US20010039313A1 - Polycarbonate resin and optical article used the same - Google Patents

Polycarbonate resin and optical article used the same Download PDF

Info

Publication number
US20010039313A1
US20010039313A1 US09/819,614 US81961401A US2001039313A1 US 20010039313 A1 US20010039313 A1 US 20010039313A1 US 81961401 A US81961401 A US 81961401A US 2001039313 A1 US2001039313 A1 US 2001039313A1
Authority
US
United States
Prior art keywords
carbon atoms
group
polycarbonate resin
general formula
compound represented
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.)
Granted
Application number
US09/819,614
Other versions
US6340737B2 (en
Inventor
Noriyoshi Ogawa
Tatsuya Kanagawa
Hidekazu Nakatani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Gas Chemical Co Inc
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Assigned to MITSUBISHI GAS CHEMICAL COMPANY, INC. reassignment MITSUBISHI GAS CHEMICAL COMPANY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KANAGAWA, TATSUYA, NAKATANI, HIDEKAZU, OGAWA, NORIYOSHI
Publication of US20010039313A1 publication Critical patent/US20010039313A1/en
Application granted granted Critical
Publication of US6340737B2 publication Critical patent/US6340737B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04Aromatic polycarbonates
    • C08G64/06Aromatic polycarbonates not containing aliphatic unsaturation
    • C08G64/08Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
    • C08G64/085Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing silicon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/445Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
    • C08G77/448Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences

