings Figures IA, IB, and 2 show the preferred multilayer optical film;
Figures 3 through 8 show trancmis~ion spectra for the multilayer optical films of Examples I through 6;
CA 02222~11 1997-11-26 Figure 9 shows a multilayer film of the invention having an ~dition~l layer adhered to one of its major surfaces, Figure 10 shows a multilayer film acco,di-,g to the invention having additional layers adhered to both of its major surfaces; and Figure 11 shows a multilayer film having one additional layer adhered to one of its major surfaces and two additional layers adhered to its other ma~or surface.
Detailed Description Multilayer Optical Film The advantages, characteristics and m~nllf~ctllring of multilayer optical films are most completely described in the above-mentioned copending andcommonly-~csigned US Patent Application 08/402,041, filed March 10, 1995, titledOPTICAL FILM, which is incorporated herein by reference. The multilayer optical film is useful, for example, as highly efficient mirrors and/or polarizers. A relatively brief description of the properties and characteristics of the multilayer optical film is presented below followed by a description of illustrative embodiments of bac~light systems using the multilayer optical film according to the present invention.
Multilayer optical films as used in conjunction with the present invention exhibit relatively low absorption of incident light, as well as high reflectivity for off-axis as well as normal light rays. These properties generally hold whether the films are used for pure reflection or reflective polarization of light. The unique properties and advantages of the multilayer optical film provides an opportunity to design highly-efficient backlight systems which exhibit low absorption losses when compared to known b~cl~light systems.
An exemplary multilayer optical film of the present invention as illustrated in Figures lA and lB includes a multilayer stack 10 having alternating layers of at least two materials 12 and 14. At least one of the materials has the property of stress induced birefringence, such that the index of refraction (n) of the material is affected by the stretching process. Figure IA shows an exemplary CA 02222~11 1997-11-26 multilayer stack before the stretching process in which both materials have the same index of refraction. Light ray 13 experiences relatively little change in index of refraction and passes through the stack. In Figure IB, the same stack has been stretched, thus h~c,easil.g the index of refraction of material 12. The di~lence in 5 refractive index at each boundary between layers will cause part of ray lS to be reflected By stretching the multilayer stack over a range of uniaxial to biaxialorientation, a film is created with a range of reflectivities for di~lelllly oriented plane-polarized inciclent light. The multilayer stack can thus be made useful asreflective polarizers or mirrors.
Multilayer optical films constructed according to the present invention exhibit a Brewster angle (the angle at which reflectance goes to zero for light inridrnt at any of the layer interfaces) which is very large or is nonexistent for the polymer layer interfaces. In contrast, known multilayer polymer films exhibit relatively small Brewster angles at layer interfaces, resulting in tr~ncmicsion of light 15 and/or undesirable iridesc~nce. The multilayer optical films according to the present invention, however, allow for the construction of mirrors and polarizers whose reflectivity for p polarized light decrease slowly with angle of incidence, are independent of angle of incidenre, or increase with angle of inridence away fromthe normal. As a result, multilayer stacks having high reflectivity for both s and p 20 polarized light over a wide bandwidth, and over a wide range of angles can be achieved.
Figure 2 shows two layers of a multilayer stack, and indicates the three dimensional indices of refraction for each layer. The indices of refraction for each layer are nlx, nly, and nlz for layer 102, and n2x, n2y, and n2z for layer 104.
25 The relationships between the indices of refraction in each film layer to each other and to those of the other layers in the film stack determine the reflectance behavior of the multilayer stack at any angle of incidence, from any ~7imllth~1 direction. The principles and design considerations described in US Patent Application 08/402,041 can be applied to create multilayer stacks having the desired optical effects for a 30 wide variety of circllmct~nces and applications. The indices of refraction of the CA 02222~11 1997-11-26 layers in the multilayer stack can be manipulated and tailored to produce the desired optical properties.
Referring again to Figure lB, the multilayer stack 10 can include tens, hundreds or thous~nrlc of layers, and each layer can be made from any of a5 number of di~~ materials. The characteristics which deterrnine the choice of materials for a particular stack depend upon the desired optical pe~rollllance of the stack. The stack can contain as many materials as there are layers in the stack. For ease of m~nllf~ct~lre, preferred optical thin film stacks contain only a few different materials.
The boundaries between the materials, or chemically identical materials with dirreren~ physical properties, can be abrupt or gradual. Except for some simple cases with analytical solutions, analysis of the latter type of stratified media with continlloucly varying index is usually treated as a much larger number of thinner uniform layers having abrupt boundaries but with only a small change in 15 properties between adjacent layers.
The p~efe~ed multilayer stack is comprised of low/high index pairs of film layers, wherein each low/high index pair of layers has a col..bined optical th;~n~ss of 1/2 the center wavelength of the band it ls designed to reflect. Stacks of such films are commonly referred to as quarterwave stacks. For multilayer 20 optical films concerned with the visible and the near infrared wavelengths, aquarterwave stack design results in each of the layers in the multilayer stack having an average thickness of not more than 0.5 microns.
In those applications where reflective films (e.g. mirrors) are desired, the desired average tr~ncmission for light of each polarization and plane of 25 inr.idence generally depends upon the intended use of the reflective film. One way to produce a multilayer mirror film is to biaxially stretch a multilayer stack. For a high efficiency reflective film, average tr~ncmiccion along each stretch direction at normal incidence over the visible spectrum (380-750 nm) is desirably less than 10 percent (reflectance greater than 90 percent), preferably less than 5 percent 30 (reflect~nce greater than 95 percent), more preferably less than 2 percent (reflectance greater than 98 percent), and even more preferably less than l percent CA 02222~11 1997-11-26 (reflect~nce greater than 99 percent). The average tr~ncmiccion at 60 degrees from the normal from 380-750 nm is desirably less than 20 percent (reflectance greater than 80 percent), preferably less than 10 percent (reflectance greater than 90 percent), more preferably less than 5 percent (reflectance greater than 95 percent), 5 and even more preferably less than 2 percent (reflectance greater than 98 percent), and even more preferably less than 1 percent (reflectance greater than 99 percent).
In addition, asymmetric reflective films may be desirable for certain applications. In that case, average trancmiCcion along one stretch direction may be desirably less than~ for example, 50 percent, while the average trancmicsion along 10 the other stretch direction may be desirably less than, for example 20 percent, over a bandwidth of, for example, the visible spectrum (380-750 nm), or over the visible spectrum and into the near infrared (e.g., 380-850 nm).
