WO2001055755A1 - Plaques de guidage optique et procede de fabrication correspondant - Google Patents
Plaques de guidage optique et procede de fabrication correspondant Download PDFInfo
- Publication number
- WO2001055755A1 WO2001055755A1 PCT/JP2000/008211 JP0008211W WO0155755A1 WO 2001055755 A1 WO2001055755 A1 WO 2001055755A1 JP 0008211 W JP0008211 W JP 0008211W WO 0155755 A1 WO0155755 A1 WO 0155755A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- light guide
- guide plate
- liters
- mass
- polycarbonate
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 239000004417 polycarbonate Substances 0.000 claims abstract description 36
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 32
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 30
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 229920001634 Copolyester Polymers 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 51
- -1 polymethylene Polymers 0.000 claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 238000000149 argon plasma sintering Methods 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 238000001746 injection moulding Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 83
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 125000005375 organosiloxane group Chemical group 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 2
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- JXDYKVIHCLTXOP-UHFFFAOYSA-N isatin Chemical compound C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WMRCTEPOPAZMMN-UHFFFAOYSA-N 2-undecylpropanedioic acid Chemical compound CCCCCCCCCCCC(C(O)=O)C(O)=O WMRCTEPOPAZMMN-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- JZVUPTMPUNLWMX-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)cyclopentyl]phenol Chemical compound C1=CC(O)=CC=C1C1CC(C=2C=CC(O)=CC=2)CC1 JZVUPTMPUNLWMX-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006353 Acrylite® Polymers 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZJMYKFLCRJIRIJ-UHFFFAOYSA-N CCCCCCCC.OC1=CC=C(C=C1)O Chemical compound CCCCCCCC.OC1=CC=C(C=C1)O ZJMYKFLCRJIRIJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 241000238558 Eucarida Species 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 239000004610 Internal Lubricant Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001118 alkylidene group Chemical group 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
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006085 branching agent Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/0001—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
Definitions
- the present invention relates to a light guide plate and a method for manufacturing the same, and more particularly, to a light guide plate used for a back lighting device such as a vehicle-mounted meter panel, a till lamp, etc. It relates to the manufacturing method.
- This surface light source is formed of a transparent plate-shaped molded body, emits surface light by receiving light from the cold cathode tube (fluorescent lamp) as the present light source, and is also called a light guide plate. That is, the light from the light source is introduced from the side of the light guide plate, and a part of the light transmitted through the plate emits scattered light by the light scattering layer provided on the back surface of the plate, and the entire surface becomes uniform. It emits light.
- dot patterns were printed on the back surface of the plate or a conical drill was cut to form the light-scattering layer.
- the method of transferring the mechanism is used.
- an acrylic resin PMMA
- acrylic resin is inferior in heat resistance, mechanical strength, and flame retardancy, so it is not suitable for lighting equipment such as displays for cars, till lamps, and turn signals, and has heat resistance and mechanical strength.
- Polycarbonate resin has begun to be used due to its good flame retardancy.
- general polycarbonate resin is inferior in fluidity, and when transferring a microprism structure to a plate, There is a problem that transferability is low.
- transferability In order to improve the transferability, there is a method of reducing the molecular weight of the polycarbonate resin.
- the mechanical strength decreases as the molecular weight decreases.
- An object of the present invention is to provide a light guide plate manufactured using the improved polycarbonate resin composition and a method for manufacturing the same.
- the gist of the present invention is as follows.
- a light guide plate made of a copolyestercarbonate having an aliphatic segment.
- A a copolyester carbonate having an aliphatic segment, and at least one resin selected from (B) an aromatic polycarbonate and (C) an acrylic resin, ) Polycarbonate blended with 0.01 to 1.0 parts by mass of (C) (A) 100 parts by mass at most up to 90 parts by mass with respect to (A) 100 parts by mass.
- a light guide plate using a net resin composition a copolyester carbonate having an aliphatic segment, and at least one resin selected from (B) an aromatic polycarbonate and (C) an acrylic resin, ) Polycarbonate blended with 0.01 to 1.0 parts by mass of (C) (A) 100 parts by mass at most up to 90 parts by mass with respect to (A) 100 parts by mass.
- the aliphatic segment in the component (A) is caused by polymethylene dicarboxylic acid, and the ratio of the polymethylene dicarboxylic acid is based on the main monomer (divalent phenol) of the entire polycarbonate resin composition. 3.