Definitions

  • the present invention relates to a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency and an optical article used the same.
  • the polycarbonate resin is applicable to uses of general molding of various materials such as medical instrument parts, food vessels, drinking bottles, photoreceptors for electro-photography, toner transfer belts, binders for dye and pigment, gas permeation membranes, toys, materials for window and building, safeguarding materials, OA apparatuses and portable telephones and boxes, and particularly, suitable to the production of optical articles such as optical discs including compact disc, laser disc, optical card, MO disc, digital versatile disc and near field recording optical disc, optical lenses including pick-up lens, spectacle lens and camera lens, optical films and optical sheets including cover layer for near field recording medium and optical filter, optical information transmission media including optical fiber and optical waveguide and photoconductive boards.
  • a bisphenol A type polycarbonate resin has been widely used as optical materials such as optical disc materials by utilizing its transparency, heat resistance, hydrolysis resistance and dimension stability.
  • use of a polycarbonate resin as optical materials caused some problems.
  • birefringence to change properties of incidence light caused the most important problem.
  • An object of the present invention is to provide a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency and an optical article used the same.
  • the present invention provides a polycarbonate resin obtained by reaction of a compound represented by the following general formula (A), a compound represented by the following general formula (B), a compound represented by the following general formula (C) and a carbonic acid ester-forming compound, wherein an amount of a compound represented by the general formula (A) is 30 to 80% by weight to total amount of a compound represented by the general formula (A) and a compound represented by the general formula (B) and a compound represented by the general formula (C) is 1 to 80% by weight to total amount of a compound represented by the general formula (A), a compound represented by the general formula (B) and a compound represented by the general formula (C) and an intrinsic viscosity of said polycarbonate resin is 0.2 to 1.0 dl/g;
  • R 1 , R 2 , R 3 and R 4 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
  • R 5 , R 6 , R 7 and R 8 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
  • R 9 , R 10 , R 11 and R 12 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has
  • R 18 and R 19 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent (s);
  • R 20 and R 21 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or an aliphatic ring or a heterocycle in combination of R 20 and R 21 and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s) and a is an integer of 0 to 20.
  • Examples of the carbonic acid ester-forming compound include phosgene and bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate and a combination of two species of the compounds thereof or above.
  • the polycarbonate resin of the present invention can be produced by reaction of the compound represented by above-mentioned general formula (A) (hereinafter, “compound of formula (A)”), the compound represented by above-mentioned general formula (B) (hereinafter, “compound of formula (B)”), the compound represented by above-mentioned general formula (C) (hereinafter, “compound of formula (C)) and a carbonic acid ester-forming compound.
  • compound of formula (A) the compound represented by above-mentioned general formula (B)
  • compound of formula (C) hereinafter, “compound of formula (C)
  • a carbonic acid ester-forming compound hereinafter, “compound of formula (C)
  • a process for producing a polycarbonate resin to be derived from bisphenol A e.g., a process comprising a direct reaction between bisphenols and phosgene (phosgene process) or a process comprising transesterification between bisphenol and a bisaryl carbonate (transesterification process) can be applied.
  • phosgene process phosgene process
  • transesterification process a process comprising transesterification between bisphenol and a bisaryl carbonate
  • the reaction of the compound of formula (A), the compound of formula (B), the compound of formula (C) and phosgene is performed usually in the presence of an acid bonding agent and a solvent.
  • Examples of the acid bonding agent include pyridine and alkali metal hydroxides including sodium hydroxide and potassium hydroxide.
  • Examples of the solvent include methylene chloride, chloroform, chlorobenzene and xylene.
  • a catalyst including tertiary amines such as triethylamine is added.
  • monofunctional compounds including phenol, p-t-butyl phenol and p-cumyl phenol alkyl-substituted phenols, hydroxy benzoic acid alkyls, and alkyl oxy phenols are added as molecular weight modifier.
  • antioxidants including sodium sulfite and hydrosulfite and a small amount of branching agents including phloroglucine, isatin bisphenol, 1,1,1-tris(4-hydroxyphenyl) ethane and ⁇ , ⁇ ′, ⁇ ′′-tris(4-hydroxyphenyl)-1,3,5-triisopropyl benzene may be added.
  • the reaction temperature is usually in the range of 0 to 150° C. and preferably in the range of 5 to 40° C.
  • the reaction time is usually 0.5 minutes to 10 hours and preferably 1 minute to 2 hours, depending on the reaction temperature. It is preferable to maintain pH of the reaction system to 10 or above during the reaction.
  • the reaction is performed usually at a temperature of 150 to 350° C. and preferably 200 to 300° C. Phenols by-produced by transesterification and derived from bisaryl carbonate are distilled off preferably under a final reduced pressure degree of 1 mmHg or below outside the reaction system.
  • the reaction time is usually about 1 to 10 hours, depending on the reaction temperature or the reduced pressure degree. It is preferable to perform the reaction under the atmosphere of an inert gas such as nitrogen, argon, etc. If necessary, an antioxidant(s) and a branching agent(s) may be added.
  • Examples of the compound of formula (A) include 9,9-bis(4-hydroxy-2-methylphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene, 9,9-bis(4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(3-methoxy-4-hydroxyphenyl) fluorene, 9,9-bis(3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis(3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis(3-methyl-4-hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis(4-hydroxyphenyl)
  • 9,9-bis(4-hydroxyphenyl) fluorene 9,9-bis(4-hydroxy-3-methylphenyl) fluorene and 9,9-bis(4-hydroxy-2-methylphenyl) fluorene are preferable.
  • a combination of two species of the compounds thereof or above may be used.
  • Examples of the compound of the formula (B) include the compounds represented by the below structural formulas and a combination of two species of the compounds thereof or above.
  • X contains 1 to 100 dimethylsiloxanes or 1 to 100 diphenylsiloxanes and is a random copolymer thereof.
  • ⁇ , ⁇ -bis[3-(o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane and ⁇ , ⁇ -bis[3-(o-hydroxyphenyl) propyl] polydimethylsiloxane are preferable.
  • Examples of the compound of formula (C) include 4,4′-biphenyl diol, bis(4-hydroxyphenyl) methane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3-methylphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) ketone, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (bisphenol A;BPA), 2,2-bis(4-hydroxyphenyl) butane, 1,1-bis(4-hydroxyphenyl) cyclohexane (bisphenol Z;BPZ), 2,2-bis(4-hydroxy-3-methylphenyl) propane (dimethyl bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis(
  • tetraammonium salt examples include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide and tetra-n-butylammonium iodide, among which trimethylbenzylammonium chloride and triethylbenzylammonium chloride are preferable. It is preferable that the amount of tetraammonium salt is usually 0.0005 to 5 mol % to total amount of bisphenols to be used.
  • mohydric phenol is preferable.
  • the molecular weight modifier include phenol, alkyl-substituted phenols including butyl phenol, octyl phenol, nonyl phenol, decanyl phenol, tetradecanyl phenol, heptadecanyl phenol and octadecanyl phenol; alkyl hydroxy benzoates including butyl hydroxy benzoate, octyl hydroxy benzoate, nonyl hydroxy benzoate, decanyl hydroxy benzoate and heptadecanyl hydroxy benzoate; alkyl oxy phenols including butoxy phenol, octyl oxy phenol, nonyl oxy phenol, decanyl oxy phenol, tetradecanyl oxy phenol, heptadecanyl oxy phenol and octadecanyl
  • the polycarbonate resin thus synthesized can be molded by known molding methods including extrusion molding, injection molding, blow molding, compression molding and wet molding. It is preferable that the intrinsic viscosity [ ⁇ ] of the polycarbonate resin is in the range of 0.2 to 1.0 dl/g since it is desirable that it can be readily extrusion-molded or injection-molded as an optical material to mold an optical article. Particularly, when a high cycle molding is required, it is preferable that it is in the range of 0.2 to 0.6 dl/g.
  • the amount of the compound of formula (A) is 30 to 80% by weight to total amount of the compound of formula (A) and the compound of formula (B), considering curvature, strength and low birefringence of the mold article.
