TWI440904B - Method of manufacturing phase difference plate - Google Patents
Method of manufacturing phase difference plate Download PDFInfo
- Publication number
- TWI440904B TWI440904B TW98100444A TW98100444A TWI440904B TW I440904 B TWI440904 B TW I440904B TW 98100444 A TW98100444 A TW 98100444A TW 98100444 A TW98100444 A TW 98100444A TW I440904 B TWI440904 B TW I440904B
- Authority
- TW
- Taiwan
- Prior art keywords
- temperature
- thermoplastic resin
- phase difference
- difference plate
- layer
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 59
- 229920005992 thermoplastic resin Polymers 0.000 claims description 117
- 229920005989 resin Polymers 0.000 claims description 46
- 239000011347 resin Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 45
- 238000005452 bending Methods 0.000 claims description 37
- 230000005684 electric field Effects 0.000 claims description 16
- 229920005668 polycarbonate resin Polymers 0.000 claims description 16
- 239000004431 polycarbonate resin Substances 0.000 claims description 16
- 230000010287 polarization Effects 0.000 claims description 11
- 229920005990 polystyrene resin Polymers 0.000 claims description 8
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 6
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 description 16
- 239000004973 liquid crystal related substance Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 11
- 238000000572 ellipsometry Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 229920006026 co-polymeric resin Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 5
- 235000019589 hardness Nutrition 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
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- 238000005266 casting Methods 0.000 description 3
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004421 Wonderlite Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- APNOOECCLHIHKN-UHFFFAOYSA-N (4-hydroxyphenyl)-(4,6,6-trihydroxycyclohexa-2,4-dien-1-yl)methanone Chemical compound C1=CC(O)=CC(O)(O)C1C(=O)C1=CC=C(O)C=C1 APNOOECCLHIHKN-UHFFFAOYSA-N 0.000 description 1
- LNOLJFCCYQZFBQ-BUHFOSPRSA-N (ne)-n-[(4-nitrophenyl)-phenylmethylidene]hydroxylamine Chemical compound C=1C=C([N+]([O-])=O)C=CC=1C(=N/O)/C1=CC=CC=C1 LNOLJFCCYQZFBQ-BUHFOSPRSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LVVJBMKONYUXEG-UHFFFAOYSA-N 2-tert-butyl-6-(4-chlorotriazol-2-yl)-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C(Cl)C=N2)=C1O LVVJBMKONYUXEG-UHFFFAOYSA-N 0.000 description 1
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 1
- 239000004262 Ethyl gallate Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910019567 Re Re Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