- R 1 represents an alkyl group having 10 to 30 carbon atoms or a branched alkyl group having 10 to 30 carbon atoms.
- a light guide plate comprising an aromatic boron resin having a substituted phenoxy group represented by the following formula as a terminal group.
- the light guide plate of the present invention uses a polycarbonate resin composition comprising (A) a copolyester carbonate having an aliphatic segment and (B) an aromatic polycarbonate.
- the copolyestercarbonate having an aliphatic segment (A) as a component of the present invention (hereinafter abbreviated as BPA-PMDC copolymer) is, for example, an aromatic polycarbonate portion and a divalent phenol.
- an aromatic polycarbonate portion comprising a structural unit represented by the following structural formula (1) and a polyester portion derived from a polymethylenedicarboxylic acid, and preferably represented by the following structural formula (2)
- Copolymers having a polyester unit composed of structural units in the molecule can be mentioned.
- R 1 and R 2 represent an alkyl group having 1 to 6 carbon atoms or a phenyl group, which may be the same or different.
- Z is a single bond, an alkylene group having 1 to 20 carbon atoms or an alkylene group having 1 to 20 carbon atoms.
- a alkylidene group, a cycloalkylene group having 5 to 20 carbon atoms or a cycloalkylidene group having 5 to 20 carbon atoms, a certain bond is one S 0 2 —, one SO —, one S 1, one O —, one CO — bond Is shown.
- it is an isopropylidene group.
- a and b are integers of 0 to 4, preferably 0.
- n represents an integer of 8 to 20.
- the BPA-PMDC copolymer is prepared by, for example, converting a previously prepared polycarbonate polyol (hereinafter abbreviated as PC oligomer) constituting an aromatic polycarbonate portion and polymethylene dicarboxylic acid into methylene chloride, Dissolved in solvents such as benzene and chlorophonolem, and added an aqueous caustic solution of divalent phenol, and used as a catalyst as a tertiary amine (such as triethylamine) or a quaternary ammonium salt (trimethylbenzene). Lummonium chloride) and interfacial polycondensation reaction in the presence of a terminal stopper.
- PC oligomer polycarbonate polyol constituting an aromatic polycarbonate portion and polymethylene dicarboxylic acid
- solvents such as benzene and chlorophonolem
- a catalyst such as a tertiary amine (such as triethylamine) or
- terminal terminating agent those usually used for the production of polycarbonate may be used, and various types can be used. Specifically, pheno-nore, p-creso-no-nore, p-tert-p-chino-reno-no-no-re, tert-octyl-pheno-nore, especially p-tert-octyl-fueno-no-no-re, p-cumino-le-no-no- —Nore, p—noninolepheno—nore, p—tert-monoaminophenol and the like are monovalent phenols. Further, as the terminal terminator, a phenol represented by the following general formula is used.
- R 1 is an alkyl group having 10 to 30 carbon atoms, preferably an alkyl group having 10 to 20 carbon atoms.
- the alkyl group may be a straight-chain or branched one. Of these, p-alkylphenol is preferred. Further, all the terminals may not be capped and the hydroxyl groups of the divalent phenol may remain, and the terminal fraction is 60. / 0 or more.
- PC oligomer is prepared by the following general formula (3) in a solvent such as methylene chloride.
- a divalent phenol represented by the following with a carbonate precursor such as phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, a reaction between a divalent phenol and a carbonate precursor such as phosgene, or a reaction between a divalent phenol and a carbonate such as diphenylene carbonate. It is produced by transesterification with precursors.
- 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) is particularly preferable.
- divalent phenols other than bisphenol A include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4— Hydroxyfeni Le) butane, 2,2-bis (4-hydroxyphenol) octane, 2,2-bis (4-hydroxy-1- 1-methylphenyl) pronocene, 1,1-bis (4-hydroxy) 1-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-13-bromopheninole) prono ⁇ .
- Dihydroxydiphenyl sulfones such as 3′-dimethyldiphenylsulfone; and dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl. These divalent phenols are Each of these may be used alone, or two or more of them may be used in combination.
- Examples of the carbonate compound include diaryl carbonate such as diphenyl carbonate, dialkyl carbonate such as dimethyl carbonate and getyl carbonate, and the like.