  • the amount of the compound of formula (A) is below 30% by weight, curvature of the disc molded article becomes large, whereas above 80% by weight strength is decreased and crack occurs during disc molding.
  • the amount of the compound of formula (C) is 1 to 80% by weight to total mount of the compound of formula (A), the compound of formula (B) and the compound of formula (C), considering a resin replacement in a molder, transparency and low birefringence of the molded article.
  • the amount of the compound of formula (C) is below 1% by weight, remarkable white turbidity occurs in a blend with a conventional bisphenol A type polycarbonate. Consequently, in case of production apparatus of other sorts to use the material in a molder in which a conventional bisphenol A type polycarbonate is usually used, necessity to disjoint and wash the apparatus occurs, so that operation efficiency of the apparatus is lowered and a return after cleaning of the apparatus is delayed.
  • the polycarbonate resin of the present invention is extrusion molded or injection molded, too large or too small flowability causes problems in molding. It is preferable that the polycarbonate resin of the present invention for extrusion molding has the range of flow rate 1 ⁇ 10 ⁇ 2 to 15 ⁇ 10 ⁇ 2 cc/sec measured with a flow tester (nozzle diameter 1 mm, length 10 mm) at 280° C. under 160 kgf/cm 2 . When the flow rate is outside the range of 1 ⁇ 10 ⁇ 2 to 15 ⁇ 10 ⁇ 2 cc/sec, a dimension precision of the molded article is deteriorated.
  • the polycarbonate resin of the present invention for injection molding has the range of flow rate 3 ⁇ 10 ⁇ 12 to 90 ⁇ 10 ⁇ 2 cc/sec measured by above-mentioned measuring flow tester and conditions.
  • flow rate 3 ⁇ 10 ⁇ 2 cc/sec
  • flowability is deteriorated, so that failure filling into a mold and a flow mark sometimes occur.
  • the flow rate is above 90 ⁇ 10 ⁇ 2 cc/sec, failure releasing from a mold and curvature readily occur.
  • the molding temperature in extrusion molding and injection molding of the polycarbonate resin is, respectively, 230 to 320° C. and 240 to 380° C.
  • the polycarboante resin is highly purified in the same manner as in conventional polycarbonate for optical disc.
  • it is purified so as to satisfy as much as possible criterions including dusts of diameter 50 ⁇ m or above: substantially undetected, dusts of diameter 0.5 to 50 ⁇ m: 3 ⁇ 10 4 or below, inorganic and organic residual chloride: 2 ppm or below, residual alkali metal: 2 ppm or below, residual hydroxyl group: 200 ppm or below, residual nitrogen content: 5 ppm or below and residual monomer: 20 ppm or below.
  • Post treatments such as extraction for removal of low molecular weight substances and removal of a solvent are sometimes performed.
  • antioxidants such as hindered phenols and phosphites
  • lubricants and mold releasing agents including silicons, fatty acid esters, fatty acids, fatty acid glycerides and natural fats and oils including bees wax
  • light stabilizers such as benzotriazoles, benzophenones, dibenzoyl methane and salicylates and antistatic agents such as polyalkylene glycols and fatty acid glycerides may be used together with the polycarbonate resin.
  • a mixture of the polycarbonate resin with an ordinary polycarbonate resin(s) other than the polycarbonate resin may optionally be used within the range not to impair performances.
  • the range not to impair performances is different depending on purposes to be used, in addition to above-mentioned properties as a molding material, it is preferable to satisfy at least one and preferably at least two conditions of a 30 degree oblique incidence light birefringence of below 110 nm, a photoelastic sensitivity of below 70 ⁇ 10 ⁇ 22 m 2 /N and total light transmissivity of 80% or above of a molded article of thickness 3 mm.
  • a cast film of thickness 50 ⁇ m was prepared from a polycarbonate resin powder sample. The measurement was performed for the cast film with auto-Elliposometer, manufactured by k.k., Mizojiri Kogaku Kogyo, in Japan under a load of 300 to 1100 g in a wave length of 632.8 nm.
  • the measurement was performed for an injection molded optical disc substrate of a polycarbonate resin sample with an atomic force microscope NV2100, manufactured by Olympus Co.
  • Intrinsic viscosity [ ⁇ ] [dl/g] was measured for a polycarbonate resin solution of 0.5 g/dl concentration in methylene chloride solvent at Huggins's constant of 0.45 at a temperature of 20° C.
  • Haze(H) is calculated as follows:
  • Tt total light transmissivity
  • Tp parallel light transmissivity
  • Td diffusion light transmissivity
  • BCFL 9,9-bis(4-hydroxy-3-methylphenyl) fluorene
  • BPA 2,2-bis(4-hydroxyphenyl) propane
  • 20 g of sodium dithionite were dissolved in 49 L of 8.8 (w/v) sodium hydroxide aqueous solution.
  • 36 L of methylene chloride was added thereto and then 1.462 kg of phosgene was injected at the rate of 0.12 kg/min while maintaining 15° C.
  • PTBF p-t-butyl phenol
  • the polymer liquid was separated into an aqueous phase and an organic phase.
  • the organic phase was neutralized with phosphoric acid.
  • Water washing was repeated until an electrical conductivity of the washed liquid became 10 ⁇ S/cm or below, thus obtaining a purified resin liquid.
  • the purified resin liquid thus obtained was slowly added in drop wise to hot water maintained to 60° C. under intense stirring, and the polymer was solidified while removing the solvent.
  • the solid substance thus obtained was filtered and dried, whereby a white powdery polymer was obtained.
  • the intrinsic viscosity [ ⁇ ] of the polymer was 0.25 dl/g.
  • the polymer was analyzed by infrared absorption spectrum. Absorption due to carbonyl group near 1770 cm ⁇ 1 and absorption due to ether bond near 1240 cm ⁇ 1 were detected. It was confirmed that the polymer had carbonate bond. Absorption due to hydroxyl group at the position of 3650 to 3200 cm ⁇ 1 was almost never detected.
  • Monomers in the polymer were determined by GPC analysis. Each content of each monomer was 20 ppm or below.
  • the polymer was a polycarbonate having the below structural units.
  • the intrinsic viscosity [ ⁇ ] of the polymer thus obtained was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. The results of measurement of properties were shown in Tables 1 and 2.
  • the intrinsic viscosity [ ⁇ ] was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer. The results of measurement of properties were shown in Tables 1 and 2.
  • the polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 4.158 kg; the amount of Si was changed to 2.772 kg; the amount of BPA was changed to 0.070 kg; the amount of phosgene was changed to 1.780 kg and the amount of PTBP was changed to 80 g.
  • the mixture thus obtained was extruded and melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 ⁇ m at 300° C.
  • the intrinsic viscosity [ ⁇ ] of melt pellets of the mixture was 0.33 dl/g.
  • the polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 2.520 kg; the amount of Si was changed to 1.680 kg; the amount of BPA was changed to 2.800 kg; the amount of phosgene was changed to 2.865 kg and the amount of PTBP was changed to 223 g.
  • the intrinsic viscosity [ ⁇ ] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum.
  • the polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 1.26 kg; the amount of Si was changed to 0.840 kg; the amount of BPA was changed to 4.900 kg; the amount of phosgene was changed to 3.216 kg and the amount of PTBP was changed to 388 g.
  • the intrinsic viscosity [ ⁇ ] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum.
  • the intrinsic viscosity [ ⁇ ] of the polymer thus obtained was 0.24 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. The results of measurement of properties shown in Tables 1 and 2.
  • the intrinsic viscosity [ ⁇ ] was 0.24 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer. The results of measurement of properties were shown in Tables 1 and 2.
  • the polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 4.200 kg; the amount of Si was changed to 2.800 kg; the amount of BPA was changed to 0 kg; the amount of phosgene was changed to 1.735 kg and the amount of PTBP was changed to 79 g.
  • the intrinsic viscosity [ ⁇ ] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum.
  • the polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 0.420 kg; the amount of Si was changed to 0.280 kg; the amount of BPA was changed to 6.300 kg; the amount of phosgene was changed to 3.421 kg and the amount of PTBP was changed to 475 g.
  • the intrinsic viscosity [ ⁇ ] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum The results of measurement of properties were shown in Tables 1 and 2.
  • a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency can be provided.
  • the polycarbonate resin is suitable to the production of optical articles such as optical discs including compact disc, laser disc, optical card, MO disc, digital versatile disc and near field recording disc, optical lenses including pick-up lens, spectacle lens and camera lens, optical films and optical sheets including cover layer for near field recording medium and optical filter, optical information transmission media including optical fiber and optical waveguide and photoconductive boards in which low birefringence is required.