Multilayer optical films can also be designed to operate as reflective polarizers. One way to produce a multilayer reflective polarizer is to uniaxially 15 stretch a multilayer stack. The resulting reflective polarizers have high reflectivity for light with its plane of polarization parallel to one axis (in the stretch direction) for a broad range of angles of incidence, and cimnlt~neously have low reflectivity and high tr~ncmiccivity for light with its plane of polarization parallel to the other axxis (in the non-stretch direction) for a broad range of angles of incidence. By 20 controlling the three indices of refraction of each film, nx, ny and nz, the desired polarizer behavior can be obtained.
For many applications, the ideal reflecting polarizer has high reflectance along one axis (the so-called extinction axis) and zero reflectance along the other (the so-called trAnsmicsion axis), at all angles of incidence. For the25 tr~ncmiccion axis of a polarizer, it generally desirable to nlaxil--i~e trancmiccion of light polarized in the direction of the tr~ncmiccion axis over the bandwidth of interest and also over the range of angles of interest.
The average tr~ncmicsion at normal incidence for a polarizer in the tr~ncmiCcion axis across the visible spectrum (380-750 nm for a bandwidth of 30030 nm) is desirably at least 50 percent, preferably at least 70 percent, more preferably at least 80 percent, and even more preferably at least 90 percent. The average CA 02222~11 1997-11-26 l,~h~,..;ccion at 60 degrees from the normal (measured along the tr~ncmicsion axis for p-polarized light) for a polarizer from 380-750 nm is desirably at least 50 percent, preferably at least 70 percent, more preferably at least 80 percent, and even more preferably at least 90 percent.
The average tr~ncmicsion for a multilayer reflective polarizer at normal in~idçnce for light polarized in the direction of the extinction axis across the visible spectrum (380-750 nm for a bandwidth of 300 nm) is desirably at less than 50 percent, preferably less than 30 percent, more preferably less than 15 percent, and even more plefe-ably less than 5 percent. The average tr~ncmiccion at 60 degrees from the normal (measured along the trancmicsion axis for p-polarized light) for a polarizer for light polarized in the direction of the extinction axis from 380-750 nm is desirably less than 50 percent, preferably less than 30 percent, more preferably less than 15 percent, and even more preferably less than 5 percent.
For certain applications, high reflectivity for p-polarized light with its plane of polarization parallel to the tr~ncmicsion axis at off-normal angles arepre~,.ed. The average reflectivity for light polarized along the tr~ncmission axis should be more than 20 percent at an angle of at least 20 degrees from the normal.
In addition, although reflective polarizing films and asymmetric reflective films are dicc~csed separately herein, it should be understood that two or more of such films could be provided to reflect substantially all light incident on them (provided they are properly oriented with respect to each other to do so).
This construction is typically desired when the multilayer optical film is used as a reflector in a bacL light system according to the present invention.
If some reflectivity occurs along the tr~ncmission axis, the efficiency of the polarizer at off-normal angles may be reduced. If the reflectivity along the trancmicsion axis is different for various wavelengths, color may be introduced into the l.~nsl,lilled light. One way to measure the color is to determine the root mean square (RMS) value of the tr~ncmicsivity at a selected angle or angles over the wavelength range of interest. The percent RMS color, CR~S, can be determined according to the equation:
CA 02222~11 1997-11-26 ¦((T- T) ) d,l r _ 1l ~'RMS - -- -where the range 11 to 12 is the wavelength range, or bandwidth, of interest, T is the tr~ncmicsivity along the tr~ncmicsion axis, and T is the average tr~ncmiccivity along the tr~ncmission axis in the wavelength range of interest. For applications where a low color polarizer is desirable, the percent RMS color should be less than 10 percent, preferably less than 8 percent, more preferably less than 3.5 percent, and even more plefel~bly less than 2 percent at an angle of at least 30 degrees from the normal, preferably at least 45 degrees from the normal, and even more preferably at least 60 degrees from the normal.
Preferably, a reflective polarizer combines the desired percent RMS
color along the tr~ncmission axis for the particular application with the desired amount of reflectivity along the extinction axis across the bandwidth of interest.
For polarizers having a bandwidth in the visible range (400-700 nm, or a bandwidth of 300 nm), average tr~ncmic.cion along the extinction axis at normal incidence is desirably less than 40 percent, more desirably less than 25 percent, preferably less than 15 percent, more preferably less than 5 percent and even more preferably less than 3 percent.
Materials Selection and Processin~
With the design considerations described in the above mentioned US
Patent Application 08/402,041, one of ordinary skill will readily appreciate that a wide variety of materials can be used to form multilayer reflective films or polarizers according to the invention when processed under conditions selected to yield thedesired refractive index relationships. The desired refractive index relationships can be achieved in a variety of ways, incl-lding stretching during or after film formation (e.g., in the case of organic polymers), extruding (e.g., in the case of liquid crystalline materials), or coating. In addition, it is pre~e,-ed that the two materials have similar rheological properties (e.g., melt viscosities) such that they can be co-extruded.
CA 02222~11 1997-11-26 In general, appropriate cor"binalions may be achieved by selecting, as the first material, a crystalline or semi-crystalline, or liquid crystalline material, preferably a polymer. The second material, in turn, may be crystalline, semi-crystalline, or amorphous. The second material may have a bil~flingel1ce opposite 5 to or the same as that of the first material. Or, the second material may have no birefringence. It should be understood that in the polymer art it is generally recognized that polymers are typically not entirely crystalline, and thelt;Çore in the context of the present invention, crystalline or semi-crystalline polymers refer to those polymers that are not amorphous and includ~s any of those materials 10 commonly referred to as crystalline, partially crystalline, semi-crystalline, etc. The second material may have a birefringence opposite to or the same as that of the first material. Or, the second material may have no birefringence.