- the PC oligomer used in the production of the PC-PMD C copolymer may be a homopolymer using the above-mentioned divalent phenol-type, or a copolymer using two or more types. . Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the above divalent phenol.
- branching agent a multifunctional aromatic compound
- polymethylene dicarboxylic acid those having 8 to 20 carbon atoms of methylene are preferable.
- octanedicarboxylic acid, decanedicarboxylic acid, and dodecanedicarboxylic acid can be mentioned, and among them, decanedicarboxylic acid is preferable.
- the component can be produced as described above, but generally aromatic polycarbonate may be produced as a by-product, and the total viscosity average molecular weight is preferably from 10,000 to 400,000. More preferably, it is from 12,000 to 30,000.
- the aromatic polycarbonate of the component ( ⁇ ) preferably has a viscosity average molecular weight of 100,000 to 40,000, more preferably 12,0,000. 0 0 to 30 and 0 0 0.
- the aromatic polycarbonate is not particularly limited, but can be easily produced by reacting a divalent phenol with phosgene or a carbonate compound.
- the divalent phenol may be the same as or different from the compound represented by the above general formula (3). Further, a homopolymer using one of the above-mentioned divalent phenols or a copolymer using two or more of the above-mentioned divalent phenols may be used. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the above-mentioned divalent phenol.
- Examples of the carbonate compound include dialkyl carbonates such as diphenyl carbonate and dimethyl carbonate, and dialkyl carbonates such as getyl carbonate.
- the terminating agent may be any of those generally used in the production of polycarbonate, and various types can be used.
- the polycarbonate resin composition comprising the component (A) and the component (B) used in the light guide plate of the present invention preferably has a viscosity average molecular weight of 100,000 to 40,000. It is more preferably from 12,000 to 25,000, and particularly preferably from 14,000 to: 9,000. If the molecular weight is too low, the mechanical strength of the resin composition of the present invention may be inferior. If the molecular weight is too high, the fluidity of the resin composition of the present invention may be inferior.
- the amount of the polymethylene dicarboxylic acid is composed of the components (A) and (B). 1 to 30 mol based on the main monomer (divalent phenol) of the entire polycarbonate resin composition.
- / 0 is preferable, more preferably 2 to 20 mol%, and particularly preferably 5 to 10 mol%. If the amount of polymethylene dicarboxylic acid is too small, the fluidity of the polycarbonate resin composition may not be improved, and if too large, the heat resistance of the polycarbonate resin composition may be reduced.
- the light guide property of (C) in order to improve the light guiding property of the polycarbonate resin composition, 0.01 to 1.0 parts by mass of (C) is used per 100 parts by mass of the polycarbonate resin composition. It is preferable to add an acrylic resin. If the amount is less than 0.01 part by mass, the light guide property may not be improved. If the amount is more than 1.0 part by mass, the light guide property may be reduced. More preferably, it is 0.05 to 0.5 part by mass.
- acryl-based resin refers to a polymer having a repeating unit of a monomer unit of acrylic acid, acrylic acid ester, acrylonitrile and a derivative thereof, and is a homopolymer or styrene, It refers to a polymer with butadiene. Specifically, polyacrylic acid, polymethyl methacrylate
- PMMA polyacrylonitrile
- ethyl acrylate-co-acrylic acid 1-2-chloromethyl copolymer acrylic acid 1-n-butyl-1-acryl ditolyl copolymer
- acrylonitrile examples thereof include a tri-styrene copolymer, an acrylonitrile butadiene copolymer, and an atalylonitributadiene styrene copolymer.
- PMMA polymethyl methacrylate
- a functional group such as a methoxy group or a vinyl group is added to the silicon-based compound as a stabilizer of the polycarbonate resin composition. It is more preferable to add a reactive silicon compound (organosiloxane or the like) into which is introduced. in this case, The addition amount is usually 0.01 to 3.0 parts by mass, preferably 0.05 to 2.0 parts by mass, based on 100 parts by mass of the polycarbonate resin composition.
- additives may be blended with the polycarbonate resin composition as long as the object of the present invention is not impaired.
- Internal lubricants such as aliphatic carboxylic acid-ester type, paraffin type, silicon oil, polyethylene wax, etc., common flame retardants, flame retardant aids, release agents, antistatic agents, etc. .