Abstract

A polycarbonate resin obtained by reaction of (A) a bisphenol compound having a fluorene structure, (B) a bisphenol compound having a polysiloxane structure, (C) other specific bisphenol compound and a carbonic acid ester-forming compound, wherein an amount of (A) bisphenol compound is 30 to 80% by weight to total amount of (A) bisphenol compound and (B) bisphenol compound,and an amount of (C) bisphenol compound is 1 to 80% by weight to total amount of (A) bisphenol compound, (B) bisphenol compound and (C) bisphenol compound and an intrinsic viscosity of said polycarbonate resin is 0.2 to 1.0 dl/g.

Description

    BACKGROUND OF THE INVENTION
  • 1) Field on the Invention [0001]
  • The present invention relates to a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency and an optical article used the same. The polycarbonate resin is applicable to uses of general molding of various materials such as medical instrument parts, food vessels, drinking bottles, photoreceptors for electro-photography, toner transfer belts, binders for dye and pigment, gas permeation membranes, toys, materials for window and building, safeguarding materials, OA apparatuses and portable telephones and boxes, and particularly, suitable to the production of optical articles such as optical discs including compact disc, laser disc, optical card, MO disc, digital versatile disc and near field recording optical disc, optical lenses including pick-up lens, spectacle lens and camera lens, optical films and optical sheets including cover layer for near field recording medium and optical filter, optical information transmission media including optical fiber and optical waveguide and photoconductive boards. [0002]
  • 2) Prior Art [0003]
  • Recently, a bisphenol A type polycarbonate resin has been widely used as optical materials such as optical disc materials by utilizing its transparency, heat resistance, hydrolysis resistance and dimension stability. However, use of a polycarbonate resin as optical materials caused some problems. Among performances as optical materials, birefringence to change properties of incidence light caused the most important problem. [0004]
  • In order to reduce birefringence, various polycarbonate resin materials have been developed (Japanese Patent Kokai (Laid Open) Nos. 60-215020 and 62-181115). However, also in these developments, reduction of birefringence was not sufficient. Further, recently, reduction of oblique incidence birefringence whose improvement is difficult by controlling molding conditions has been required. [0005]
  • On the other hand, optical disc materials containing polyorganosiloxane have been developed (Japanese Patent Kokai (Laid Open) No. 3-106931). However, in these materials, when the polyorganosiloxane content is increased, transparency to be required for an optical disc could not be maintained, Thus, satisfactory reduction of birefringence could not be attained because the polyorganosiloxane content could not be increased. [0006]
  • Further, in the blend of some resins different in refractive index from each other, white turbidity occurred since it was difficult to disperse uniformly them, so that there occurred problems that use of replaced article in production of other sorts was limited and recycling was difficult. [0007]
  • SUMMARY OF THE INVENTION
  • An object of the present invention is to provide a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency and an optical article used the same. [0008]
  • As a result of extensive studies to solve above-mentioned prior art problems, the inventors have found that a copolymerization resin derived from specific three kinds of bisphenols and a mixture of said copolymerization resin and conventional bisphenol A type polycarbonate resin can be used as high quality optical materials with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency, and accomplished the present invention. [0009]
  • That is, the present invention provides a polycarbonate resin obtained by reaction of a compound represented by the following general formula (A), a compound represented by the following general formula (B), a compound represented by the following general formula (C) and a carbonic acid ester-forming compound, wherein an amount of a compound represented by the general formula (A) is 30 to 80% by weight to total amount of a compound represented by the general formula (A) and a compound represented by the general formula (B) and a compound represented by the general formula (C) is 1 to 80% by weight to total amount of a compound represented by the general formula (A), a compound represented by the general formula (B) and a compound represented by the general formula (C) and an intrinsic viscosity of said polycarbonate resin is 0.2 to 1.0 dl/g; [0010]
    Figure US20010039313A1-20011108-C00001
  • wherein R[0011] 1, R2, R3 and R4 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
    Figure US20010039313A1-20011108-C00002
  • wherein R[0012] 5, R6, R7 and R8 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s); R9, R10, R11 and R12 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s); R13 is an aliphatic group having 1 to 6 carbon atoms or absent; X is —SiO(R14)(R15)—, —SiO(R16)(R17)—, a homopolymer of —SiO(R14)(R15)— or —SiO(R16)(R17)— having an average polymerization degree of more than 0 and 200 or below or a random copolymer of —SiO(R14)(R15)— and —SiO(R16)(R17)— having an average polymerization degree of more than 0 and 200 or below; R14, R15, R16 and R17 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
    Figure US20010039313A1-20011108-C00003
  • wherein R[0013] 18 and R19 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent (s);
  • Y is; [0014]
    Figure US20010039313A1-20011108-C00004
  • wherein R[0015] 20 and R21 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or an aliphatic ring or a heterocycle in combination of R20 and R21 and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s) and a is an integer of 0 to 20.
  • DETAILED DESCRIPTION OF THE INVENTION
  • The invention will be described in detail below. [0016]
  • Examples of the carbonic acid ester-forming compound include phosgene and bisaryl carbonates such as diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate and dinaphthyl carbonate and a combination of two species of the compounds thereof or above. [0017]
  • The polycarbonate resin of the present invention can be produced by reaction of the compound represented by above-mentioned general formula (A) (hereinafter, “compound of formula (A)”), the compound represented by above-mentioned general formula (B) (hereinafter, “compound of formula (B)”), the compound represented by above-mentioned general formula (C) (hereinafter, “compound of formula (C)) and a carbonic acid ester-forming compound. Known processes for producing a polycarbonate resin to be derived from bisphenol A, e.g., a process comprising a direct reaction between bisphenols and phosgene (phosgene process) or a process comprising transesterification between bisphenol and a bisaryl carbonate (transesterification process) can be applied. [0018]
  • Among the phosgene process and the transesterification process, it is preferable to apply the phosgene process, considering reactivity between the compound of formula (A) and the compound of formula (B). [0019]
  • In the phosgene process, the reaction of the compound of formula (A), the compound of formula (B), the compound of formula (C) and phosgene is performed usually in the presence of an acid bonding agent and a solvent. [0020]
  • Examples of the acid bonding agent include pyridine and alkali metal hydroxides including sodium hydroxide and potassium hydroxide. [0021]
  • Examples of the solvent include methylene chloride, chloroform, chlorobenzene and xylene. [0022]
  • Further, in order to promote polycondensation, a catalyst including tertiary amines such as triethylamine is added. In order to adjust polymerization degree, monofunctional compounds including phenol, p-t-butyl phenol and p-cumyl phenol alkyl-substituted phenols, hydroxy benzoic acid alkyls, and alkyl oxy phenols are added as molecular weight modifier. [0023]
  • If necessary, a small amount of antioxidants including sodium sulfite and hydrosulfite and a small amount of branching agents including phloroglucine, isatin bisphenol, 1,1,1-tris(4-hydroxyphenyl) ethane and α,α′,α″-tris(4-hydroxyphenyl)-1,3,5-triisopropyl benzene may be added. [0024]
  • The reaction temperature is usually in the range of 0 to 150° C. and preferably in the range of 5 to 40° C. The reaction time is usually 0.5 minutes to 10 hours and preferably 1 minute to 2 hours, depending on the reaction temperature. It is preferable to maintain pH of the reaction system to 10 or above during the reaction. [0025]
  • In the transesterification process, a mixture of the compound of formula (A), the compound of formula (B), the compound of formula (C) and bisaryl carbonate is reacted under a reduced pressure at a high temperature. In this reaction, a monofunctional compound(s) including p-t-butyl phenol, p-cumyl phenol alkyl-substituted phenols, hydroxy benzoic acid alkyls and alkyl oxy phenols may be added as molecular weight modifier. [0026]
  • The reaction is performed usually at a temperature of 150 to 350° C. and preferably 200 to 300° C. Phenols by-produced by transesterification and derived from bisaryl carbonate are distilled off preferably under a final reduced pressure degree of 1 mmHg or below outside the reaction system. The reaction time is usually about 1 to 10 hours, depending on the reaction temperature or the reduced pressure degree. It is preferable to perform the reaction under the atmosphere of an inert gas such as nitrogen, argon, etc. If necessary, an antioxidant(s) and a branching agent(s) may be added. [0027]
  • Examples of the compound of formula (A) include 9,9-bis(4-hydroxy-2-methylphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene, 9,9-bis(4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(3-methoxy-4-hydroxyphenyl) fluorene, 9,9-bis(3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis(3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis(3-methyl-4-hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis(4-hydroxyphenyl)fluorene. Among them, 9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene and 9,9-bis(4-hydroxy-2-methylphenyl) fluorene are preferable. A combination of two species of the compounds thereof or above may be used. [0028]
  • Examples of the compound of the formula (B) include the compounds represented by the below structural formulas and a combination of two species of the compounds thereof or above. [0029]
    Figure US20010039313A1-20011108-C00005