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- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- SODJJEXAWOSSON-UHFFFAOYSA-N bis(2-hydroxy-4-methoxyphenyl)methanone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=C(OC)C=C1O SODJJEXAWOSSON-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005685 electric field effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
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- 239000002052 molecular layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
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- 239000005268 rod-like liquid crystal Substances 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/045—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique in a direction which is not parallel or transverse to the direction of feed, e.g. oblique
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D11/00—Producing optical elements, e.g. lenses or prisms
- B29D11/0073—Optical laminates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/10—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment
- B29C59/12—Surface shaping of articles, e.g. embossing; Apparatus therefor by electric discharge treatment in an environment other than air
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2025/00—Use of polymers of vinyl-aromatic compounds or derivatives thereof as moulding material
- B29K2025/04—Polymers of styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
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Description
本發明係關於位相差板之製造方法。詳言之,係關於適於液晶顯示裝置之雙折射補償之位相差板之製造方法。
在於液晶顯示裝置,為提升顯示對比,調整色調,要求用於液晶顯示裝置之位相差板,對可視光區域的所有入射光,均可充分發揮其機能,即,在短波長的光之延遲小,在長波長的光之延遲大,具體而言,於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係。
滿足R450
<R550
<R650
之關係之膜,於專利文獻1,揭示有將位向差大之小阿貝數延伸膜,與相位差小之大阿貝數延伸膜,使光軸大致正交地黏貼而成之位相差板。
於專利文獻2,記載有將450nm的位向差與波長550nm的位向差之比為1.00~1.05之延伸膜,及450nm的位向差與波長550nm的位向差比為1.05~1.20之延伸膜黏貼而成之位相差板。
於該專利文獻1及2,在黏貼時需要正確地對軸。
於專利文獻3以及專利文獻4,記載有將具有正的固有雙折射的樹脂層單軸與具有負的固有雙折射的樹脂層所構成之層積體單軸延伸,使具有正的固有雙折射的樹脂層及負的固有雙折射的樹脂層的分子配向成平行之位相差板。
[專利文獻1]日本特開平2-285304號公報
[專利文獻2]日本特開平5-27119號公報
[專利文獻3]特開2002-40258號公報
[專利文獻4]特開2002-156525號公報
又,在液晶顯示裝置,為使液晶顯示裝置之色調角度依存性變小,提案有使在於入射角0度之位向差Re,與在於入射角40度之位向差R40
,滿足0.92≦R40
/Re≦1.08之關係之位相差板;或面內的遲相軸方向的折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足nx
>nz
>ny
之關係之位相差板。
於專利文獻5,揭示有將聚碳酸酯樹脂之膜單軸延伸得到第一異向性膜,一方面將聚苯乙烯樹脂之膜單軸延伸得到第二異向性膜,藉由使第一異向性膜與第二異向性膜之延伸方向直角疊合,可得滿足nx
>nz
>ny
之關係之位相差板。
另外,於專利文獻6,揭示有將聚碳酸酯樹脂之膜單軸延伸得到第一異向性膜,一方面將聚苯乙烯樹脂之膜單軸延伸得到第二異向性膜,藉由使第一異向性膜與第二異向性膜之延伸方向直角疊合,得到呈(Re-Re40
)/Re≦0.07之位相差板。
於該專利文獻5及專利文獻6,在黏貼時需要正確地對軸。
於專利文獻7,揭示將樹脂膜延伸處理的時候,於該樹脂膜之單面或兩面接著收縮性膜形成層積體,藉由將該層積體加熱延伸處理面賦予向上述樹脂膜延伸方向正交之方向收縮能力,可得滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之位相差板。
該專利文獻7之製法需要正確地控制收縮力。
於專利文獻8,揭示有將聚碳酸酯樹脂熔融押出得到杆棒,將該杆棒切成圓片得到圓板,由該圓板切出長邊的板,藉由將該長方型板單軸延伸,得到0.92≦Re40
/Re≦1.08之位相差板。
但是,專利文獻8的製法難以製造大面積之位相差板。
[專利文獻5]日本特開平3-24502號公報
[專利文獻6]日本特開平3-141303號公報
[專利文獻7]日本特開平5-157911號公報
[專利文獻8]日本特開平2-160204號公報
本發明的目的係在於提供可將複數層以分子配向軸正交地層積而成之位相差板,無須為了對軸之黏貼步驟,而可生產性良好地製造之方法。