Specific examples of suitable materials include polyethylene naphth~l~te (PEN) and isomers thereof (e.g., 2,6-, 1,4-, 1,5-, 2,7-, and 2,3-PEN), 15 polyalkylene terephth~l~tes (e.g., polyethylene terephthalate, polybutylene terephth~l~te, and poly-1,4-cyclohex~nerlimethylene terephthalate), polyimides (e.g., polyacrylic imides), polyetherimides, atactic polystyrene, polycarbonates, polymethacrylates (e.g., polyisobutyl methacrylate, polypropylmethacrylate, polyethylmeth~crylate, and polymethylmethacrylate), polyacrylates (e.g., 20 polybutylacrylate and polymethylacrylate), syndiotactic polystyrene (sPS), syndiotactic poly-alpha-methyl styrene, syndiotactic polydichlorostyrene, copolymers and blends of any of these polystyrenes, cellulose derivatives (e.g., ethyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate butyrate, and cellulose nitrate), polyalkylene polymers (e.g., polyethylene, polypropylene, 25 polybutylene, polyisobutylene, and poly(4-methyl)pentene), fluorinated polymers (e.g., perfluoroalkoxy resins, polytetrafluoroethylene, fluorinated ethylene-propylene copolymers, polyvinylidene fluoride, and polychlorotrifluoroethylene), chlorinated polymers (e.g., polyvinylidene chloride and polyvinylchloride), polysulfones, polyethersulfones, polyacrylonitrile, 30 polyamides, silicone resins, epoxy resins, polyvinylacetate, polyether-amides, ionomeric resins, elastomers (e.g., polybutadiene, polyisoprene, and neoprene), and CA 02222~11 1997-11-26 WO 97/01440 PCTtUS96/10691 polyurethanes. Also suitable are copolymers, e.g., copolymers of PEN (e.g., copolymers of 2,6-, 1,4-, 1,5-, 2,7-, and/or 2,3-naphthalene dicarboxylic acid, or esters thereof, with (a) terephthalic acid, or esters thereof; (b) isophthalic acid, or esters thereof; (c) phthalic acid, or esters thereof; (d) alkane glycols; (e) cycloalkane glycols (e.g., cyclohexane ~imPth~ne diol); (f) alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxylic acids (e.g., cyclohexane dicarboxylic acid)), copolymers of polyalkylene terephth~l~tec (e.g., copolymers of terephthalic acid, or esters thereof, with (a) n~phth~l~ne dicarboxylic acid, or esters thereof; (b) isophthalic acid, or esters thereof; (c) phthalic acid, or esters thereof; (d) alkane glycols; (e) cycloalkane glycols (e.g., cyclohexane tlimeth~nel diol); (f) alkane dicarboxylic acids; and/or (g) cycloalkane dicarboxylic acids (e.g., cyclohexane dicarboxylic acid)), and styrene copolymers (e.g., styrene-butadiene copolymers and styrene-acrylonitrile copolymers), 4,4'-bibenzoic acid and ethylene glycol. In addition, each individual layer may include blends of two or more of the above-described polymers or copolymers (e.g., blends of sPS and atactic polystyrene). The coPEN desc,;bed may also be a blend of pellets where at least one component is a polymer based on n~rhth~ltone dicarboxylic acid and other components are other polyesters or polycarbonates, such as a PET, a PEN or a coPEN.
Particularly prefe~,ed combinations of layers in the case of polarizers include PEN/coPEN, polyethylene terephth~l~te (PET)/coPEN, PEN/sPS, PET/sPS, PEN/Estar, and PET/Estar, where "coPEN" refers to a copolymer or blend based upon naphthalene dicarboxylic acid (as described above) and Estar ispolycyclohexanedimethylene terephthalate commercially available from F~ctm~n Chemical Co.
Particularly preferred combinations of layers in the case of reflective films include PET/Ecdel, PEN/Ecdel, PEN/sPS, PEN/THV, PEN/co-PET, and PET/sPS, where "co-PET" refers to a copolymer or blend based upon terephthalic acid (as described above), Ecdel is a thermoplastic polyester commercially available from F~ctm~n Chemical Co., and THV is a fluoropolymer co~-l...elcially available30 from Minnesota Mining and Manufacturing Company, St. Paul, Minnesota.
CA 02222~11 1997-11-26 WO 97/01440 PCTrUS96/1069 The number of layers in the film is selected to achieve the desired optical properties using the minimllm number of layers for reasons of film thickness, flexibility and economy. In the case of both polarizers and reflective films, the number of layers is preferably less than 10,000, more preferably less than 5,000, and 5even more preferably less than 2,000.
As tliccucsed above, the ability to achieve the desired relationships among the various indices of refraction (and thus the optical propellies of the multilayer film) is influenced by the processing conditions used to prepare the multilayer film. In the case of organic polymers which can be oriented by 10stretching, the films are generally prepared by co-extruding the individual polymers to form a multilayer film and then orienting the film by stretching at a selected temperature, optionally followed by heat-setting at a selected temperature.
Alternatively, the extrusion and orientation steps may be performed simult~neously.
In the case of polarizers, the film is stretched substantially in one direction (uniaxial 15orientation), while in the case of reflective films the film is stretched subslalllially in two directions (biaxial orientation).
The film may be allowed to dimensionally relax in the cross-stretch direction from the natural reduction in cross-stretch (equal to the square root of the stretch ratio); it may simply be constrained to limit any substantial change in cross-20stretch dimension; or it may be actively stretched in the cross-stretch dimension.
The film may be stretched in the machine direction, as with a length orienter, or in width using a tenter.
The pre-stretch temperature, stretch temperature, stretch rate, stretch ratio, heat set temperature, heat set time, heat set relaxation, and cross-25stretch relaxation are selected to yield a multilayer film having the desired refractive index relationship. These variables are interdependent; thus, for example, a relatively low stretch rate could be used if coupled with, e.g., a relatively low stretch temperature. It will be apparent to one of ordinary skill how to select the appiopliate combination of these variables to achieve the desired multilayer film. In 30general, however, a stretch ratio in the range from 1:2 to 1:10 (more preferably 1:3 CA 02222~11 1997-11-26 to 1:7) in the stretch direction and from 1:0.2 to 1:10 (more ple~,~bly from 1:0.2 to 1:7) orthogonal to the stretch direction is ple~.,ed.
Suitable multilayer films may also be prepared using techniques such as spin coating (e.g., as described in Boese et al., J. Polym. Sci.: Part B, 30:1321 5 (1992) for birefringent polyimides, and vacuum deposition (e.g., as described by Zang et. al., Appl. Phys. Letters, 59:823 (1991) for crystalline organic compounds;
the latter technique is particularly useful for certain combinations of crystalline organic compounds and inorganic materials.
Exemplary multilayer reflective mirror films and multilayer reflective 10 polarizers will now be described in the following examples.
Example I
PEN:THV 500~ 449. Mirror) A coextruded film co~ inil-Sg 449 layers was made by extruding the 15 cast web in one operation and later orienting the film in a laboratory film-sl~e~cl~h~g appa,al~s. A Polyethylene naphth~l~te (PEN) with an Intrinsic Viscosity of 0.53 dVg (60 weight percent phenoW0 weight percent dichlorobenzene) was delivered by one extruder at a rate of 56 pounds per hour and THV 500 (a fluoropolymer available from Minnesota Mining and M~nuf~ctlJring Company) was 20 delivered by another extruder at a rate of 11 pounds per hour. The PEN was on the skin layers and 50 percent of the PEN was present in the two skin layers. The feedblock method was used to generate 57 layers which was passed through three multipliers producing an extrudate of 449 layers. The cast web was 20 mils thickand 12 inches wide. The web was later biaxially oriented using a laboratory 25 stretching device that uses a pantograph to grip a square section of film andsimultaneously stretch it in both directions at a uniform rate. A 7.46 cm square of web was loaded into the stretcher at about 100 degrees C and heated to 140 degrees C in 60 seconds. Stretching then commenced at 10 percent/sec (based on original dimloncinns) until the sample was stretched to about 3.5x3.5. Tmme~i~tely 30 after the stretching the sample was cooled by blowing room temperature air at it.