  • It is preferable that X contains 1 to 100 dimethylsiloxanes or 1 to 100 diphenylsiloxanes and is a random copolymer thereof. Among them, particularly, α,ω-bis[3-(o-hydroxyphenyl) propyl] polydimethyldiphenyl random copolymer siloxane and α,ω-bis[3-(o-hydroxyphenyl) propyl] polydimethylsiloxane are preferable. [0030]
  • Examples of the compound of formula (C) include 4,4′-biphenyl diol, bis(4-hydroxyphenyl) methane, bis(4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxy-3-methylphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) ketone, 1,1-bis(4-hydroxyphenyl) ethane, 2,2-bis(4-hydroxyphenyl) propane (bisphenol A;BPA), 2,2-bis(4-hydroxyphenyl) butane, 1,1-bis(4-hydroxyphenyl) cyclohexane (bisphenol Z;BPZ), 2,2-bis(4-hydroxy-3-methylphenyl) propane (dimethyl bisphenol A), 2,2-bis(4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane(bisphenol AP;BPAP), bis(4-hydroxyphenyl) diphenylmethane, 2,2-bis(4-hydroxy-3-allylphenyl) propane and 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl) cyclohexane. A combination of two species of above-mentioned compounds or above may be used. Among them, particullarly, 2,2-bis(4-hydroxyphenyl) propane is preferable. [0031]
  • When the phosgene process is applied to the present invention, it is possible to inject phosgene in the presence of a tetraammonium salt in order to perform efficiently the reaction. Examples of tetraammonium salt include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide and tetra-n-butylammonium iodide, among which trimethylbenzylammonium chloride and triethylbenzylammonium chloride are preferable. It is preferable that the amount of tetraammonium salt is usually 0.0005 to 5 mol % to total amount of bisphenols to be used. [0032]
  • Further, when a molecular weight modifier is used in the present invention, mohydric phenol is preferable. Examples of the molecular weight modifier include phenol, alkyl-substituted phenols including butyl phenol, octyl phenol, nonyl phenol, decanyl phenol, tetradecanyl phenol, heptadecanyl phenol and octadecanyl phenol; alkyl hydroxy benzoates including butyl hydroxy benzoate, octyl hydroxy benzoate, nonyl hydroxy benzoate, decanyl hydroxy benzoate and heptadecanyl hydroxy benzoate; alkyl oxy phenols including butoxy phenol, octyl oxy phenol, nonyl oxy phenol, decanyl oxy phenol, tetradecanyl oxy phenol, heptadecanyl oxy phenol and octadecanyl oxy phenol. The amount of the molecular weight modifier is 0.1 to 50 mol % and preferably 0.5 to 10 mol % to total amount of bisphenols. [0033]
  • The polycarbonate resin thus synthesized can be molded by known molding methods including extrusion molding, injection molding, blow molding, compression molding and wet molding. It is preferable that the intrinsic viscosity [η] of the polycarbonate resin is in the range of 0.2 to 1.0 dl/g since it is desirable that it can be readily extrusion-molded or injection-molded as an optical material to mold an optical article. Particularly, when a high cycle molding is required, it is preferable that it is in the range of 0.2 to 0.6 dl/g. [0034]
  • It is preferable that the amount of the compound of formula (A) is 30 to 80% by weight to total amount of the compound of formula (A) and the compound of formula (B), considering curvature, strength and low birefringence of the mold article. When the amount of the compound of formula (A) is below 30% by weight, curvature of the disc molded article becomes large, whereas above 80% by weight strength is decreased and crack occurs during disc molding. [0035]
  • It is preferable that the amount of the compound of formula (C) is 1 to 80% by weight to total mount of the compound of formula (A), the compound of formula (B) and the compound of formula (C), considering a resin replacement in a molder, transparency and low birefringence of the molded article. When the amount of the compound of formula (C) is below 1% by weight, remarkable white turbidity occurs in a blend with a conventional bisphenol A type polycarbonate. Consequently, in case of production apparatus of other sorts to use the material in a molder in which a conventional bisphenol A type polycarbonate is usually used, necessity to disjoint and wash the apparatus occurs, so that operation efficiency of the apparatus is lowered and a return after cleaning of the apparatus is delayed. Furthermore, there are defects that it substantially becomes impossible to mix a conventional bisphenol A polycarbonate in order to reduce a production cost and a replaced article at the time of exchange to other sort becomes opaque, so that recycling use is limited. When the amount of formula (C) is above 80% by weight, the value of birefringence becomes insufficient. [0036]
  • When the polycarbonate resin of the present invention is extrusion molded or injection molded, too large or too small flowability causes problems in molding. It is preferable that the polycarbonate resin of the present invention for extrusion molding has the range of flow rate 1×10[0037] −2 to 15×10−2 cc/sec measured with a flow tester (nozzle diameter 1 mm, length 10 mm) at 280° C. under 160 kgf/cm2. When the flow rate is outside the range of 1×10−2 to 15×10−2 cc/sec, a dimension precision of the molded article is deteriorated. Further, it is preferable that the polycarbonate resin of the present invention for injection molding has the range of flow rate 3×10−12 to 90×10−2 cc/sec measured by above-mentioned measuring flow tester and conditions. When the flow rate is below 3×10−2 cc/sec, flowability is deteriorated, so that failure filling into a mold and a flow mark sometimes occur. When the flow rate is above 90×10−2 cc/sec, failure releasing from a mold and curvature readily occur.
  • It is preferable that the molding temperature in extrusion molding and injection molding of the polycarbonate resin is, respectively, 230 to 320° C. and 240 to 380° C. [0038]
  • It is preferable that the polycarboante resin is highly purified in the same manner as in conventional polycarbonate for optical disc. In detail, it is purified so as to satisfy as much as possible criterions including dusts of diameter 50 μm or above: substantially undetected, dusts of diameter 0.5 to 50 μm: 3×10[0039] 4 or below, inorganic and organic residual chloride: 2 ppm or below, residual alkali metal: 2 ppm or below, residual hydroxyl group: 200 ppm or below, residual nitrogen content: 5 ppm or below and residual monomer: 20 ppm or below. Post treatments such as extraction for removal of low molecular weight substances and removal of a solvent are sometimes performed.
  • Regarding the compound of formula (A), the compound of formula (B), the compound of formula (C) and a carbonic ester-forming compound as raw materials, it is preferable to use materials reduced impurities and isomers as much as possible. [0040]
  • In the polycarbonate resin of the present invention, in order to ensure stability and mold releasing be required during extrusion molding or injection molding, if necessary, antioxidants such as hindered phenols and phosphites; lubricants and mold releasing agents including silicons, fatty acid esters, fatty acids, fatty acid glycerides and natural fats and oils including bees wax; light stabilizers such as benzotriazoles, benzophenones, dibenzoyl methane and salicylates and antistatic agents such as polyalkylene glycols and fatty acid glycerides may be used together with the polycarbonate resin. [0041]
  • Further, in order to reduce cost and recycle, a mixture of the polycarbonate resin with an ordinary polycarbonate resin(s) other than the polycarbonate resin may optionally be used within the range not to impair performances. Although the range not to impair performances is different depending on purposes to be used, in addition to above-mentioned properties as a molding material, it is preferable to satisfy at least one and preferably at least two conditions of a 30 degree oblique incidence light birefringence of below 110 nm, a photoelastic sensitivity of below 70×10[0042] −22 m2/N and total light transmissivity of 80% or above of a molded article of thickness 3 mm.
  • PREFERRED EMBODIMENT OF THE INVENTION
  • The present invention will be described in more below, referring to Examples, which are not intended to limit the scope of the present invention. [0043]
  • Each properties were measured according to the following methods. [0044]
  • [Birefringence][0045]
  • The measurement was performed for an injection molded optical disc substrate of a polycarbonate resin sample with auto-Ellipsometer, manufactured by k.k., Mizojiri Kogaku Kogyo, in Japan by a light of 30 degree oblique incidence angle and wave length 632.8 nm. [0046]
  • [Photoelastic Sensitivity][0047]
  • A cast film of thickness 50 μm was prepared from a polycarbonate resin powder sample. The measurement was performed for the cast film with auto-Elliposometer, manufactured by k.k., Mizojiri Kogaku Kogyo, in Japan under a load of 300 to 1100 g in a wave length of 632.8 nm. [0048]
  • [Transcription][0049]
  • The measurement was performed for an injection molded optical disc substrate of a polycarbonate resin sample with an atomic force microscope NV2100, manufactured by Olympus Co. [0050]
  • [Intrinsic Viscosity [η]][0051]
  • Intrinsic viscosity [η] [dl/g] was measured for a polycarbonate resin solution of 0.5 g/dl concentration in methylene chloride solvent at Huggins's constant of 0.45 at a temperature of 20° C. [0052]
  • [Total Light Transmissivity and Haze][0053]
  • Total light transmissivity (%) and haze (%) were measured for an injection molded board article of a polycarbonate resin sample with HM-100, manufactured by Murakami Color Technology Research Laboratory in Japan by a transmission light of 1.9 mmφ. [0054]
  • Haze(H) is calculated as follows: [0055]
  • Tp=Tt−Td
  • H=(Td/Tt)×100
  • Tt: total light transmissivity [0056]
  • Tp: parallel light transmissivity [0057]
  • Td: diffusion light transmissivity[0058]
  • EXAMPLE 1
  • 2.604 kg of 9,9-bis(4-hydroxy-3-methylphenyl) fluorene (hereinafter “BCFL” ), 3.906 kg of a polyorganosiloxane random copolymer having the below structure of dimethylsiloxane and diphenylsiloxane having 3-(o-hydroxyphenyl) propyl group at α and ω positions and having average polymerization degree a=26 and C=13 (hereinafter, “Si” ), 0.490 kg of 2,2-bis(4-hydroxyphenyl) propane (hereinafter, “BPA” ) and 20 g of sodium dithionite were dissolved in 49 L of 8.8 (w/v) sodium hydroxide aqueous solution. 36 L of methylene chloride was added thereto and then 1.462 kg of phosgene was injected at the rate of 0.12 kg/min while maintaining 15° C. [0059]
  • After the completion of injection, 66 g of p-t-butyl phenol (hereinafter, “PTBF” ) was added thereto and vigorous stirring was continued for 10 minutes. Then, 10 ml of triethylamine was added thereto and polymerization was performed for about one hour with stirring. [0060]