再者,本發明的目的係在於提供可簡便地,於大面積,精度良好地製造,於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係之位相差板或者折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之位相差板之方法。
本發明者,為達成上述目的研究的結果,發現將熱可塑性樹脂A與熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜單軸延伸至少2次,使熱可塑性樹脂A之層的分子配向軸與熱可塑性樹脂B之層的分子配向軸大致直角地交叉,則可簡便地,於大面積,高精度而容易地製造滿足R450
<R550
<R650
之關係之位相差板或滿足0<(nx-nz)/(nx-ny)<1之關係之位相差板。本發明係基於該等見識進一步研討,以至完成。
即,本發明包含以下的態樣。
(1)一種位相差板之製造方法,將熱可塑性樹脂A與熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜單軸延伸至少2次,使熱可塑性樹脂A之層的分子配向軸與熱可塑性樹脂B之層的分子配向軸大致直角地交叉。
(2)如(1)所述的位相差板之製造方法,其中熱可塑性樹脂A之荷重彎曲溫度TSA
,與熱可塑性樹脂B之荷重彎曲溫度TSB
之差絕對值為5℃以上。
(3)如(1)或(2)所述的位相差板之製造方法,其中熱可塑性樹脂A在溫度TSB
之斷裂伸度,及熱可塑性樹脂B在溫度TSA
之斷裂伸度,均為50%以上。
(4)如(1)~(3)之任何一項所述的位相差板之製造方法,其中熱可塑性樹脂A係具有正或負的固有雙折射,且熱可塑性樹脂B具有與熱可塑性樹脂A相同符號的固有雙折射。
(5)如(4)所述的位相差板之製造方法,其中位相差板,係於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係者。
(6)如(1)~(3)之任何一項所述的位相差板之製造方法,其中熱可塑性樹脂A係具有正或負的固有雙折射,且熱可塑性樹脂B具有與熱可塑性樹脂A不同符號的固有雙折射。
(7)如(6)或者(7)所述的位相差板之製造方法,其中位相差板面內的遲相軸方向的折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係。
(8)如(1)~(7)之任何一項所述的位相差板之製造方法,其中在於各次單軸延伸之延伸溫度係不同的溫度。
(9)一種位相差板,其係以上述(1)~(8)之任何一項所述的製造方法而得者。
根據本發明之位相差板之製造方法,可簡便地,於大面積,精度良好地製造,於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係之位相差板或者折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之位相差板。
本發明之位相差板之製造方法,包含:將熱可塑性樹脂A與熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜單軸延伸至少2次,使熱可塑性樹脂A之層的分子配向軸與熱可塑性樹脂B之層的分子配向軸大致直角地交叉。
所謂大致直角,係指熱可塑性樹脂A之層的分子配向之方向,與熱可塑性樹脂B之層的分子配向之方向所形成之角度大約是直角。該角度以70度~110度為佳,以80度~100度更佳,以85度~95度最佳。
用於本發明之熱可塑性樹脂A及熱可塑性樹脂B係具有正或負的固有雙折射之熱可塑性樹脂。再者,所謂正的固有雙折射係指延伸方向的折射率較其正交方向之折射率大,係指延伸方向的折射率較其正交方向之折射率小。固有雙折射亦可由介電常數分佈計算。
具有正的固有雙折射之熱可塑性樹脂,可舉聚乙烯、聚丙烯等之烯烴樹脂;聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯等聚酯樹脂;聚苯硫醚等聚芳硫醚樹脂;聚乙烯醇樹脂、聚碳酸酯樹脂、聚烯丙酯樹脂、纖維素酯樹脂、聚醚碸樹脂、聚碸樹脂、聚芳碸樹脂、聚氯乙烯樹脂、降冰片烯樹脂、棒狀液晶聚合物等。該等可以單獨一種或組合兩種以上使用。於本發明,該等之中,以相位差發現性、低溫的延伸性以及與他層之接著性之觀點,以聚碳酸酯樹脂為佳。
具有負的固有雙折射之熱可塑性樹脂,可舉包含苯乙烯或苯乙烯衍生物之單獨聚合體或與其他的單體共聚合體的聚苯乙烯系樹脂;聚丙烯腈樹脂、聚甲基丙烯酸甲酯樹脂、或該等之多元共聚合聚合物等。該等可以單獨一種或組合兩種以上使用。含於聚苯乙烯樹脂之其他的單體,較佳者可舉丙烯腈、馬來酐、甲基丙烯酸甲酯、及丁二烯。在於本發明,該等之中,由相位差顯現性高的觀點,以聚苯乙烯系樹脂為佳,進一步以耐熱性高之點,以苯乙烯或苯乙烯衍生物與馬來酐的共聚合體特別佳。
上述熱可塑性樹脂之荷重彎曲溫度TS
以80℃以上為佳,以110℃上更佳,以120℃以上特別佳。荷重彎曲溫度較上述下限值低,則容易緩和配向。
熱可塑性樹脂A之荷重彎曲溫度TSA
與熱可塑性樹脂B之荷重彎曲的與溫度TSB
的差的絕對值,以5℃以上為佳,以5~40℃更佳,以8~20℃特別佳。若荷重彎曲溫度之差過小,則顯現相位差的溫度依存性會變小。若荷重彎曲溫度之差過大,則難以將荷重彎曲溫度高的熱可塑性樹脂延伸,容易降低位相差板的平面性。
在於溫度TSB
之熱可塑性樹脂A之斷裂伸度,及在於溫度TSA
之熱可塑性樹脂B之斷裂伸度均以50%以上為佳,以80%以上特別佳。只要是斷裂伸度在此範圍之熱可塑性樹脂,則可藉由延伸安定地製作相位差膜。斷裂伸度,係使用JISK7127所記載的試驗片型式1B的試驗片,以拉張速度100mm/分求得。
熱可塑性樹脂A及/或熱可塑性樹脂B,只要是可於1mm之厚度維持全光線穿透率80%以上,則亦可添加調合劑。
添加之調合劑並無特別限定,例如滑劑;層狀結晶化合物;無機粒子;氧化防止劑、熱穩定劑、光穩定劑、耐候穩定劑、紫外線吸收劑、近紅外線吸收劑等的穩定劑;可塑劑;染料與顏料等著色劑;帶電防止劑等。調合劑量可在不損及本發明之目的之範圍適宜決定。特別是藉由添加滑劑或紫外線吸收劑可提升可僥性及耐候性而佳。
滑劑,可舉二氧化矽、二氧化鈦、氧化鎂、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鍶等無機粒子;聚甲基丙烯酸酯、聚甲基丙烯酸甲酯、聚丙烯腈、聚苯乙烯、醋酸纖維素、醋酸丙酸纖維素等有機粒子。於本發明作為滑劑以有機粒子為佳。