- the above components may be blended and kneaded in a usual manner, for example, a ribbon blender, a drum tumbler, a henshenole mixer, a mixer, a single screw extruder, and a twin screw extruder. It can be carried out by a screw extruder, a kneader, a multi-screw single screw extruder, etc.
- An appropriate heating temperature for kneading is usually 280 to 320 ° C.
- the light guide plate of the present invention is formed of a plate-like molded body formed using the above-mentioned polycarbonate resin composition, and has a light scattering layer on its front surface or back surface.
- a dot pattern can be printed or a conical drill can be cut, but it is preferable to transfer the prism structure of the microphone opening.
- the microprism is not particularly limited, but is preferably a tetrahedron. Further, the height is preferably from 10 to 300 / im, more preferably from 20 to 200 m, and particularly preferably from 50 to 100 / im.
- a micro prism structure as a light scattering layer is formed by using a stamper during injection molding of the plate-like molded body. What is necessary is just to transfer to a surface or a back surface. In that case, the light scattering layer may be the entire surface of the light guide plate or a part thereof.
- the injection molding is preferably performed with a cylinder temperature of 260 to 330 ° C and a mold temperature of 50 to 120 ° C.
- the light guide plate is not particularly limited, and may be a flat plate having a thickness of about 3 mm. Further, the shape is not necessarily limited to a flat plate shape, but may be a curved plate having a lens effect, and may be appropriately selected according to the purpose and application. For example, a structure having a wedge-shaped cross section in which the thickness of the light guide plate becomes gradually thinner as the distance from the light source increases. Further, a structure in which a display unit made of a separate member is integrally provided on the front surface of the planar light-emitting body may be adopted.
- the tubular reactor used here was a double tube, and the outlet temperature of the reaction solution was kept at 25 ° C by passing cooling water through the jacket.
- the pH of the discharged liquid was adjusted to be 10 to 11.
- the reaction solution thus obtained was allowed to stand, and the aqueous phase was separated and removed, and the methylene chloride phase (220 liters) was collected. 7 g Z Liter).
- the degree of polymerization of the polycarbonate oligomer obtained here was 2 to 4 and the concentration of the black mouth homemate group was 0.7 normal.
- the viscosity average molecular weight (M v) of the BPA-PMD C copolymer and the aromatic polycarbonate resin was determined by measuring the viscosity of a methylene chloride solution at 20 ° C using an Ubbelohde viscometer. After obtaining the intrinsic viscosity [77], it was calculated by the following equation.
- the obtained flaky polymer was dried at 120 ° C for 48 hours.
- the terminal fraction of p-dodecylphenoxy groups was 99.5%, and the viscosity average molecular weight of the polymer was 17,000.
- Production Example 4 was the same as Production Example 4 except that p-tert-butylphenol was used in an amount of 95.9 g instead of p-dodecylphenol 167 g. Similarly, a flaky polymer was obtained. The terminal fraction of p-tert-butylphenoxy group was 99.5%, and the viscosity average molecular weight of the polymer was 17,000.
- the viscosity-average molecular weight (Mv) of the polycarbonate resin was determined by measuring the viscosity of a methylene chloride solution at 20 ° C with an Ube-Ide-type viscometer, and the limiting viscosity [;?] was obtained. After calculating, it was calculated by the following equation.
- the polycarbonate oligomer 10 liters obtained in Production Example 1 was placed in a stirred container having an internal volume of 50 liters, and p-tert-octynolephenol 155 g was dissolved. Then, an aqueous solution of sodium hydroxide (53 g of sodium hydroxide, 1 liter of water) and 5.8 cc of triethylamine were added, and the mixture was stirred at 300 rpm for 1 hour to react. Was. Then, a sodium hydroxide solution of bisphenol A (bisphenol: 720 g, sodium hydroxide 41 g, 5.5 liters of water) was mixed with the above system.
- bisphenol A bisphenol: 720 g, sodium hydroxide 41 g, 5.5 liters of water
- a flaky polymer was obtained in the same manner as in Production Example 6, except that p-tert-octylphenol in Example 6 was replaced by 3 g of p-tert-butylphenol 1] instead of 5.5 g of p-tert-octylphenol.
- the terminal fraction of p-tert-butylbutyloxy group was 99.5%, and the viscosity-average molecular weight of the polymer was 15,000.
- a flake polymer was obtained in the same manner as in Production Example 6, except that 71 g of phenol was used instead of 5.5 g of p-tert-octylphenol in Production Example 6.