    Figure US20010039313A1-20011108-C00006
  • The polymer liquid was separated into an aqueous phase and an organic phase. The organic phase was neutralized with phosphoric acid. Water washing was repeated until an electrical conductivity of the washed liquid became 10 μS/cm or below, thus obtaining a purified resin liquid. The purified resin liquid thus obtained was slowly added in drop wise to hot water maintained to 60° C. under intense stirring, and the polymer was solidified while removing the solvent. The solid substance thus obtained was filtered and dried, whereby a white powdery polymer was obtained. [0061]
  • The intrinsic viscosity [η] of the polymer was 0.25 dl/g. The polymer was analyzed by infrared absorption spectrum. Absorption due to carbonyl group near 1770 cm[0062] −1 and absorption due to ether bond near 1240 cm−1 were detected. It was confirmed that the polymer had carbonate bond. Absorption due to hydroxyl group at the position of 3650 to 3200 cm−1 was almost never detected. Monomers in the polymer were determined by GPC analysis. Each content of each monomer was 20 ppm or below.
  • Thus, it was confirmed that the polymer was a polycarbonate having the below structural units. [0063]
    Figure US20010039313A1-20011108-C00007
  • 300 ppm of stearic acid monoglyceride was added to the polycarbonate powder thus obtained, Then, the mixture thus obtained was melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 μm at 300° C. A portion of the pellets thus obtained was injection molded with a disc molder, SD-4, manufactured by Sumitomo Jukikai Kogyo, k.k., in Japan at a resin temperature of 300° C. at a mold temperature of 100° C. in a molding cycle of 10 sec/plate, whereby an optical disc substrate of outer diameter 120 mm and thickness 1.2 mm was prepared. Further, a portion of the pellets thus obtained was injection molded with a molder, FS120S18ASE, manufactured by Nissei Jusi Kogyo k.k., in Japan at a resin temperature of 260° C. at a mold temperature of 100° C. in a molding cycle of 50 sec/plate, whereby a board article of thickness 3 mm was prepared. Each molded article was standing in a room for two days. Then, the 30 degree oblique incidence birefringence and transcription of the optical disc substrate and the total light transmissivity and haze of the board article were measured. A cast film of thickness 50 μm was prepared from the polycarboante powder. The photoelastic sensitivity of the cast film was measured. The results were shown in Tables 1 and 2. [0064]
  • EXAMPLE 2
  • The experiment was performed in the same manner as in Example 1 except that the amount of BCFL was changed to 3.906 kg; the amount of Si was changed to 2.604 kg; the amount of phosgene was changed to 1.933 kg and amount of PTBP was changed to 87.9 g. [0065]
  • The intrinsic viscosity [η] of the polymer thus obtained was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. The results of measurement of properties were shown in Tables 1 and 2. [0066]
  • EXAMPLE 3
  • The experiment was performed in the same manner as in Example 1 except that the amount of BCFL was changed to 5.208 kg; the amount of Si was changed to 1.302 kg; the amount of phosgene was changed to 2.405 kg and amount of PTBP was changed to 110 g. [0067]
  • The intrinsic viscosity [η] was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer. The results of measurement of properties were shown in Tables 1 and 2. [0068]
  • EXAMPLE 4
  • The polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 4.158 kg; the amount of Si was changed to 2.772 kg; the amount of BPA was changed to 0.070 kg; the amount of phosgene was changed to 1.780 kg and the amount of PTBP was changed to 80 g. [0069]
  • The intrinsic viscosity [η] of the polycarbonate powder thus obtained was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. 1 kg of polycarbonate powder thus obtained, 4 kg of conventional optical BPA type polycarbonate, H-4000, manufactured by Mitsubishi Gas Chemical Co., Inc., in Japan, having [η]=0.35 dl/g (hereinafter, “H-4000” and 1.5 g of stearic acid monoglyceride were mixed. The mixture thus obtained was extruded and melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 μm at 300° C. The intrinsic viscosity [η] of melt pellets of the mixture was 0.33 dl/g. [0070]
  • The pellets thus obtained were molded in the same manner as in Example 1 and evaluated. The results of measurement of properties were shown in Tables 1 and 2. [0071]
  • EXAMPLE 5
  • The polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 2.520 kg; the amount of Si was changed to 1.680 kg; the amount of BPA was changed to 2.800 kg; the amount of phosgene was changed to 2.865 kg and the amount of PTBP was changed to 223 g. [0072]
  • The intrinsic viscosity [η] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. [0073]
  • 1.65 kg of polycarbonate powder thus obtained, 3.35 kg of H-4000 and 1.5 g of stearic acid monoglyceride were mixed. The mixture thus obtained was extruded and melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 μm at 300° C. [0074]
  • The intrinsic viscosity [η] of melt pellets of the mixture was 0.32 dl/g. The pellets thus obtained were molded in the same manner as in Example 1 and evaluated. The results of measurement of properties were shown in Tables 1 and 2. [0075]
  • EXAMPLE 6
  • The polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 1.26 kg; the amount of Si was changed to 0.840 kg; the amount of BPA was changed to 4.900 kg; the amount of phosgene was changed to 3.216 kg and the amount of PTBP was changed to 388 g. [0076]
  • The intrinsic viscosity [η] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. [0077]
  • 3.35 kg of polycarbonate powder thus obtained, 1.65 kg of H-4000 and 1.5 g of stearic acid monoglyceride were mixed. The mixture thus obtained was extruded and melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 μm at 300° C. [0078]
  • The intrinsic viscosity [η] of melt pellets of the mixture was 0.28 dl/g. The pellets thus obtained were molded in the same manner as in Example 1 and evaluated. The results of measurement of properties were shown in Tables 1 and 2. [0079]
  • COMPARATIVE EXAMPLE 1
  • The molding and evaluation were performed in the same manner as in Example 1 except that H-4000 was used instead of the polycarbonate of Example 1. The results of measurement of properties were shown in Tables 1 and 2. [0080]
  • COMPARATIVE EXAMPLE 2
  • The experiment was performed in the same manner as in Example 1 except that the amount of BCFL was changed to 1.823 kg; the amount of Si was changed to 4.687 kg; the amount of phosgene was changed to 1.226 kg and the amount of PTBP was changed to 56 g. [0081]
  • The intrinsic viscosity [η] of the polymer thus obtained was 0.24 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. The results of measurement of properties shown in Tables 1 and 2. [0082]
  • COMPARATIVE EXAMPLE 3
  • The experiment was performed in the same manner as in Example 1 except that the amount of BCFL was changed to 5.859 kg; the amount of Si was changed to 0.651 kg; the amount of phosgene was changed to 2.640 kg and the amount of PTBP was changed to 120.0 g. [0083]
  • The intrinsic viscosity [η] was 0.24 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer. The results of measurement of properties were shown in Tables 1 and 2. [0084]
  • COMPARATIVE EXAMPLE 4
  • The polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 4.200 kg; the amount of Si was changed to 2.800 kg; the amount of BPA was changed to 0 kg; the amount of phosgene was changed to 1.735 kg and the amount of PTBP was changed to 79 g. [0085]
  • The intrinsic viscosity [η] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum. [0086]
  • 1 kg of polycarbonate powder thus obtained, 4 kg of H-4000 and 1.5 g of stearic acid monoglyceride were mixed. The mixture thus obtained was extruded and melt pelletized with a vent type biaxial extruder of 30 mm, equipped with a polymer filter of 10 μm at 300° C. [0087]
  • The intrinsic viscosity [η] of melt pellets of the mixture was 0.33 dl/g. [0088]
  • The pellets thus obtained were molded in the same manner as in Example 1 and evaluated. The results of measurement of properties were shown in Tables 1 and 2. [0089]
  • COMPARATIVE EXAMPLE 5
  • The polycarbonate powder was obtained in the same manner as in Example 1 except that the amount of BCFL was changed to 0.420 kg; the amount of Si was changed to 0.280 kg; the amount of BPA was changed to 6.300 kg; the amount of phosgene was changed to 3.421 kg and the amount of PTBP was changed to 475 g. [0090]
  • The intrinsic viscosity [η] of the polycarbonate powder was 0.25 dl/g. It was confirmed that the polymer had a polycarbonate structure identical to that of Example 1 except the polymerization ratio of monomer by infrared absorption spectrum The results of measurement of properties were shown in Tables 1 and 2. [0091]
  • According to the present invention, a polycarbonate resin with a remarkably reduced oblique incidence birefringence, excellent moldability, excellent transcription and good transparency can be provided. The polycarbonate resin is suitable to the production of optical articles such as optical discs including compact disc, laser disc, optical card, MO disc, digital versatile disc and near field recording disc, optical lenses including pick-up lens, spectacle lens and camera lens, optical films and optical sheets including cover layer for near field recording medium and optical filter, optical information transmission media including optical fiber and optical waveguide and photoconductive boards in which low birefringence is required. [0092]
    TABLE 1
    (A) (C) Oblique incidence
    Example Copolymeri- Copolymeri- H-4000 birefringence
    & zation zation mixed (nm) Photoelastic
    Comparative proportion*1 proportion*2 amount*3 Distance from center sensitivity
    Example (wt %) (wt %) (wt %) R = 24 mm R = 42 mm R = 56 mm (×10−22 m2/N)
    Example
    1 40 7 0 10 8 20 33
    2 60 7 0 8 10 15 30
    3 80 7 0 10 12 18 28
    4 60 1 80 98 95 100 65
    5 60 40 67 80 90 103 66
    6 60 70 33 90 80 105 63
    Comp. Ex.
    1 0 0 100 125 130 120 77
    2 28 7 0 30
    3 90 7 0 32
    4 60 0 80
    5 60 90 0 120 130 120 74
  • [0093]
    TABLE 2
    Example
    & Intrinsic Light total
    Comparative Transcription viscosity transmissivity haze
    Example (%) (dl/g) (%) (%) Appearance
    Example 1 99 0.25 91.5 0.6 good
    2 98 0.25 89.2 0.8 good
    3 90 0.25 89 0.8 good
    4 99 0.33 85 4 good
    5 98 0.32 85.1 3.9 good
    6 98 0.28 85.3 3.8 good
    Comp. Ex. 1 98 0.35 91.7 0.6 good
    2 99 0.24 91.5 0.6 curvature
    3 80 0.24 89 0.8 crack
    4 0.33 70 80 white trubidity
    5 98 0.25 91.5 0.7 good