CA 02222~11 1997-11-26 Figure 3 shows the tr~ncmiscion of this multilayer film. Curve (a) shows the response at normal incidence for light polarized in the tr~ncmicsion direction, while curve (b) shows the response at 60 degrees for p-polarized light polarized in the tr~ncmiCcion direction.
Example 2 (PEN.PMMA. 601. Mirror) A coextruded film cont~ining 601 layers was made on a sequential flat-film-making line via a coextrusion process. Polyethylene Naphth~l~te (PEN) with an Intrinsic Viscosity of 0.57 dUg (60 weight percent phenoU40 weight percent dichlorobenzene) was delivered by extruder A at a rate of 114 pounds per hour with 64 pounds per hour going to the feedblock and the rest going to skin layers described below. PMM:A (CP-82 from ICI of Americas) was delivered by extruder B at a rate of 61 pounds per hour with all of it going to the feedblock. PEN was on the skin layers of the ,feedblock. The feedblock method was used to generate 151layers using the feedblock such as those described in US Patent 3,801,429, after the feedblock two symmetric skin layers were coextruded using extruder C metering about 30 pounds per hour of the same type of PEN delivered by extruder A. This extrudate passed through two multipliers producing an extrudate of about 601 layers. US Patent 3,565,985 describes similar coextrusion multipliers.- The extrudate passed through another device that coextruded skin layers at a total rate of 50 pounds per hour of PEN from extruder A. The web was length oriented to a draw ratio of about 3.2 with the web temperature at about 280 degrees F. The film was subsequently preheated to about 310 degrees F in about 38 seconds and drawn in the transverse direction to a draw ratio of about 4.5 at a rate of about 11 percent per second. The film was then heat-set at 440 degrees F with no relaxation allowed. The finished film thickness was about 3 mil.
As seen in Figure 4, curve (a), the bandwidth at normal incidence is about 350 nm with an average in-band extinction of greater than 99 percent. The amount of optical absorption is difficult to measure because of its low value, but is less than I percent. At an incidence angle of 50 percent from the normal both s CA 02222~11 1997-11-26 (curve (b)) and p-polarized (curve (c)) light showed similar extinctions, and the bands were shifted to shorter wavelengths as expected. The red band-edge for s-polarized light is not shifted to the blue as much as for p-polarized light due to the expected larger bandwidth for s-polarized light, and due to the lower index seen by the p-polarized light in the PEN layers.
(PEN:PCTG, 449~ Polarizer) A coextruded film cont~ining 481 layers was made by extruding the cast web in one operation and later orienting the film in a laboratory film-stretching appa~alLIs. The feedblock method was used with a 61 layer feedblock and three (2x) multipliers. Thick skin layers were added between the final multiplier and the die. Polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.47 dl/g (60weight percent phenol/40 weight percent dichlorobenzene) was delivered to the feedblock by one ext~ruder at a rate of 25.0 pounds per hour. Glycol modified polyethylene dimethyl cyclohexane terephthalate (PCTG 5445 from F~ctm~n) was delivered by another extruder at a rate of 25.0 pounds per hour. Another stream of PEN from the above extruder was added as skin layers after the multipliers at a rate of 25.0 pounds per hour. The cast web was 0.007 inches thick and 12 inches wide.The web was layer uniaxially oriented using a laboratory stretching device that uses a pantograph to grip a section of film and stretch it in one direction at a uniform rate while it is allowed to freely relax in the other direction. The sample of web loaded was about 5.40 cm wide (the unconstrained direction) and 7.45 cm long between the g-ippe,~ of the pantograph. The web was loaded into the stretcher atabout 100 degrees C and heated to 135 degrees C for 45 seconds. Stretching was then comm~nced at 20 percent/second (based on original dimensions) until the sample was stretched to about 6:1 (based on gripper to gripper measurements).
Tmme(ii~tely after stretching, the sample was cooled by blowing room temperatureair at it. In the center, the sample was found to relax by a factor of 2Ø
Figure 5 shows the tr~ncmicsion of this multilayer film where curve a shows tr~ncmiscion of light polarized in the non-stretch direction at normal CA 02222~11 1997-11-26 incidçnce, curve b shows tr~ncmission of p-polarized light polarized in the non-stretched direction at 60 degree incidence, and curve c shows the tr~ncmicsion of light polarized in the stretch direction at normal incidence. Average tr~ncmiccion for curve a from 400-700 nm is 89.7 percent, average tr~ncmiCcion for curve b from 400-700 nm is 96.9 percent, and average trancmission for curve c from 400-700 nmis 4.0 percent. Percent RMS color for curve a is 1.05 percent, and percent RMS
color for curve b is 1.44 percent.
(PEN:CoPEN. 601. Polarizer) A coextruded film cont~ining 601 layers was made on a sequential flat-film-making line via a coextrusion process. A Polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.54 dltg (60 weight percent Phenol plus 40 weight percent dichlorobenzene) was delivered by on extruder at a rate of 75 pounds perhour and the coPEN ~was delivered by another extruder at 65 pounds per hour. ThecoPEN was a copolymer of 70 mole percent 2,6 naphthalene dicarboxylate methyl ester, 15 percent dimethyl isophthalate and 15 percent dimethyl terephth~l~te with ethylene glycol. The feedblock method was used to generate 151 layers. The feedblock was dçsigned to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. The PEN skin layers were coextruded on the outside of the optical stack with a total thickness of 8 percent of the coextruded layers. The optical stack was multiplied by two sequçnti~l multipliers. The nominal multiplication ratio of the multipliers were 1.2 and 1.27, respectively. The film was subsequently preheated to 310 degree F in about 40 seconds and drawn in the transverse direction to a drawratio of about 5.0 at a rate of 6 percent per second. The finished film thickness was about 2 mils.
Figure 6 shows the tr~ncmicsion for this multilayer film. Curve a shows trancmiccion of light polarized in the non-stretch direction at normal incirl~nce, curve b shows tr~ncmiscion of p-polarized light at 60 degree incidence, and curve c shows trancrnicsion of light polarized in the stretch direction at normal CA 02222~11 1997-11-26 incidence. Note the very high tr~ncmission of p-polarized light in the non-stretch direction at both normal and 60 degree incidence (80-100 percent). Also note thevery high reflectance of light polarized in the stretched direction in the visible range (400-700 nm) shown by curve c. Reflect~nce is nearly 100 percent between 500 5 and 650 nm.