紫外線吸收劑,可舉氧基二苯甲酮系化合物、苯並三唑系化合物、柳酸酯系化合物、二苯甲酮系紫外線吸收劑、苯並三唑系紫外線吸收劑、丙烯腈系紫外線吸收劑、三嗪系化合物、鎳錯鹽系化合物、無機粉體等。合適的紫外線吸收劑,可舉2,2’-亞甲基雙(4-(1,1,3,3-四甲基丁基)-6-(2H-苯並三唑-2-基)酚)、2-(2’-羥基3’-第三丁基-5’一甲基苯基)-5-氯三唑、2,4-二第三丁基-6-(5-氯三唑-2-基)酚、2,2’-二羥4,4’-二甲氧基二苯甲酮、2,2,4,4’-四羥基二苯甲酮等,特別合適者可舉2,2’-亞甲基雙(4-(1,1,3,3-四甲基丁基)-6-(2H-苯並三唑-2-基)酚)。
層積膜包含熱可塑性樹脂A之層(A層)與熱可塑性樹脂B之層(B層)。該層積膜可藉由共押出或共流延熱可塑性樹脂A與熱可塑性樹脂B而得。
由製造效率,或在膜中不會殘留溶劑等的揮發性成分之觀點,以共押出成形法為佳。共押出成形法之中,以共押出T型模具法為佳。於共押出T型模具法有分流器方式以及多重分歧管方式,而在可使層A厚度之離散較少之點,以多重分歧管方式特別佳。
作為得到多層膜之方法,採用共押出T型模具法時,在於具有T型模具之押出機之樹脂材料之熔融溫度,係以較所使用之各樹脂材料之熱可塑性樹脂玻璃轉移溫度(Tg)高80~180℃之溫度為佳,以較玻璃轉移溫度高100~150℃之溫度更佳。於押出機之熔融溫度過低,則有樹脂材料流動性不足之虞,相反地熔融溫度過度大,則有樹脂惡化的可能性。
押出溫度只要按照所使用之熱可塑性樹脂適宜選擇即可。押出機內的溫度,於樹脂投入口以Tg~(Tg+100)℃、押出機出口以(Tg+50)℃~(Tg+170)℃、模具溫度以(Tg+50)℃~(Tg+170)℃為佳。在此,Tg係用於樹脂材料之熱可塑性樹脂A的玻璃轉移溫度。
於押出成形法,係將模具開口部所押出的片狀熔融樹脂材料密著於冷卻滾筒。使熔融樹脂材料密著於冷卻滾筒之方法,並無特別限制,可舉例如,空刀方式、真空箱方式、靜電密著方式等。
冷卻滾筒的數量並無特別限制,通常是2支以上。又,冷卻滾筒的配置方法,可舉例如直線型、Z型、L型等,並無特別限制。又,由模具開口部押出之熔融樹脂通過冷卻滾筒的方法亦並無特別限制。
於本發明,根據冷卻滾筒的溫度,押出的片狀樹脂材料與冷卻滾筒的密著情形會變化。升高冷卻滾筒的溫度密著性雖會提高,但是溫度升的過高,則片狀樹脂材料會無法從冷卻滾筒剝落,有產生捲繞於滾筒的不良狀況之虞。因此,冷卻滾筒的溫度,以模具押出之熱可塑性樹脂A的玻璃轉移溫度為Tg,以(Tg+30)℃為佳,以(Tg-5)℃~(Tg-45)℃的範圍更加。藉由如此可防止產生滑移與傷痕等的不良狀況。
又,減少含於膜中的殘留溶劑的含量為佳。為此之手段,可舉(1)減少成為原料之熱可塑性樹脂之殘留溶劑;(2)在成形膜之前將樹脂材料予備乾燥;等的手段。預備乾燥,係例如將樹脂材料作成膠粒等的形態,以熱風乾燥機等進行。乾燥溫度以100℃以上為佳,乾燥時間以2小時以上為佳。藉由進行予備乾燥,可減低膜中的殘留溶劑,並且可預防押出的片狀樹脂材料的起泡。
位相差板製造用之層積膜的總厚度,以10~500μm為佳,以20~200μm更佳,以30~150μm特別佳。較10μm薄則難以得到充分的相位差,機械強度亦會變弱。較500μm厚則柔軟性會惡化而有損及操作性之虞。
A層及B層之厚度,係使用市售之接觸式厚度計,測定膜之總厚度,接著將厚度測定部分切斷用光學顯微鏡觀察剖面,求各層之厚度,尤其比例計算A層及B層之厚度。將以上的操作於膜的MD方向以及TD方向每一定間隔進行,求厚度的平均值以及離散。
再者,厚度的離散,係將上述測定之測定值之算術平均值Tave
作為基準,測定之厚度T中的最大值為Tmax
,最小值為Tmin
,以下式算出。
厚度的離散(μm)=Tave
-Tmin
,及Tmax
-Tave
之中較大者。
藉由A層及B層之厚度的離散在全面以1μm以下,可使色調的離散變小。另外,長期使用後之色調變化也會較均勻。
為使A層及B層之厚度的離散在全面為1μm以下,需進行(1)於押出機內設置網眼為20μm以下之聚合物過過濾器;(2)使齒輪幫浦以5轉/分鐘以上旋轉;(3)在模具周圍配置框圍手段;(4)使空隙為200mm以下;(5)於冷卻輥輪上澆鑄時進行邊緣固定;及(6)押出機使用雙軸押出機或者螺桿形式為雙軸型的單軸押出機。
位相差板製造用之層積膜,亦可具有A層及B層以外之層。例如接著A層與B層之接著層、使膜的滑性變好的墊層、耐衝擊性聚甲基丙烯酸酯樹脂層等的硬塗層、反射防止層、防污層等。
位相差板製造用之層積膜,全光線穿透率以85%以上為佳。未滿85%,不適合作光學構件。上述光線穿透率係遵照JIS K0115,使用分光光度計(日本分光公司製,紫外可視近紅外分光光度計「V-570」)測定。
位相差板製造用之層積膜之霧度以5%以下為佳,以3%以下更佳,以1%以下特別佳。霧度高,則顯示影像的鮮明性會成下降傾向。在此,霧度係遵照JIS K7361-1997,使用日本電色工業公司製「濁度計NDH-300A」,測定5處,由此求平均值。
位相差板製造用之層積膜,ΔYI以5以下為佳,以3以下更佳。該ΔYI在於上述範圍,則不會有著色而視認性會變好。ΔYI係遵照ASTM E313,使用日本電色工業公司製「分光色差計SE2000」測定。進行五次同樣的測定,以其算術平均值求得。
位相差板製造用之層積膜,以JIS鉛筆硬度具有H或其以上的硬度為佳。該JIS鉛筆硬度之調整,可藉由變更樹脂之種類或變更樹脂之層而進行。JIS鉛筆硬度係遵照JIS K 5600-5-4,將各種硬度的鉛筆傾斜45度,由上施加500g重的荷重刮拭膜表面,開始帶傷的鉛筆硬度。
位相差板製造用之層積膜之外表面,大體上並不具有延向MD方向之不規則地產生的線狀凹部或線狀凸部之平坦為佳。在此所謂「大體上並不具有不規則地產生的線狀凹部或線狀凸部之平坦」,係指即使有形成線狀凹部或線狀凸部,其係深度未滿50nm未滿或寬度較500nm為大之線狀凹部;及高度未滿50nm或寬度較500nm為大的線狀凸部。以深度未滿30nm或寬度較700nm為大的線狀凹部;高度未滿30nm或寬度較700nm大的線狀凸部為佳。藉由如此之構成,可防止基於線撞狀凹部或線狀凸部之光折射等,而產生光的干涉或漏光,可提升光學性能。再者,所謂不規則地產生,係指在於非意圖之位置,形成非意圖的尺寸、形狀等。
上述之線狀凹部之深度、線狀凸部之高度,及該等之寬度,可藉由如下所述之方法求得。對位相差板製造用膜照射光,將穿透光投影至螢幕,將於螢幕上出現光明或暗條紋的部分(該部分係線狀凹部之的深度及線狀凸部之高度較大的部分。)以30mm角裁切。將裁切之膜片表面使用三次元表面構造分析顯微鏡(視野區域5mm×7mm)觀察,將此轉換成3次元圖像,由該3次元圖像求剖面輪廓。剖面輪廓係於視野區域以1mm的間隔求得。