Claims (13)

What is claimed is:
1. A polycarbonate resin obtained by reaction of a compound represented by the following general formula (A), a compound represented by the following general formula (B), a compound represented by the following general formula (C) and a carbonic acid ester-forming compound, wherein an amount of a compound represented by the general formula (A) is 30 to 80% by weight to total amount of a compound represented by the general formula (A) and a compound represented by the general formula (B) and a compound represented by the general formula (C) is 1 to 80% by weight to total amount of a compound represented by the general formula (A), a compound represented by the general formula (B) and a compound represented by the general formula (C) and an intrinsic viscosity of said polycarbonate resin is 0.2 to 1.0 dl/g;
Figure US20010039313A1-20011108-C00008
wherein R1, R2, R3 and R4 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
Figure US20010039313A1-20011108-C00009
wherein R5, R6, R7 and R8 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s) R9, R10, R11 and R12 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s); R13 is an aliphatic group having 1 to 6 carbon atoms or absent; X is —SiO(R14)(R15)—, —SiO(R16)(RP17)—, a homopolymer of —SiO(R14)(R15)— or —SiO(R16)(R17)— having an average polymerization degree of more than 0 and 200 or below or a random copolymer of —SiO(R14)(R15)— and —SiO(R16)(R17)— having an average polymerization degree of more than 0 and 200 or below; R14, R15, R16 and R17 are, each independently, hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
Figure US20010039313A1-20011108-C00010
wherein R18 and R19 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aralkyl group having 7 to 17 carbon atoms and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s);
Y is;
Figure US20010039313A1-20011108-C00011
wherein R20 and R21 are, each independently, hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, or an aliphatic ring or a heterocycle in combination of R20 and R21 and when said group has carbon atom, said group can have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms as a substituent(s) and a is an integer of 0 to 20.
2. A polycarbonate resin according to
claim 1
, wherein said compound represented by the general formula (A) is at least one selected from the group consisting of 9,9-bis(4-hydroxyphenyl) fluorene, 9,9-bis(4-hydroxy-3-methylphenyl) fluorene and 9,9-bis(4-hydroxy-2-methylphenyl) fluorene.
3. A polycarbonate resin according to
claim 1
, wherein said carbonic acid ester-forming compound is phosgene.
4. A polycarbonate resin according to
claim 1
, wherein each said R9, R10, R11, and R12 in the compound represented by the general formula (B) are at least one group selected from the group consisting of methyl group and phenyl group.
5. A polycarbonate resin according to
claim 1
, wherein said compound represented by the general formula (B) is at least one compound selected from the group consisting of a random copolymer of dimethylsiloxane and diphenylsiloxane having 3-(o-hydroxyphenyl)propyl group at α,ω positions and α,ω-bis[3-(o-hydroxyphenyl) propyl]polydimethylsiloxane.
6. A polycarbonate resin according to
claim 1
, wherein said compound represented by the general formula (C) is 2,2-bis(4-hydroxyphenyl)propane.
7. A polycarbonate resin composition comprising of a mixture of the polycarbonate resin described in
claim 1
and a polycarbonate resin derived from 2,2-bis(4-hydroxyphenyl)propane.
8. An optical article used the polycarbonate resin in described in
claim 1
, having a 30 degree oblique incidence birefringence of below 110 nm.
9. An optical article used the polycarbonate resin in described in
claim 7
, having a 30 degree oblique incidence birefringence of below 110 nm.
10. An optical article used the polycarbonate resin in described in
claim 1
, having a photoelastic sensitivity of below 70×10−22 m2/N.
11. An optical article used the polycarbonate resin in described in
claim 7
, having a photoelastic sensitivity of below 70×10−22 m2/N.
12. An optical article used the polycarbonate resin in described in
claim 1
, having a total light transmissivity of 80% or above in a molded article of 3 mm.
13. An optical article used the polycarbonate resin in described in
claim 7
, having a total light transmissivity of 80% or above in a molded article of 3 mm.
US09/819,614 2000-03-29 2001-03-29 Polycarbonate resin and optical article used the same Expired - Lifetime US6340737B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP12-090094 2000-03-29
JP2000090094 2000-03-29
JP2000-090094 2000-03-29
JP2000383918A JP4525881B2 (en) 2000-03-29 2000-12-18 Polycarbonate resin and optical member
JP12-383918 2000-12-18

Publications (2)

Publication Number Publication Date
US20010039313A1 true US20010039313A1 (en) 2001-11-08
US6340737B2 US6340737B2 (en) 2002-01-22

Family

ID=26588643

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/819,614 Expired - Lifetime US6340737B2 (en) 2000-03-29 2001-03-29 Polycarbonate resin and optical article used the same

Country Status (5)

Country Link
US (1) US6340737B2 (en)
EP (1) EP1138714B1 (en)
JP (1) JP4525881B2 (en)
DE (1) DE60108992T2 (en)
TW (1) TW572933B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050048252A1 (en) * 2003-08-26 2005-03-03 Irene Dris Substrate and storage media for data prepared therefrom
US20050271879A1 (en) * 2004-06-08 2005-12-08 Canon Kabushiki Kaisha Transfer medium carrying member, intermediate transfer member and image forming apparatus using the same
CN100412718C (en) * 2004-06-08 2008-08-20 佳能株式会社 Transfer medium carrying member, intermediate transfer member and image forming apparatus using the same
USRE43604E1 (en) 2004-05-20 2012-08-28 Idemitsu Kosan Co. Ltd. Polycarbonate resin and electrophotographic photosensitive member using same
US20120271009A1 (en) * 2009-07-29 2012-10-25 Teijin Chemicals, Ltd. Polycarbonate-polydiorganosiloxane copolymer
KR20160002783A (en) * 2013-04-19 2016-01-08 이데미쓰 고산 가부시키가이샤 Polycarbonate-type resin composition and molded article
US20170139262A1 (en) * 2015-04-29 2017-05-18 Shenzhen China Star Optoelectronics Technology Co., Ltd. Polarizers and the manufacturing methods thereof, and liquid crystal panels

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6492481B1 (en) * 2000-07-10 2002-12-10 General Electric Company Substantially single phase silicone copolycarbonates, methods, and optical articles made therefrom
US6630562B2 (en) 2001-01-16 2003-10-07 Mitsubishi Gas Chemical Company, Inc. Polycarbonate resin
JP4492774B2 (en) * 2001-04-19 2010-06-30 三菱瓦斯化学株式会社 Cover layer film for optical information recording media
JP4484131B2 (en) * 2001-04-24 2010-06-16 三菱瓦斯化学株式会社 Film for flat panel display
CN1435823A (en) * 2002-02-01 2003-08-13 日本胜利株式会社 Optical disk
AU2003227193B8 (en) * 2002-03-28 2009-08-06 Teijin Chemicals, Ltd. Copolycarbonate and heat-resistant part comprising the copolymer
DE60309285T2 (en) * 2003-04-25 2007-05-24 Ricoh Co., Ltd. Binder for the granular forming of powdered particles and granulated molded parts
JP2005060628A (en) * 2003-08-20 2005-03-10 Teijin Chem Ltd Polycarbonate resin having excellent reflow resistance
JP4810099B2 (en) 2005-01-20 2011-11-09 株式会社メニコン Transparent gel and contact lens comprising the same
CN102276819A (en) * 2006-10-18 2011-12-14 出光兴产株式会社 Polycarbonate copolymer, molded body, optical material, and electrophotographic photosensitive body
JP5337365B2 (en) * 2007-10-18 2013-11-06 出光興産株式会社 Aromatic polycarbonate resin composition for resin stamper, method for producing resin stamper, and resin stamper
WO2015002427A1 (en) 2013-07-01 2015-01-08 (주) 엘지화학 Polyorganosiloxane compound, method for preparing same, and copolycarbonate resin comprising same
KR101636128B1 (en) * 2013-07-01 2016-07-04 주식회사 엘지화학 Polycarbonate resin composition
WO2015011669A2 (en) * 2013-07-24 2015-01-29 Sabic Innovative Plastics Ip B.V. Phenolic compounds as end-capping agents for polysiloxanes in polycarbonate-polysiloxane block copolymers
WO2016044695A1 (en) * 2014-09-18 2016-03-24 Momentive Performance Materials Inc. Polysiloxane co-or terpolymers and polymers made therefrom
WO2021002347A1 (en) * 2019-07-03 2021-01-07 出光興産株式会社 Molded body including polycarbonate-based resin composition
CN111171546A (en) * 2020-02-18 2020-05-19 江苏博云塑业股份有限公司 PC/ABS laser etching composite material and preparation method thereof