- the terminal fraction of the phenoxy groups was 99.5%, and the viscosity-average molecular weight of the polymer was 15,100.
- the viscosity average molecular weight (Mv) of the polycarbonate resin was determined by measuring the viscosity of a methylene chloride solution at 20 ° C using a Ube-Machine-type viscometer, and the intrinsic viscosity [ ⁇ ?] was determined from this. Then, it was calculated by the following equation.
- a flake polymer was obtained in the same manner as in Production Example 10 except that 71 g of phenol was used in place of 5.5 g of p-tert-octylphenol in Production Example 10.
- the viscosity average molecular weight of the polymer was 15,100.
- the height of the regular tetrahedron of the microphone prism was measured using a scanning laser microscope manufactured by Olympus Optical.
- the transferability of the microprism structure can be improved when manufacturing the light guide plate.
- the light guide plate is excellent in both mechanical strength and light guide.
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00976400A EP1251371B1 (en) | 2000-01-27 | 2000-11-21 | Light guide plates and process for producing the same |
CA002386934A CA2386934A1 (en) | 2000-01-27 | 2000-11-21 | Light guide plates and process for producing the same |
US10/110,135 US6941057B1 (en) | 2000-01-27 | 2000-11-21 | Light guide plates and process for producing the same |
DE60033568T DE60033568T2 (de) | 2000-01-27 | 2000-11-21 | Lichtleiterplatten und verfahren zu deren herstellung |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000018621A JP4156162B2 (ja) | 2000-01-27 | 2000-01-27 | 導光板及びその製造方法 |
JP2000-018620 | 2000-01-27 | ||
JP2000018620A JP4156161B2 (ja) | 2000-01-27 | 2000-01-27 | 導光板及びその製造方法 |
JP2000-018621 | 2000-01-27 | ||
JP2000021407A JP4156163B2 (ja) | 2000-01-31 | 2000-01-31 | 導光板及びその製造方法 |
JP2000-021407 | 2000-01-31 |
Publications (1)
Publication Number | Publication Date |
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WO2001055755A1 true WO2001055755A1 (fr) | 2001-08-02 |
Family
ID=27342153
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/008211 WO2001055755A1 (fr) | 2000-01-27 | 2000-11-21 | Plaques de guidage optique et procede de fabrication correspondant |
Country Status (7)
Country | Link |
---|---|
US (1) | US6941057B1 (ja) |
EP (1) | EP1251371B1 (ja) |
KR (1) | KR100726037B1 (ja) |
CA (1) | CA2386934A1 (ja) |
DE (1) | DE60033568T2 (ja) |
TW (1) | TW487811B (ja) |
WO (1) | WO2001055755A1 (ja) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
USRE36268E (en) * | 1988-03-15 | 1999-08-17 | Boehringer Mannheim Corporation | Method and apparatus for amperometric diagnostic analysis |
JP5230098B2 (ja) * | 2004-04-26 | 2013-07-10 | 出光興産株式会社 | 熱可塑性樹脂組成物及びそれを用いた成形体 |
KR100665781B1 (ko) * | 2004-09-10 | 2007-01-09 | 주식회사 새 한 | 광학특성 및 내열성과 내흡습성이 우수한 광확산판 |
KR101479113B1 (ko) * | 2006-01-06 | 2015-01-07 | 미쓰비시 엔지니어링-플라스틱스 코포레이션 | 도광판용 방향족 폴리카보네이트 수지 조성물 및 도광판 |
US7848025B2 (en) | 2008-12-31 | 2010-12-07 | Sabic Innovative Plastics Ip B.V. | Transparent articles prepared from thermoplastic compositions having high flow and ductility, and method of preparing articles |
US8064140B2 (en) | 2008-12-31 | 2011-11-22 | Sabic Innovative Plastics Ip B.V. | Transparent articles prepared from thermoplastic compositions having low birefringence |