在該剖面輪廓,拉平均線,由該平均線到線狀凹部之底的長度與線狀凹部深度,又由平均線到線狀凸部的頂部的長度成線狀凸部高度。平均線與輪廓的交點間的距離成寬度。由該等線狀凹部的深度及線狀凸部的高度之測定值分別求最大值,分別求得顯示該最大值之線狀凹部或線狀凸部之寬度。將由以上求得之線狀凹部的深度及線狀凸部的高度的最大值,顯示其最大值之線狀凹部的寬度及線狀凸部的寬度,作為該膜之線狀凹部的深度、線狀凸部的高度及該等之寬度。
在延伸層積膜之前,亦可設置預先加熱位相差板製造用膜之步驟(預熱步驟)。加熱位相差板製造用膜的手段,可舉烘箱型加熱裝置、循環式加熱裝置、或浸泡於液體中等。其中以烘箱型加熱裝置為佳。在預熱步驟之加熱溫度,通常為延伸溫度-40℃~延伸溫度+20℃,以延伸溫度-30℃~延伸溫度+15℃為佳。延伸溫度,係指加熱裝置之設定溫度。
於本發明,於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係之位相差板[1]之製造方法,使用具有正或者負的固有雙折射者作為熱可塑性樹脂A,使用具有與熱可塑性樹脂A與同符號的固有雙折射者作為熱可塑性樹脂B為佳。熱可塑性樹脂A之層及熱可塑性樹脂B之層,可分別1層或具有2層以上。
於位相差板[1]之製造方法,熱可塑性樹脂A或熱可塑性樹脂B之中,一方的阿貝數以40以上為佳,而另一方的阿貝數以30以下為佳。
在此,阿貝數係表示因光波長之不同所顯現折射率差(分散)的容易度,而以下式表示。
νD
=(nD
-1)/(nF
-nC
)
在此,νD
係阿貝數。nC
、nD
、nF
分別係對C線(波長656nm)、D線(589nm)波長及F線(波長486nm)之折射率。
位相差板[1)製造用之層積膜,使單軸延伸方向為X軸,對單軸延伸方向於膜面內正交之方向為Y軸,及膜厚度方向為Z軸時,對膜面垂直入射且電場向量的振動面在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位,在任一延伸溫度T1及T2,在X軸方向單軸延伸時會遲緩或前進之一方者為佳。
位相差板[1]製造用之層積膜,於低的溫度TL
之延伸,使荷重彎曲溫度高的樹脂所顯現的相位差之絕對值較荷重彎曲溫度低的樹脂所顯現的相位差之絕對值小,而在於高的溫度TH
之延伸,使荷重彎曲溫度低的樹脂所顯發現的位相差之絕對值較荷重彎曲溫度高的樹脂所顯現的相位差之絕對值小地調整兩樹脂層之厚度為佳。位相差板[1]製造用之層積膜,係相位差會大大地顯現的樹脂層依存於延伸溫度之膜。再者,溫度T1係TH
或TL
的任一溫度,溫度T2係與T1不同的TH
或TL
的任一溫度。
於本發明,面內的遲相軸方向的折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之位相差板[2]之製造方法,使用具有正或者負的固有雙折射者作為熱可塑性樹脂A,使用具有與熱可塑性樹脂A與同符號的固有雙折射者作為熱可塑性樹脂B為佳。熱可塑性樹脂A之層及熱可塑性樹脂B之層,可分別1層或具有2層以上。
位相差板[2]製造用之層積膜,單軸延伸方向為X軸,對單軸延伸方向在膜面內正交之方向為Y軸及膜之厚度方向為Z時,對膜面垂直入射且電場向量的振動面在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位,在溫度T1向X軸方向單軸延伸時會遲緩,以與溫度T1不同的溫度T2向X軸方向單軸延伸時為前進者為佳。
於藉由單軸延伸在X軸顯現遲相軸之膜,振動面在於XZ面之直線偏光,對振動面在於YZ面之直線偏光相位會遲緩。相反地藉由單軸延伸在X軸顯現進相軸之膜,振動面在於XZ面之直線偏光,對振動面在於YZ面之直線偏光相位會前進。
位相差板[2]製造用之層積膜,係顯現遲相軸或進相軸之方向依存於延伸溫度之膜。
相位差,係延伸方向之X軸方向之折射率nx
與面向延伸方法相似的正交之方向之Y軸方向之折射率ny
之差(=nx
-ny
)乘以厚度d所求得之值。層積由熱可塑性樹脂A所組成之層(A層)及由熱可塑性樹脂B所組成之層(B層)時之相位差,係由A層的相位差與B層的相位差所合成。為使A層與B層所組成之層積體的相位差的符號,可藉由在於高的溫度TH
及低的溫度TL
之延伸而相反,而在於低的溫度TL
之延伸,使荷重彎曲溫度高的樹脂所顯現的相位差之絕對值較荷重彎曲溫度低的樹脂所顯現的相位差之絕對值小,而在於高的溫度TH
之延伸,使荷重彎曲溫度低的樹脂所顯發現的位相差之絕對值較荷重彎曲溫度高的樹脂所顯現的相位差之絕對值小地調整兩樹脂層之厚度為佳。如此地,藉由單軸延伸調整A層及B層所分別顯現之X軸方向之折射率nx
與Y軸方向之折射率ny
之差,A層厚之總和與B層厚之總和,可得對膜面垂直入射且電場向量的振動面在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位在溫度T1向X軸方向單軸延伸時會遲緩、以與溫度T1不同的溫度T2向X軸方向單軸延伸時為前進之膜。再者,溫度T1,係TH
或TL
之任意一方之溫度,溫度T2,係與T1不同之TH
或TL
之任意一方之溫度。
圖1係表示將位相差板[2]製造用之層積膜的A層(荷重彎曲溫度高之熱可塑性樹脂A之層)及B層(荷重彎曲溫度低之熱可塑性樹脂B之層)分別延伸時的相位差溫度依存性;及延伸位相差板[2]製造用之層積膜(A層+B層)時的相位差溫度依存性。以溫度Tb之延伸由於B層所顯現的負的相位差較A層所顯現之正的相位差大,故A層+B層顯現負的相位差Δ。以另一溫度Ta之延伸由於B層所顯現的負的位相差較A層所顯現的正的相位差小,故A層+B層顯現正的相位差Δ。
例如,A層為聚碳酸酯系樹脂,B層為苯乙烯-馬來酐共聚合體時,A層之厚度的總和與B層之厚度的總之比,以1:5~1:15為佳,以1:5~1:10更佳。A層變的過厚,B層變的過厚,顯現相位差的溫度依存性會變小。
於本發明,其次至少單軸延伸2次上述位相差板製造用之層積膜。在各次的延伸溫度以不同溫度為佳。又延伸方向,於各次使用不同的方向。然後,使熱可塑性樹脂A之層的分子配向軸,與熱可塑性樹脂B之層的分子配向軸大致直角地交叉。
於第一次的單軸延伸,以溫度T1或T2之任一溫度單軸延伸。
於位相差板[1]製造用之層積膜,即使以任一溫度延伸,膜面垂直入射且電場向量的振動面是在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位將會遲緩或前進之一方。