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE41435T1 (en) 1984-01-27 1989-04-15 Ici Plc FIBER REINFORCED PRODUCT AND METHOD OF MANUFACTURE.
JPH0628871B2 (en) 1986-02-05 1994-04-20 三菱化成株式会社 Method for producing molded article having excellent optical properties
KR970002664B1 (en) * 1989-07-07 1997-03-07 이데미쓰 세끼유 가가꾸 가부시끼가이샤 Polycarbonate-polydimethylsiloxane copolymer and method of production thereof
DE3928097A1 (en) 1989-08-25 1991-02-28 Bayer Ag POLYORGANOSILOXANE-POLYCARBONATE BLOCK COPOLYMERS AND THEIR USE FOR THE PRODUCTION OF OPTICAL DATA STORAGE
JP3254029B2 (en) * 1993-01-26 2002-02-04 出光興産株式会社 Electrophotographic photoreceptor using polycarbonate copolymer
JPH06329781A (en) * 1993-03-25 1994-11-29 Idemitsu Petrochem Co Ltd Polycarbonate/polyorganosiloxane copolymer and resin composition
JP3263486B2 (en) * 1993-05-27 2002-03-04 出光興産株式会社 Polycarbonate copolymer and method for producing the same
EP0633292B1 (en) * 1993-07-09 1998-12-30 General Electric Company Compositions of siloxane polyestercarbonate block terpolymers and high heat polycarbonates
DE4416325C2 (en) * 1993-09-22 1996-09-19 Bayer Ag Special polycarbonates and their use in the manufacture of optical articles
US5616674A (en) * 1994-05-10 1997-04-01 General Electric Company Method of preparing polycarbonate-polysiloxane block copolymers
US5530083A (en) * 1994-07-21 1996-06-25 General Electric Company Silicone-polycarbonate block copolymers and polycarbonate blends having reduced haze, and method for making
JP3486989B2 (en) 1994-11-14 2004-01-13 三菱瓦斯化学株式会社 Molding material for optical recording media
US5504177A (en) * 1995-03-02 1996-04-02 General Electric Company Method for preparation of block copolysiloxanecarbonates
JP3106931B2 (en) 1995-10-24 2000-11-06 財団法人シップ・アンド・オーシャン財団 Spiral lithium battery and method of manufacturing the same
US5859833A (en) * 1997-09-02 1999-01-12 General Electric Company Optical disk grade copolyestercarbonates derived from hydroxyphenylindanols
JP3775911B2 (en) * 1998-01-14 2006-05-17 大阪瓦斯株式会社   Polycarbonate polymer and method for producing the same
JP4021542B2 (en) * 1998-02-27 2007-12-12 出光興産株式会社 Polycarbonate resin, process for producing the same and electrophotographic photosensitive member
JP4286417B2 (en) * 2000-01-26 2009-07-01 出光興産株式会社 Electrophotographic photoreceptor

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050048252A1 (en) * 2003-08-26 2005-03-03 Irene Dris Substrate and storage media for data prepared therefrom
USRE43604E1 (en) 2004-05-20 2012-08-28 Idemitsu Kosan Co. Ltd. Polycarbonate resin and electrophotographic photosensitive member using same
US20050271879A1 (en) * 2004-06-08 2005-12-08 Canon Kabushiki Kaisha Transfer medium carrying member, intermediate transfer member and image forming apparatus using the same
CN100412718C (en) * 2004-06-08 2008-08-20 佳能株式会社 Transfer medium carrying member, intermediate transfer member and image forming apparatus using the same
US20120271009A1 (en) * 2009-07-29 2012-10-25 Teijin Chemicals, Ltd. Polycarbonate-polydiorganosiloxane copolymer
US8962780B2 (en) * 2009-07-29 2015-02-24 Teijin Chemicals, Ltd. Polycarbonate-polydiorganosiloxane copolymer
KR20160002783A (en) * 2013-04-19 2016-01-08 이데미쓰 고산 가부시키가이샤 Polycarbonate-type resin composition and molded article
US20160060428A1 (en) * 2013-04-19 2016-03-03 Idemitsu Kosan Co., Ltd. Polycarbonate-type resin composition and molded article
US10072134B2 (en) * 2013-04-19 2018-09-11 Idemitsu Kosan Co., Ltd. Polycarbonate-type resin composition and molded article
KR102140433B1 (en) 2013-04-19 2020-08-03 이데미쓰 고산 가부시키가이샤 Polycarbonate-type resin composition and molded article
US20170139262A1 (en) * 2015-04-29 2017-05-18 Shenzhen China Star Optoelectronics Technology Co., Ltd. Polarizers and the manufacturing methods thereof, and liquid crystal panels
US10012860B2 (en) * 2015-04-29 2018-07-03 Shenzhen China Star Optoelectronics Technology Co., Ltd Polarizers and the manufacturing methods thereof, and liquid crystal panels

Also Published As

Publication number Publication date
JP2001342247A (en) 2001-12-11
JP4525881B2 (en) 2010-08-18
DE60108992D1 (en) 2005-03-31
DE60108992T2 (en) 2006-04-13
EP1138714A3 (en) 2003-04-23
EP1138714B1 (en) 2005-02-23
TW572933B (en) 2004-01-21
US6340737B2 (en) 2002-01-22
EP1138714A2 (en) 2001-10-04

Similar Documents

Publication Publication Date Title
US6340737B2 (en) Polycarbonate resin and optical article used the same
EP1302785B1 (en) Plastic lens
EP2149587B1 (en) Polycarbonate resin and method for producing the same
JP2009062501A (en) Molded optical element and molding material therefor
SG172559A1 (en) Polycarbonate compositions having improved surface hardness
JP2001055435A (en) Molding material for optical recording medium
EP1223184B1 (en) Polycarbonate resin
TWI540152B (en) Polycarbonate resin and method for producing the same
JP3856115B2 (en) Polycarbonate resin
JP3486989B2 (en) Molding material for optical recording media
US20220195123A1 (en) Siloxane-containing block copolycarbonates having a small domain size
US6576735B2 (en) Polycarbonate resin
JP3525963B2 (en) Molding material for optical recording media
EP1097956B1 (en) Polycarbonat resin
JP4492774B2 (en) Cover layer film for optical information recording media
JP2002030140A (en) Polycarbonate resin and its manufacturing method
JP4314695B2 (en) Molding material for optical recording media
JP3791641B2 (en) New polycarbonate polymer
JPH03106931A (en) Polyorganosiloxane-polycarbonate block copolymer
WO2020138050A1 (en) Thermoplastic resin composition and optical member using same
JP2005206699A (en) Contact lens material
JP2001055436A (en) Molding material for optical recording medium
JP4484131B2 (en) Film for flat panel display
JP3992564B2 (en) Molding material for plastic mirror
JP2000319375A (en) Molding material for optical recording medium

Legal Events

Date Code Title Description
AS Assignment

Owner name: MITSUBISHI GAS CHEMICAL COMPANY, INC., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:OGAWA, NORIYOSHI;KANAGAWA, TATSUYA;NAKATANI, HIDEKAZU;REEL/FRAME:011662/0433

Effective date: 20010309

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

FPAY Fee payment

Year of fee payment: 12