KR101252092B1 (ko) * | 2009-04-01 | 2013-04-12 | 엘지디스플레이 주식회사 | 백라이트 유닛과 이를 이용한 액정표시장치 |
WO2014004801A1 (en) * | 2012-06-29 | 2014-01-03 | Sabic Innovative Plastics Ip B.V. | Optical waveguide, method of manufacturing thereof, and polymeric composition |
CN104955575A (zh) | 2013-01-24 | 2015-09-30 | 沙特基础全球技术有限公司 | 由聚酯-聚碳酸酯制成的微流体装置和微孔 |
CN104955577A (zh) | 2013-01-24 | 2015-09-30 | 沙特基础全球技术有限公司 | 由聚酯-聚碳酸酯制造的微孔板 |
US9168532B2 (en) | 2013-01-24 | 2015-10-27 | Sabic Global Technologies B.V. | Microwell plate |
CN105431488B (zh) | 2013-07-26 | 2017-06-13 | 三菱工程塑料株式会社 | 薄壁光学构件用聚碳酸酯树脂组合物及薄壁光学构件 |
CN107266894B (zh) | 2013-12-10 | 2019-07-19 | 住化Pc有限公司 | 聚碳酸酯树脂组合物及光学用成形品 |
JP6101745B2 (ja) | 2015-01-07 | 2017-03-22 | 三菱エンジニアリングプラスチックス株式会社 | 薄肉光学部品用ポリカーボネート樹脂組成物および薄肉光学部品 |
WO2019187876A1 (ja) | 2018-03-27 | 2019-10-03 | 三菱エンジニアリングプラスチックス株式会社 | ポリカーボネート樹脂組成物 |
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JPH02113455A (ja) * | 1988-08-25 | 1990-04-25 | Bayer Ag | 燃可塑性ポリカーボネートとスチレンおよび(メタ)アクリル酸エステルの共重合体との混合物の光学的データ記憶用サブストレートとしての利用 |
WO1991009896A1 (en) * | 1989-12-22 | 1991-07-11 | General Electric Company | Polyestercarbonate composition |
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2000
- 2000-11-20 TW TW089124567A patent/TW487811B/zh not_active IP Right Cessation
- 2000-11-21 DE DE60033568T patent/DE60033568T2/de not_active Expired - Lifetime
- 2000-11-21 CA CA002386934A patent/CA2386934A1/en not_active Abandoned
- 2000-11-21 WO PCT/JP2000/008211 patent/WO2001055755A1/ja active IP Right Grant
- 2000-11-21 EP EP00976400A patent/EP1251371B1/en not_active Expired - Lifetime
- 2000-11-21 KR KR1020027005039A patent/KR100726037B1/ko not_active IP Right Cessation
- 2000-11-21 US US10/110,135 patent/US6941057B1/en not_active Expired - Fee Related
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US4902735A (en) * | 1987-06-03 | 1990-02-20 | Idemitsu Petrochemical Co., Ltd. | High impact resistant polycarbonate and process for producing said polycarbonate |
EP0335214A2 (en) * | 1988-03-28 | 1989-10-04 | Idemitsu Petrochemical Co. Ltd. | Polycarbonate |
JPH02113455A (ja) * | 1988-08-25 | 1990-04-25 | Bayer Ag | 燃可塑性ポリカーボネートとスチレンおよび(メタ)アクリル酸エステルの共重合体との混合物の光学的データ記憶用サブストレートとしての利用 |
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JPH0589827A (ja) * | 1991-09-26 | 1993-04-09 | Sony Corp | 集光型バツクライト |
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EP0736574A2 (en) * | 1995-04-08 | 1996-10-09 | General Electric Company | Thermoplastic resin composition comprising carbonate and acrylic resin |
JPH09131770A (ja) * | 1995-11-10 | 1997-05-20 | Kuraray Co Ltd | 導光板の成形方法およびそれに用いる金型 |
EP0794209A2 (en) * | 1996-03-07 | 1997-09-10 | Idemitsu Petrochemical Co., Ltd. | End group modified polycarbonates for digital video discs |
JPH11323324A (ja) * | 1998-05-13 | 1999-11-26 | Mitsubishi Chemical Corp | 蛍光性樹脂シート |
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Also Published As
Publication number | Publication date |
---|---|
TW487811B (en) | 2002-05-21 |
DE60033568D1 (de) | 2007-04-05 |
KR20020084061A (ko) | 2002-11-04 |
EP1251371A4 (en) | 2003-02-05 |
DE60033568T2 (de) | 2007-05-31 |
CA2386934A1 (en) | 2001-08-02 |
US6941057B1 (en) | 2005-09-06 |
EP1251371A1 (en) | 2002-10-23 |
EP1251371B1 (en) | 2007-02-21 |
KR100726037B1 (ko) | 2007-06-08 |
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