於位相差板[2]製造用之層積膜,以溫度T1延伸,則膜面垂直入射且電場向量的振動面是在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位會遲緩。另一方面,以溫度T2單軸延伸時,膜面垂直入射且電場向量的振動面是在於XZ面之直線偏光,對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位會前進。
熱可塑性樹脂A,使用具有正的固有雙折射率,熱可塑性樹脂B使用具有負的固有雙折射率時,TSA
>TSB
時,溫度T1,以TSB
+3℃以上且TSA
+5℃以下為佳,以TSB
+5℃以上且TSA
+3℃以下更佳。又,溫度T2以TSB
+3℃以下為佳,以TSB
以下更佳。在於第一延伸處理以溫度T1進行為佳。
TSB
>TSA
時,溫度T2以TSA
+3℃以上且TSB
+5℃以下為佳,TSA
+5℃以上且TSB
+3℃以下更佳。又,溫度T1以TSA
+3℃以下為佳,以TSA
以下更佳。在於第一延伸處理以溫度T2進行為佳。
第一次的單軸延伸處理,可以先前習知之方法進行。可舉例如,利用輥輪之間的周速差向縱方向單軸延伸之方法,或使用張布機向橫方向單軸延伸之方法等。向縱方向單軸延伸之方法,可舉於輥輪之間的IR加熱方式或浮動方式等。由可得光學均勻性高之位相差板之點以浮動方式較佳。向橫方向單軸延伸之方法,可舉張布機法。
為減小延伸不均與厚度不均,可於延伸區域在寬度方向具有溫度差。為於延伸區域在寬度方向有溫度差,可使用調整溫風噴嘴在寬度方向的開口度,將IR加熱器在寬度方向排列進行加熱控制等習知之手法。
其次,以與上述第一次單軸延伸處理之溫度不同的溫度T2或者T1,向與上述單軸延伸正交之方向做第二次單軸延伸。在於第二次單軸延伸處理,TSA
>TSB
時以溫度T2進行為佳,TSB
>TSA
時以溫度T1進行為佳。在第二次單軸延伸處理,可直接使用第一次單軸延伸處理所採用的方法。第二次單軸延伸處理,以較第一次單軸延伸處理的延伸倍率小的延伸倍率進行為佳。
熱可塑性樹脂A之層的分子配向軸及熱可塑性樹脂B之層的分子配向軸的方向,可如下進行確認。使用橢偏法,求折射率在位相差板面內成最大的方向,由與熱可塑性樹脂之固有雙折射值的符號之關係,按照以下條件判斷配向軸。
熱可塑性樹脂的固有雙折射為正時:配向軸,係折射率在面內成最大的方向。熱可塑性樹脂的固有雙折射為負時:配向軸,係與折射率在面內成最大的方向正交之方向。
於第一次單軸延伸及/或第二次單軸延伸之後,亦可將延伸之膜進行固定處理。於固定處理之溫度,通常為室溫~延伸溫度+30℃,以延伸溫度-40℃~延伸溫度+20℃為佳。
根據本發明之位相差板之製造方法,使用位相差板[1]製造用之層積膜時,可得於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係之位相差板[1]。另外使用位相差板[2]製造用之層積膜時,可得面內的遲相軸方向的折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之位相差板[2]得到。
藉由本發明之製造方法所得之位相差板,其位向差R550
,以50~400nm為佳,以100~350nm更佳。位向差R450
、R550
及R650
係使用平行尼科爾旋轉法[王子測量機器公司製、KOBRA-WR]測定之值。折射率nx
、nz
、及ny
係以橢偏法在波長550nm測定之值。
以本發明之製造方法所得之位相差板,於60℃、相對濕度90%、100小時的熱處理,於縱方向及橫方向的收縮率以0.5%以下為佳,以0.3%以下更佳。收縮率超過此範圍,則在高溫高濕環境下使用時,會因收縮應力而發生位相差板的變形、由顯示裝置剝離。
以本發明之製造方法所得之位相差板,由於可作雙折射之高度補償,故以其單獨或與其他的構件組合,可使用於液晶顯示裝置、有機EL顯示裝置、電漿顯示裝置、FED(電場發射)顯示裝置、SED(表面電場)顯示裝置等。
液晶顯示裝置,係具備將光入射側偏光板、液晶胞、光出射側偏光板以該順序配置之液晶面板者。藉由將本發明之製造方法所得之位相差板,配置於液晶胞與光入射側偏光板之間及/或在液晶胞與光出射側偏光板之間,可大幅提升液晶顯示裝置的視認性。液晶胞的驅動方式,可舉橫向電場效應(IPS)模式、垂直配向(VA)模式、多象限垂直配向(MVA)模式、連續燄火狀排列(CPA)模式、混合式配向(HAN)模式、扭轉向列(TN)模式、超扭轉向列(STN)模式、光學補償彎曲(OCB)模式等。
藉由本發明之製造方法所得之位相差板,亦可黏貼於液晶胞或偏光板。可將該位相差板黏貼於偏光板的兩面,亦可僅黏貼於單面。又,亦可使用2片以上該位相差板。於黏貼可使用習知之接著劑。
偏光板,係由偏光子與黏貼於其兩面之保護膜所組成。亦可取代該保護膜,直接將本發明之製造方法所得之位相差板黏貼於偏光板,將位相差板作為保護膜。由於省略保護膜,可使液晶顯示裝置變薄。
以實施例,更加詳細地說明本發明,惟本發明並不應該限定於以下實施例。再者部以及%,若無特別提及係重量基準。
使用高速分光橢偏法(J. A. Woollam公司製,產品名「M-2000U」)求折射率在面內成最大的方向,以下述所示與固有雙折射值的符號關係決定配向軸。
固有雙折射為正時:配向軸,係折射率在面內成最大的方向
固有雙折射為負時:配向軸,係與折射率在面內成最大的方向正交之方向
再者,測定係以溫度20℃±2℃,相對濕度60±5%的條件下進行,在面內成最大的折射率,係將入射角度55度,60度及65度的3點,於波長區域400~1000nm的光譜所算出的數據,作為在於波長550nm之值。
將膜包埋於環氧樹脂後,使用切片機(大和工業公司製產品名「RUB-2100」)切片,使用掃描式電子顯微鏡觀察剖面,測定。
折射率nx
、nz
及ny
,係使用分光橢偏法(J. A. Woollam公司製,產品名「M-2000U」),於溫度20℃±2℃、相對濕度60±5%之條件下進行,折射率,係將入射角度55、60、65度的3點,波長區域400~1000nm的光譜算出的數據,作為在波長550nm之值。
遵照JIS K0115,使用分光光度計(日本分光公司製,紫外可視近紅外分光光度計「V-570」)測定。
樹脂荷重彎曲溫度係遵照JISK6717-2作成試驗片測定之。
使用平行尼科爾旋轉法(王子測量機器公司製、KOBRA-WR)測定在於各波長之位向差及對膜長邊方向之遲相軸之角度。將同樣的測定,向相位差膜的寬幅方向以等間隔測定10點,算出平均值。
使用阿貝折射計(ATAGO公司製、DR-M2),以溫度20℃±2℃、相對濕度60±5%之條件下測定。
準備二種三層共押出成形用膜成形裝置,將聚碳酸酯樹脂(旭化成公司製,WONDERLITE PC-110,荷重彎曲溫度145度,固有雙折射是正,阿貝數30)之膠粒,投入雙軸型螺桿的一邊的單軸押出機,使之熔融。