(PEN:sPS, 481, Polarizer) A 481 layer multilayer film was made from a polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.56 dVg measured in 60 weight percent phenol and 40 weight percent dichlorobenzene purchased from F.actm~n ChPmic~lc and a syndiotactic polystyrene (sPS) homopolymer (weight average molecular weight = 200,000 Daltons, sampled from Dow Corporation). The PEN
was on the outer layers and was extruded at 26 pounds per hour and the sPS at 23pounds per hour. The~ feedblock used produced 61 layers with each of the 61 being approximately the same thickness. After the feedblock three (2x) multipliers were used. Equal thickness skin layers cont~ining the same PEN fed to the feedblock were added after the final multiplier at a total rate of 22 pounds per hour. The web was extruded through a 12 inch wide die to a thickness of about 0.011 inches (0.276 mm). The extrusion temperature was 290 degrees C.
This web was stored at ambient conditions for nine days and then uniaxially oriented on a tenter. The film was preheated to about 320 degrees F (160 degrees C) in about 25 seconds and drawn in the transverse direction to a draw ratio of about 6:1 at a rate of about 28 percent per second. No relaxation was allowed in the stretched direction. The finished film thickness was about 0.0018inches (0.046 mm).
Figure 7 shows the optical performance of this PEN:sPS reflective polarizer containing 481 layers. Curve a shows transmission of light polarized in the non-stretch direction at normal incidence, curve b shows transmission of p-polarized light at 60 degree incidence,.and curve c shows tr~ncmicsion of light polarized in the stretch direction at normal incidence. Note the very high -CA 02222~11 1997-11-26 tr~n~micsion of p-polarized light at both normal and 60 degree inci~ence Averagetr~ncmicsion for curve a over 400-700 nm is 86.2 percent, the average tr~ncmicsion for curve b over 400-700 nm is 79.7 percent. Also note the very high reflect~nce of light polarized in the stretched direction in the visible range (400-700 nm) shown by 5 curve c. The film has an average transmicsion of 1.6 percent for curve c between 400 and 700 nm. The percent RMS color for curve a is 3.2 percent, while the percent RMS color for curve b is 18.2 percent.
(PEN:CoPEN~ 603, Polarizer) A reflecting polarizer comprising 603 layers was made on a sequçnti~l flat-film making line via a coextrusion process. A polyethylene naphth~l~te (PEN) with an intrinsic viscosity of 0.47 dl/g (in 60 weight percent15 phenol plus 40 weight percent dichlorobenzene) was delivered by an extruder at a rate of 83 pounds (38 kg) per hour and the CoPEN was delivered by another extruder at 75 pounds (34 kg) per hour. The CoPEN was a copolymer of 70 mole percent, 2,6 naphthalene dicarboxylate methyl ester, 15 mole percent dimethyl terephthalate, and 15 mole percent dimethyl isophthalate with ethylene glycol. The 20 feedblock method was used to generate 151 layers. The feedblock was designed to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. This optical stack was multiplied by two sequential multipliers. The nominal multiplication ratio of the multipliers was 1.2 and I .4, respectively. Between the final multiplier and the 25 die, skin layers were added composed of the same CoPEN described above, delivered by a third extruder at a total rate of 106 pounds (48 kg) per hour. The film was subsequently preheated to 300 degrees F (150 degrees C) in about 30 seconds and drawn in the transverse direction to a draw ratio of approximately 6 at an initial rate of about 20 percent per second. The finished film thickness was 30app,oxil"ately 0.0035 inch (0.089 mm).
Figure 8 shows the optical performance of the polarizer of Example 6. Curve a shows transmission of light polarized in the non-stretch direction at CA 02222~11 1997-11-26 normal incidçnce, curve b shows tr~ncmicsion of p-polarized light in the nonstretch direction at 50 degree angle of incidence, and curve c shows trancmiCcion of light polarized in the stretch direction at normal incidence. Note the very high tr~ncmiccion of light polarized in the non-stretch direction. Average ~li.nc,n;cs;on for curve a over 400-700 nm is 87 percent. Also note the very high reflectance of light polarized in the stretched direction in the visible range (400-700 nm) shown by curve b. The film has an average tr~ncmiccion of 2.5 percent for curve b between400 and 700 nm. In addition, the percent RMS color of this polarizer is very low.
The percent RMS color for curve b is 5 percent.
While the multilayer optical stacks, as described above, can provide significant and desirable optical properties, other properties, which may be mloc.h~nical, optical, or chemical, are difficult to provide in the optical stack itself without degrading the performance of the optical stack. Such properties may be provided by inclurling,one or more layers with the optical stack that provide these properties while not contributing to the primary optical function of the optical stack itself. Since these layers are typically provided on the major surfaces of the optical stack, they are often known as "skin layers."
A skin layer may be coextruded on one or both major surfaces of the multilayer stack during its rn~n~lf~cture to protect the multilayer stack from the high shear along the feedblock and die walls, and often an outer layer with the desired chemical or physical properties can be obtained by mixing an additive, such as, for example, a UV stabilizer, into the polymer melt that makes up the skin layer, and coextruding the skin layer with altered properties onto one or both sides of themultilayer optical stack during m~nllf~cture. Alternately, additional layers may be coextruded on the outside of the skin layers during m~nllf~cture of the multilayer film; they may be coated onto the multilayer film in a separate coating operation; or they may be laminated to the multilayer film as a separate film, foil, or rigid or semi-rigid reinforcing substrate such as polyester (PET), acrylic (PMMA), polycarbonate, metal, or glass. Adhesives useful for l~min~ting the multilayer polymer film to another surface include both optically clear and diffuse adhesives CA 02222~11 1997-11-26 and include both pressure sensitive and non-pressure sensitive adhesives. Pressure sensitive adhesives are normally tacky at room te"-pe,~ re and can be adhered to a surface by application of, at most, light finger pressure, while non-pressure sensitive adhesives include solvent, heat, or radiation activated adhesive systems. Examples 5 of adhesives useful in the present invention include those based on general compositions of polyacrylate; polyvinyl ether; diene-con~ -;ng rubber such as natural rubber, polyisoprene, and polyisobutylene; polychloropl~ne; butyl rubber;
but~diene-acrylonitrile polymer; thermoplastic elastomer;. block copolymers such as styrene-isoprene and styrene-isoprene-styrene block copolymers, ethylene-10 propylene-diene polymers, and styrene-butadiene polymer; poly-alpha-olefin;
amorphous polyolefin; silicone; ethylene-containing copolymer such as ethylene vinyl acetate, ethylacrylate, and ethyl methacrylate; polyurethane; polyamide; epoxy;
polyvinylpyrrolidone and vinylpyrrolidone copolymers; polyesters; and mixtures of the above. Additionally, the adhesives can contain additives such as t~ç~ifiPrs,15 plasticizers, fillers, an,tioxidants, stabilizers, pigments, difflsing particles, curatives, biocides, and solvents. Preferred adhesives useful in the present invention include VITEL 3300, a hot melt adhesive available from Shell Chemical Co. (Akron, OH), or an acrylic pressure sensitive adhesive such as a 90/10 IOA/AA acrylic adhesive from Minnesota Mining and M~nuf~ctllring Company, St. Paul, Minnesota. When a 20 l~..,;n~ling adhesive is used to adhere the multilayer film to another surface, the adhesive composition and thickness are preferably selected so as not to interfere with the optical properties of the multilayer stack. For example, when l~min~ting additional layers to a multilayer polymer polarizer or mirror wherein a high degree of tr~ncmiccion is desired, the i~min~ting adhesive should be optically clear in the 25 wavelength region that the polarizer or mirror is designed to be transparent.Figures 10 and 11 illustrate multilayer stacks having respectively one and two additional layers, respectively. Figures 10 and 11 will be used below todescribe a variety of additional layers that could be applied.
One area in which a skin layer having differing mechanical properties 30 is desirable relates particularly to uniaxially oriented multilayer optical stacks, such as reflective polarizers. Such stacks often tend to show a low tear recict~nce in the CA 02222~11 1997-11-26 principal draw direction. This can lead to reduced yields during the m~mlf~ct~lring process or to subsequent breakage of the film during h~n~ling In order to resistthis, tear resistant layers may be adhered to the outer major surfaces of the optical stack. These tough layers may be of any appro~l iate material and could even be the same as one of the materials used in the optical stack. Factors to be considered in selectin~ a material for a tear resistant layer include percent elongation to break, Young's modulus, tear strength, adhesion to interior layers, percent ~ nc~ Ance and absorbance in an ele.;l,o~ netic bandwidth of interest, optical clarity or haze, refractive indices as a function of frequency, texture and roughn~ss, melt thermal stability, molecular weight distribution, melt rheology and coextrudability, miscibility and rate of inter-diffusion between materials in the tough and optical layers, viscoelastic response, relaxation and crystallization behavior under draw conditions, thermal stability at use temperatures, weatherability, ability to adhere to coatings and permeability to various gases and solvents. Of course, as previously stated, it is importa,nt that the material chosen not have optical properties deleterious to those of the optical stack. They may be applied during the m~nnf~cturing process or later coated onto or laminated to the optical stack.
Adhering these layers to the optical stack during the manufacturing process, such as by a coextrusion process, provides the advantage that the optical stack is protected during the m~nuf~ctllring process.
Using Figure 10 to illustrate this aspect of the invention, a multilayer optical stack having tear resistant layers 400 is shown. Film 400 includes an optical stack 410. Optical stack 410 includes alternating layers 412 and 414 of two polymers having differing optical properties. Attached to the major surfaces of optical stack 410 are tear resistant layers 416 and 418. It should be noted that, although layers 416 and 418 are shown in Figure 10 as thicker than layers 412 and 414, Figure 10 is not to scale for a generally preferred embodiment. In general it is desirable that each of layers 416 and 418 have a thickness greater than 5 percent of the thickness of the optical stack. It is plerel,ed that each of layers 416 and 418 have a thickness in the range of 5 percent to 60 percent of the thickness of theoptical stack to provide tear resistance without unnecessarily increasing the amount _19_ CA 02222=,11 1997-11-26 WO 97/01440 PCTtUS96/10691 of material used. Thus, if the optical stack has 600 layers, in such a plefelledembodiment the thickness of each of tear resistant layers 416 and 418 would be equal to the thickness of 30 to 360 of the layers of the stack. In a more pl~r~ d embodiment each ofthe tear le~ Lanl layers 416 and 418 would have a thickness in5 the range of 30 percent to S0 percent of that of the optical stack.
In a particularly desirable embodiment, tear resistant outer layers may be of one of the same materials used in alternating layers 412 and 414. In particular, it has been discovered that in a reflective polarizer comprising alternating layers of PEN and coPEN, tear resistant outer layers of coPEN may be coextruded 10 during the manufacturing process.
Example 7 A multilayered composite of alternating PEN and coPEN layers to form a reflective polarizer was coextruded with thick skin layers of coPEN to form 15 a tear resistant reflective polarizer. A coextruded film conl~inil-v 603 layers was made on a sequential flat-film extruder. A polyethylene naphthalate (PEN) with an intrinsic viscosity of 0.47 dl/g (in 60 weight percent phenol plus 40 weight percent dichlorobenzene) was delivered by an extruder at a rate of 86 pounds per hour and the coPEN was delivered by another extruder at 78 pounds per hour. The coPEN
20 was a copolymer of 70 mole percent, 2,6 naphthalene dicarboxylate methyl ester and 30 percent dimethyl terephthalate with ethylene glycol. The feedblock extruded 151 layers. The feedblock was designed to produce a stack of films having a thickness gradient from top to bottom, with a thickness ratio of 1.22 from the thinnest layers to the thickest layers. This optical stack was multiplied by two25 sequential multipliers. The nominal multiplication ratio of the multipliers was 1.2 and 1.27, respectively. Between the final multipliers and the die, composed of coPEN as described above, layers were added. These layers were charged and delivered by a third extruder at a total rate of 187 pounds per hour. The film with the additional coPEN outer layers was preheated to 320 degrees F in about 40 30 seconds and drawn in the transverse direction to a draw ratio of applo~illlately 6 at an initial rate of about 20 percent per second. The finished film had a thickness of CA 02222~11 1997-11-26 WO 97/01440 PCT/US96t10691 app~ ely 100 ~lm inclutling an inner multilayered optical stack of about 50 ~m thickness and two exterior outer layers (one on each side of the film) of about 25 ~Lm thicL n-oss~ each. Tear resist~nce improved over the case without skins allowing the creation of wound rolls of tough reflective polarizer. Specifically, tear reCi~t~nce was measured on films made according to this example and on film madeunder similar conditions but without coPEN skin layers using a trouser tear testalong the principal draw direction, according to ASTM D-1938. Average film thir~nesses were 100 ~Lm and 48 llm, respectively. The average tear force valueswere 60.2 and 2.9 grams force, with standard deviations of 4.44 and 0.57 grams force, respectively. Analysis of the coPEN skin layers showed low orientation with indices of refraction of 1.63, 1.62, and 1.61 at 633 nm. Good interlayer adhesion was demonstrated by the difficulty of cleanly separating the construction. For further comparison a 48 ~Im optical stack having 3.8 ~lm outer layers of PEN wastested and found to have an average tear force of 2.8 grams with a standard deviation of 1.07.