將降冰片系聚合體樹脂(日本ZEON公司製,ZEONOR1420R,荷重彎曲溫度136℃,固有雙折射為正,阿貝數56)之膠粒,投入具有雙軸型螺桿的另一邊的單軸押出機,使之熔融。
作為接著劑,將苯乙烯-乙烯-丁烯-苯乙烯-嵌段共聚合體(SEBS),投入具有雙軸型螺桿的一邊的單軸押出機,使之熔融。
將熔融的260℃的聚碳酸酯樹脂透過10μm網目的葉盤形狀的聚合物過濾器供給於多歧管模具(模唇的表面粗糙度Ra:0.1μm)之一邊的多歧管,將熔融的260℃的降冰片烯系聚合體樹脂透過10μm網目的葉盤形狀的聚合物過濾器供給於另一邊的多歧管。又,將熔融的260℃的SEBS透過10μm網目的葉盤形狀的聚合物過濾器供給於接著劑用的多歧管。
將聚碳酸酯樹脂、降冰片烯系共聚合體樹脂、及SEBS由該多歧管模具,以260℃同時押出成膜狀。將該膜狀熔融樹脂澆鑄於表面溫度調整為130℃的冷卻輥輪,接著通過表面溫度調整為50℃的2支冷卻輥輪之間,得到由聚碳酸酯樹脂層(A層:20μm)、SEBS層(5μm)與降冰片烯系共聚合體樹脂層(B層:160μm)所組成之寬1350mm且厚度為185μm之層積膜1。
將製造例1所得之層積膜1供給於縱方向單軸延伸機,以延伸溫度145℃,延伸倍率1.5向縱方向延伸。接著,將延伸之膜供給於張布延伸機,以延伸溫度125℃,延伸倍率1.25向寬方向延伸,得到位相差板1。
以橢偏法測定位相差板1之A層的折射率,確認到A層的配向軸與膜的長邊方向大致平行,同樣地以橢偏法測定B層的折射率,確認B層的配向軸存在於與膜的長邊方向大致正交之方向。係為顯示R450<R550<R650之關係者。將評估結果示於表1。
於實施例1向寬方向延伸的延伸溫度改為145℃之外,以與實施例1同樣地得到位向差板2。
以橢偏法測定位相差板2之A層的折射率,確認到A層的配向軸與膜的長邊方向大致平行,同樣地以橢偏法測定B層的折射率,確認B層的配向軸存在於與膜的長邊方向大致平行之方向。係為顯示R450>R550>R650之關係者。將評估結果示於表1。
如表1所示,將具有同符號的固有雙折射之熱可塑性樹脂A與熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜單軸延伸至少2次使熱可塑性樹脂A層之分子配向軸與熱可塑性樹脂B層之分子配向軸大致以直角交叉,可容易且高精度地得到於波長450nm的光在入射角0度之位向差R450
,波長550nm的光在入射角0度之位向差R550
,於波長650nm的光在入射角0度之位向差R650
,滿足R450
<R550
<R650
之關係者之大面積的位向差板。
準備二種雙層共押出成形用膜成形裝置,將聚碳酸酯樹脂(旭化成公司製、WONDERLITE PC-110,荷重彎曲溫度145度)之膠粒,投入具有雙軸型螺桿的一邊的單軸押出機,使之熔融。
將苯乙烯-馬來酐共聚合體樹脂(NovaChemicals公司製、DylarkD332、荷重彎曲溫度135℃,固有雙折射為負,阿貝數31)之膠粒,投入具有雙軸型螺桿的另一邊的單軸押出機,使之熔融。
將熔融的260℃的聚碳酸酯樹脂透過10μm網目的葉盤形狀的聚合物過濾器供給於多歧管模具(模唇的表面粗糙度Ra:0.1μm)之一邊的多歧管,將熔融的260℃的苯乙烯馬來酐共聚合體樹脂透過10μm網目的葉盤形狀的聚合物過濾器供給於另一邊的多歧管。
將聚碳酸酯樹脂及苯乙烯馬來酐共聚合體樹脂由該多歧管模具,以260℃同時押出成膜狀。將該膜狀熔融樹脂澆鑄於表面溫度調整為130℃的冷卻輥輪,接著通過表面溫度調整為50℃的2支冷卻輥輪之間,得到由聚碳酸酯樹脂層(A層:20μm)與苯乙烯馬來酐共聚合體樹脂層(B層:160μm)所組成之寬1350mm且厚度為180μm之層積膜2。
取代DylarkD332使用聚苯乙烯樹脂(日本聚苯乙烯公司製,HF44,荷重彎曲溫度73℃,固有雙折射為負,阿貝數31),A層之厚度為80μm,B層之厚度為80μm以外以與製造例2同樣地得到聚碳酸酯樹脂層(A層:80μm)-聚苯乙烯樹脂層(B層:80μm)所組成之寬1350mm且厚度為160μm之層積膜3。
取代實施例1所使用之層積膜1使用層積膜2之外,與實施例1同樣地得到位向差板3。
以橢偏法測定位相差板3之A層的折射率,確認到A層的配向軸與膜的長邊方向大致平行,同樣地以橢偏法測定B層的折射率,確認B層的配向軸存在於與膜的長邊方向大致正交之方向。(nx
-nz
)/(nx
-ny
)為0.6849。將評估結果示於表2。
取代實施例1所使用之層積膜1使用層積膜3,將橫向延伸溫度改為70℃之外,以與實施例1同樣地得到位向差板4。
以橢偏法測定位相差板4之A層的折射率,確認到A層的配向軸配向軸存在於與膜的長邊方向大致正交之方向,同樣地以橢偏法測定B層的折射率,確認B層的配向軸存在於與膜的長邊方向大致正交之方向。(nx
-nz
)/(nx
-ny
)為2.3815。將評估結果示於表2。
如表2所示,將具有不同符號的固有雙折射之熱可塑性樹脂A與熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜至少單軸延伸2次使熱可塑性樹脂A層的分子配向軸與熱可塑性樹脂B層的分子配向軸大致以直角交叉,可容易且高精度地得到面內的遲相軸方向的折射率nx
、與其於面內正交之方向之折射率ny
、及厚度方向之折射率nz
,滿足0<(nx
-nz
)/(nx
-ny
)<1之關係之大面積的位相差板。
圖1係表示A層、B層、及A層與B層之層積體之相位差溫度依存性之圖。
Claims (19)
- 一種位相差板之製造方法,將具有正或負的固有雙折射且荷重彎曲溫度為TSA 之熱可塑性樹脂A與具有與熱可塑性樹脂A不同符號的固有雙折射且荷重彎曲溫度TSB 且TSA 與TSB 之差絕對值為5~40℃之熱可塑性樹脂B共押出或共流延,得到包含熱可塑性樹脂A之層與熱可塑性樹脂B之層之層積膜,藉由將該層積膜單軸延伸至少2次,使熱可塑性樹脂A之層的分子配向軸與熱可塑性樹脂B之層的分子配向軸大致直角地交叉。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中上述至少2次的單軸延伸,是由第一次單軸延伸與第二次單軸延伸構成,該第二次單軸延伸是在與該第一次單軸延伸的方向直交的方向進行。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中熱可塑性樹脂A在溫度TSB 之斷裂伸度,及熱可塑性樹脂B在溫度TSA 之斷裂伸度,均為50%以上。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中位相差板,係於波長450nm的光在入射角0度之位向差R450 ,波長550nm的光在入射角0度之位向差R550 ,於波長650nm的光在入射角0度之位向差R650 ,滿足R450 <R550 <R650 之關係者。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中該熱可塑性樹脂A為聚碳酸酯系樹脂、該熱可塑 性樹脂B為聚苯乙烯樹脂。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中該熱可塑性樹脂A為聚碳酸酯系樹脂、該熱可塑性樹脂B為苯乙烯-馬來酐共聚合體。