The appearance and/or performance of a film may be altered by including a skin layer having a dye or pigment that absorbs in one or more selected regions of the spectrum. This can include portions or all of the visible spectrum as well as ultraviolet and infrared. Of course, if all of the visible spectrum is absorbed, the layer will be opaque. These can be selected in order to change the appare"l color of light transmitted or reflected by the film. They can also be used to compliment the properties of the film, particularly where the film transmits some frequencies while reflecting others. The use of an UV absorptive material in a cover layer is particularly desirable because it may be used to protect the inner layers that may be unstable when exposed to UV radiation. Thus, Figure 9 illustrates such a film with layer 316 representing a layer containing an electrom~gnetic absorbingmaterial.
Similar to the electrom~gnetic absorbing materials described above, a fluol esce." material could be incorporated in layer 316 of Figure 9 or one or both of layers 416 and 418 of Figure 9. Fluorescent materials absorb electrom~gnetic energy in the ultraviolet region of the spectrum and reemit in the visible. Desirable CA 02222~11 1997-11-26 fluorescelll materials include hindered amine light stabilizers (HALS) and are desc,;l)ed in more detail in United States Patent Application 08/34S,608, filed November 28, 1994, the disclosure of which is incorporated herein by reference.
Pressure sensitive adhesives form another desirable class of materials 5 that may be applied to a multilayer stack as layer 316 of Figure 9 or one of layers 416 or 418 of Figure 10. Generally pressure sensitive adhesives may be applied when the optical stack is inten~ed for later l~min~tion to another material, such as a glass or metal substrate.
Another material that could be incorporated in a skin layer such as layer 316 or one of layers 416 or 418 would be a slip agent. A slip agent will make the film easier to handle during the m~n~lf~cturing process. Typically a slip agent would be used with a mirror film rather than a film intended to ll~hSIIIil a portion of the light striking it. The side inclu~ling the slip agent would typically be the side inten-led to be l~min~ted to a supporting substrate in order to prevent the slip agent 15 from increasing haze associated with the reflection.
Another type of additional layer that could be used is a protective layer. Such a layer could be abrasion resistant or resistant to weathering and/or .hPmic~l action. Such coatingc would be particularly useful in situations where the multilayer film is to be exposed to a harsh or corrosive environment. Examples of 20 abrasion-resistant or hard coatings include acrylic hardcoats such as Acryloid A-l l and Paraloid K-120N, available from Rohm & Haas; urethane acrylates, such as described in US Patent No. 4,249,011 and those available from Sartomer Corp.;
and urethane hardcoats such as those obtained from reacting an aliphatic polyisocyanate such as Desmodur N-3300, available from Miles, Inc. with a 25 polyester such as Tone Polyol 0305, available from Union Carbide. Such layerscould also provide protection against trancmicsion of gases such as oxygen or carbon dioxide or water vapor through the film. Again this could be a single layer as shown in Figure 9 or layers on both sides as shown in Figure 10.
Other layers that could be added include layers cont~ining 30 holographic images, holographic diffusers, or other ~liffilcinsg layers. Such layers could be in a hard polymer or in an adhesive CA 02222~11 1997-11-26 Figure 11 shows alternative multilayer film 500 having alternating layers 512 and 514 with protective layers 516, 518, and 520. Thus, multiple additional layers could be provided adjacent a single major surface of the multilayer optical stack. An example of a use for a structure of the type shown in Figure 11 would be one in which protective layers 516 and 518 were tear resistant structures, as described above, and layer 520 was abrasion recict~nt The foregoing has been examples of various coatings that could be applied to the exterior of a multilayer stack to alter its properties. In general, any additional layers could be added that would have di~ren~ mechanical, chemical, or optical properties than those of the tayers of the stack itself.
Claims (14)
1. A multilayer layer film including an optical stack comprising layers of a semi-crystalline having an average thickness of not more than 0.5 microns and layers of a second polymer having an average thickness of not more than 0.5 microns wherein said optical stack has been stretched in at least one direction to at least twice that direction's unstretched dimension, said optical stack having first and second major surfaces, said film further comprising a first additional layer adhered to said first major surface, said additional layer being of a material selected for its mechanical properties, said mechanical properties differing from mechanical properties of said layers of said optical stack.
2. The multilayer film of Claim 1 further comprising a second additional layer adhered.
3. A multilayer optical film having layers of first and second polymers, said first and second polymers differing in composition, each of said layers having a thickness of no more than 0.5 microns, said optical stack having first and second major surfaces, said first major surface having adhered thereto a first tear resistant layer.
4. The multilayer optical film of Claim 3 wherein said second major surface has adhered thereto a second tear resistant layer.
5. The multilayer optical film of Claim 4 wherein each of said tear resistant layers has a thickness greater than 5 percent of the thickness of said optical stack.
6. The multilayer optical film of Claim 5 wherein each of said tear resistant layers has a thickness in the range of 5 percent to 60 percent of the thickness of said optical stack.
7. The multilayer optical film of Claim 6 wherein each of said tear resistant layers has a thickness in the range of 30 percent to 50 percent of the thickness of said optical stack.
8. The multilayer optical film of Claim 5 wherein said tear resistant layers have a composition that is substantially the same as the composition of said second polymers.
9. The multilayer optical film of Claim 8 wherein said first polymer is polyethylene naphthalate and said second polymer is a copolyester comprising naphthalate and terephthalate units.
10. The multilayer optical film of Claim 3 wherein said first polymer has a positive stress coefficient.
11. A multilayer layer film including an optical stack comprising layers of a semi-crystalline having an average thickness of not more than 0.5 microns and layers of a second polymer having an average thickness of not more than 0.5 microns wherein said optical stack has been stretched in at least one direction to at least twice that direction's unstretched dimension, said optical stack having first and second major surfaces, said film further comprising a first additional layer adhered to said first major surface, said additional layer being of a material selected for its chemical properties, said chemical properties differing from chemical properties of said layers of said optical stack.
12. The multilayer film of Claim 11 further comprising a second additional layer adhered.
13. A multilayer layer film including an optical stack comprising layers of a semi-crystalline having an average thickness of not more than 0.5 microns and layers of a second polymer having an average thickness of not more than 0.5 microns wherein said optical stack has been stretched in at least one direction to at least twice that direction's unstretched dimension, said optical stack having first and second major surfaces, said film further comprising a first additional layer adhered to said first major surface, said additional layer being of a material selected for its optical properties, said optical properties differing from optical properties of said layers of said optical stack.