- 如申請專利範圍第6項所述的位相差板之製造方法,其中該熱可塑性樹脂A之層之厚度的總和與該熱可塑性樹脂B之層之厚度的總和之比為1:5~1:15。
- 如申請專利範圍第2項所述的位相差板之製造方法,其中該層積膜為:以單軸延伸方向為X軸、對單軸延伸方向於膜面內正交之方向為Y軸、及膜厚度方向為Z軸時,對膜面垂直入射且電場向量的振動面在於XZ面之直線偏光之對膜面垂直入射且電場向量的振動面在於YZ面之直線偏光的相位,在溫度T1、在X軸方向單軸延伸時會遲緩,在異於溫度T1的溫度T2、在X軸方向單軸延伸時會前進。
- 如申請專利範圍第8項所述的位相差板之製造方法,其中該熱可塑性樹脂A具有正的固有雙折射,且該熱可塑性樹脂B具有負的固有雙折射;該熱可塑性樹脂A之荷重彎曲溫度TSA 高於該熱可塑性樹脂B之荷重彎曲溫度TSB ;以及該溫度T1為TSB +5℃以上、該溫度T2為TSB +3℃以下。
- 如申請專利範圍第8項所述的位相差板之製造方 法,其中該熱可塑性樹脂A具有正的固有雙折射,且該熱可塑性樹脂B具有負的固有雙折射;該熱可塑性樹脂B之荷重彎曲溫度TSB 高於該熱可塑性樹脂A之荷重彎曲溫度TSA ;以及該溫度T2為TSA +5℃以上、該溫度T1為TSA +3℃以下。
- 如申請專利範圍第8項所述的位相差板之製造方法,其中該熱可塑性樹脂A之荷重彎曲溫度TSA 高於該熱可塑性樹脂B之荷重彎曲溫度TSB ;以及在該溫度T1進行該第一次單軸延伸、在該溫度T2進行該第二次單軸延伸。
- 如申請專利範圍第8項所述的位相差板之製造方法,其中該熱可塑性樹脂B之荷重彎曲溫度TSB 高於該熱可塑性樹脂A之荷重彎曲溫度TSA ;以及在該溫度T2進行該第一次單軸延伸、在該溫度T1進行該第二次單軸延伸。
- 如申請專利範圍第8項所述的位相差板之製造方法,其中該溫度T1及該溫度T2為125℃以上、145℃以下。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中位相差板面內的遲相軸方向的折射率nx 、與其於面內正交之方向之折射率ny 、及厚度方向之折射率nz ,滿足0<(nx -nz )/(nx -ny )<1之關係。
- 如申請專利範圍第1項所述的位相差板之製造方法,其中在於各次單軸延伸之延伸溫度係不同的溫度。
- 如申請專利範圍第2項所述的位相差板之製造方法,其中是以小於該第一次單軸延伸的延伸倍率之延伸倍率來進行該第二次單軸延伸。
- 一種位相差板,以上述申請專利範圍第1至16項中任一項所述的製造方法而得者。
- 如申請專利範圍第17項所述的位相差板,其中於波長450nm的光在入射角0度之位向差R450 、波長550nm的光在入射角0度之位向差R550 、於波長650nm的光在入射角0度之位向差R650 ,是滿足R450 <R550 <R650 之關係。
- 如申請專利範圍第17項所述的位相差板,其中面內的遲相軸方向的折射率nx 、與其於面內正交之方向之折射率ny 、厚度方向之折射率nz ,是滿足0<(nx -nz )/(nx -ny )<1之關係。
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- 2008-02-14 JP JP2008033781A patent/JP5104373B2/ja active Active
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2009
- 2009-01-08 TW TW98100444A patent/TWI440904B/zh active
- 2009-02-12 KR KR1020090011464A patent/KR101576290B1/ko active IP Right Grant
- 2009-02-13 US US12/371,307 patent/US9050763B2/en not_active Expired - Fee Related
- 2009-02-13 EP EP09002052.0A patent/EP2090420B1/en active Active
- 2009-02-16 CN CN200910006373.9A patent/CN101508166B/zh active Active
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2015
- 2015-05-01 US US14/702,312 patent/US10261227B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
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US10261227B2 (en) | 2019-04-16 |
CN101508166B (zh) | 2015-05-20 |
US9050763B2 (en) | 2015-06-09 |
KR20090088322A (ko) | 2009-08-19 |
TW200942877A (en) | 2009-10-16 |
US20090214869A1 (en) | 2009-08-27 |
KR101576290B1 (ko) | 2015-12-09 |
JP5104373B2 (ja) | 2012-12-19 |
EP2090420A2 (en) | 2009-08-19 |
CN101508166A (zh) | 2009-08-19 |
US20150234107A1 (en) | 2015-08-20 |
EP2090420B1 (en) | 2019-07-17 |
JP2009192844A (ja) | 2009-08-27 |
EP2090420A3 (en) | 2014-06-04 |
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