14. The multilayer film of Claim 13 further comprising a second additional layer adhered.
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US49441695A | 1995-06-26 | 1995-06-26 | |
US08/494,416 | 1995-06-26 |
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CA002222511A Abandoned CA2222511A1 (en) | 1995-06-26 | 1996-06-20 | Multilayer polymer film with additional coatings or layers |
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US (2) | US6368699B1 (en) |
EP (2) | EP1537992A3 (en) |
JP (2) | JP4122057B2 (en) |
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CN (1) | CN1106937C (en) |
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CA (1) | CA2222511A1 (en) |
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US5828488A (en) | 1993-12-21 | 1998-10-27 | Minnesota Mining And Manufacturing Co. | Reflective polarizer display |
WO1995017303A1 (en) * | 1993-12-21 | 1995-06-29 | Minnesota Mining And Manufacturing Company | Multilayered optical film |
MY121195A (en) | 1993-12-21 | 2006-01-28 | Minnesota Mining & Mfg | Reflective polarizer with brightness enhancement |
US5424119A (en) | 1994-02-04 | 1995-06-13 | Flex Products, Inc. | Polymeric sheet having oriented multilayer interference thin film flakes therein, product using the same and method |
US5629055A (en) | 1994-02-14 | 1997-05-13 | Pulp And Paper Research Institute Of Canada | Solidified liquid crystals of cellulose with optically variable properties |
US5481445A (en) | 1994-02-15 | 1996-01-02 | Lexalite International Corp. | Transflection reflector having controlled reflected and transmitted light distribution |
DE69527515T2 (en) | 1994-04-06 | 2003-05-08 | Minnesota Mining & Mfg | POLARIZED LIGHT SOURCE |
US5451449A (en) | 1994-05-11 | 1995-09-19 | The Mearl Corporation | Colored iridescent film |
JP3447744B2 (en) | 1994-11-28 | 2003-09-16 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Products with persistent coloring and / or fluorescent properties |
US5816238A (en) | 1994-11-28 | 1998-10-06 | Minnesota Mining And Manufacturing Company | Durable fluorescent solar collectors |
DE19502418C1 (en) | 1995-01-26 | 1996-02-22 | Topac Verpackung Gmbh | Film pocket for accommodating then laminating document, e.g. identity document |
JP4034365B2 (en) | 1995-03-09 | 2008-01-16 | 大日本印刷株式会社 | Ultrafine particle-containing antireflection film, polarizing plate and liquid crystal display device |
US5751388A (en) | 1995-04-07 | 1998-05-12 | Honeywell Inc. | High efficiency polarized display |
US6080467A (en) | 1995-06-26 | 2000-06-27 | 3M Innovative Properties Company | High efficiency optical devices |
US5699188A (en) | 1995-06-26 | 1997-12-16 | Minnesota Mining And Manufacturing Co. | Metal-coated multilayer mirror |
US6737154B2 (en) * | 1995-06-26 | 2004-05-18 | 3M Innovative Properties Company | Multilayer polymer film with additional coatings or layers |
US5686979A (en) | 1995-06-26 | 1997-11-11 | Minnesota Mining And Manufacturing Company | Optical panel capable of switching between reflective and transmissive states |
KR100468560B1 (en) | 1995-06-26 | 2005-08-04 | 미네소타 마이닝 앤드 매뉴팩춰링 캄파니 | Multilayer polymer film with additional coatings or layers |
EP0855043B1 (en) | 1995-06-26 | 2003-02-05 | Minnesota Mining And Manufacturing Company | Diffusely reflecting multilayer polarizers and mirrors |
US5767935A (en) | 1995-08-31 | 1998-06-16 | Sumitomo Chemical Company, Limited | Light control sheet and liquid crystal display device comprising the same |
US5783120A (en) | 1996-02-29 | 1998-07-21 | Minnesota Mining And Manufacturing Company | Method for making an optical film |
DE69721505T2 (en) | 1996-02-29 | 2003-11-20 | Minnesota Mining & Mfg | FILM FOR BRIGHTNESS INCREASE |
US5825543A (en) | 1996-02-29 | 1998-10-20 | Minnesota Mining And Manufacturing Company | Diffusely reflecting polarizing element including a first birefringent phase and a second phase |
JPH1024514A (en) | 1996-07-09 | 1998-01-27 | Eeru Kasei Shoji:Kk | Reflective film with hologram pattern |
US5808794A (en) | 1996-07-31 | 1998-09-15 | Weber; Michael F. | Reflective polarizers having extended red band edge for controlled off axis color |
US6024455A (en) * | 1998-01-13 | 2000-02-15 | 3M Innovative Properties Company | Reflective article with concealed retroreflective pattern |
-
1996
- 1996-06-20 KR KR1019970709696A patent/KR100468560B1/en not_active IP Right Cessation
- 1996-06-20 CA CA002222511A patent/CA2222511A1/en not_active Abandoned
- 1996-06-20 EP EP04028333A patent/EP1537992A3/en not_active Withdrawn
- 1996-06-20 IL IL12224496A patent/IL122244A0/en unknown
- 1996-06-20 JP JP50448497A patent/JP4122057B2/en not_active Expired - Lifetime
- 1996-06-20 BR BR9609314A patent/BR9609314A/en not_active Application Discontinuation
- 1996-06-20 WO PCT/US1996/010691 patent/WO1997001440A1/en not_active Application Discontinuation
- 1996-06-20 CN CN96196475A patent/CN1106937C/en not_active Expired - Lifetime
- 1996-06-20 EP EP96923376A patent/EP0836554A1/en not_active Ceased
- 1996-06-20 AU AU63903/96A patent/AU6390396A/en not_active Abandoned
-
1997
- 1997-08-13 US US08/910,660 patent/US6368699B1/en not_active Expired - Lifetime
-
1999
- 1999-10-18 US US09/419,946 patent/US6459514B2/en not_active Expired - Lifetime
-
2008
- 2008-01-28 JP JP2008016934A patent/JP2008162289A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
KR100468560B1 (en) | 2005-08-04 |
JPH11508706A (en) | 1999-07-27 |
US6459514B2 (en) | 2002-10-01 |
US20010008700A1 (en) | 2001-07-19 |
WO1997001440A1 (en) | 1997-01-16 |
US6368699B1 (en) | 2002-04-09 |
EP1537992A3 (en) | 2011-12-28 |
MX9710372A (en) | 1998-03-29 |
BR9609314A (en) | 1999-07-06 |
JP4122057B2 (en) | 2008-07-23 |
CN1106937C (en) | 2003-04-30 |
CN1195317A (en) | 1998-10-07 |
IL122244A0 (en) | 1998-04-05 |
JP2008162289A (en) | 2008-07-17 |
EP1537992A2 (en) | 2005-06-08 |
EP0836554A1 (en) | 1998-04-22 |
KR19990028380A (en) | 1999-04-15 |
AU6390396A (en) | 1997-01-30 |
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Legal Events
Date | Code | Title | Description |
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EEER | Examination request | ||
FZDE | Discontinued |