WO2012133856A1 - Procédé pour la préparation d'une résine de polycarbonate, pellets de résine de polycarbonate et film étiré - Google Patents

Procédé pour la préparation d'une résine de polycarbonate, pellets de résine de polycarbonate et film étiré Download PDF

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Publication number
WO2012133856A1
WO2012133856A1 PCT/JP2012/058748 JP2012058748W WO2012133856A1 WO 2012133856 A1 WO2012133856 A1 WO 2012133856A1 JP 2012058748 W JP2012058748 W JP 2012058748W WO 2012133856 A1 WO2012133856 A1 WO 2012133856A1
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polycarbonate resin
reactor
dihydroxy compound
reaction
group
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PCT/JP2012/058748
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English (en)
Japanese (ja)
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慎悟 並木
小田　康裕
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三菱化学株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/701—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
    • B01F27/706—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with all the shafts in the same receptacle
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/307—General preparatory processes using carbonates and phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/11—Stirrers characterised by the configuration of the stirrers
    • B01F27/112—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades
    • B01F27/1125—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades with vanes or blades extending parallel or oblique to the stirrer axis
    • B01F27/11251—Stirrers characterised by the configuration of the stirrers with arms, paddles, vanes or blades with vanes or blades extending parallel or oblique to the stirrer axis having holes in the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/701—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
    • B01F27/702—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with intermeshing paddles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/708—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms characterised by the shape of the stirrer as a whole, i.e. of Z- or S-shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/1862—Stationary reactors having moving elements inside placed in series
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • B01J19/20—Stationary reactors having moving elements inside in the form of helices, e.g. screw reactors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00004—Scale aspects
    • B01J2219/00006—Large-scale industrial plants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00083—Coils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00076—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements inside the reactor
    • B01J2219/00085—Plates; Jackets; Cylinders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates

Definitions

  • the present invention relates to a method for efficiently and stably producing a polycarbonate resin excellent in optical characteristics, hue and thermal stability and having few foreign matters, and a stretched film obtained therefrom.
  • Polycarbonate resins generally contain bisphenols as monomer components and take advantage of transparency, heat resistance, mechanical strength, etc., so-called electrical / electronic parts, automotive parts, optical recording media, lenses, and other optical fields. Widely used as engineering plastic.
  • Patent Document 4 discloses that a retardation film made of a polycarbonate resin containing a fluorene structure has a low photoelastic coefficient and a reverse wavelength dispersion that decreases as the retardation becomes shorter. It is disclosed that it is useful for optical applications such as films.
  • the copolymer polycarbonate resin using the dihydroxy compound having the above fluorene structure is produced, it is produced by a method called a transesterification method or a melting method in which various dihydroxy compounds can be used as raw materials.
  • a dihydroxy compound and a carbonic acid diester such as diphenyl carbonate are transesterified in the presence of a polymerization catalyst at a high temperature of 200 ° C. or higher, and polymerization is advanced by removing by-product phenol out of the system to obtain a polycarbonate resin. It was.
  • a dihydroxy compound having a fluorene structure has poor heat stability, and particularly has a problem of coloring when a copolymerization reaction with a bisphenol compound or the aliphatic dihydroxy compound is performed.
  • the aliphatic dihydroxy compound has a problem that the thermal stability is lower than that of bisphenols, and the resin is easily colored by thermal decomposition during the polycondensation reaction performed at a high temperature.
  • the present invention solves the above-described problems in the production of a polycarbonate resin using a dihydroxy compound having a fluorene structure, and produces a polycarbonate resin having excellent characteristics such as optical properties and mechanical properties with little coloring.
  • the object is to produce a product with stable quality and high yield, and in particular, to solve the above problems even when an aliphatic dihydroxy compound having lower thermal stability than bisphenols is used in combination.
  • the present invention is as follows. 1.
  • the final polymerization reactor is a horizontal stirring reactor having a plurality of horizontal rotation shafts therein, and the reaction conditions satisfy the following formula (3): Method. 500 ⁇ ⁇ ⁇ 20000 (3) [ ⁇ : stirring blade rotation speed (rpm), ⁇ : melt viscosity (Pa ⁇ s) of the reaction liquid at the outlet of the horizontal reactor] 4). 4.
  • the amount of the monohydroxy compound in the reaction liquid at the outlet of the reactor immediately before the final polymerization reactor is 10 ppm or more and 3 wt% or less, and the monohydroxy compound in the reaction liquid at the outlet of the final polymerization reactor 9.
  • R 1 to R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 carbon atoms, It represents a cycloalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the same or different groups are arranged as each of the four substituents on each benzene ring.
  • X is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 20 carbon atoms.
  • m and n are each independently an integer of 0 to 5.
  • 13 In addition to the dihydroxy compound having a fluorene moiety represented by the formula (1), a dihydroxy compound containing a specific dihydroxy compound having a moiety represented by the following formula (5) in a part of the structure is used for the reaction.
  • the method for producing a polycarbonate resin according to any one of the above.
  • the stretched film according to any one of items 23 to 28, wherein the dihydroxy compound having a fluorene structure is a compound represented by the following formula (1).
  • R 1 to R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 carbon atoms, It represents a cycloalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the same or different groups are arranged as each of the four substituents on each benzene ring.
  • X is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 20 carbon atoms.
  • m and n are each independently an integer of 0 to 5. ] 30. Any of 23 to 29 above, wherein a dihydroxy compound containing a specific dihydroxy compound having a site represented by the following formula (5) as a part of the structure in addition to the dihydroxy compound having a fluorene site represented by the formula (1) is used. 2.
  • the site represented by the formula (5) is a site constituting a part of —CH 2 —OH and the case where it is a site constituting a part of the dihydroxy compound having the fluorene structure are excluded.
  • the polycarbonate resin is molded into an unstretched film having a thickness of 100 ⁇ m ⁇ 10 ⁇ m, and stretched to break when subjected to a tensile test at a glass transition temperature of + 6 ° C. and a tensile speed of 625% / min. 35.
  • the stretched film according to any one of items 23 to 34, wherein the degree (tensile elongation at break) is 220% or more.
  • the polycarbonate resin production method of the present invention it is possible not only to efficiently and stably produce a polycarbonate resin excellent in optical characteristics, hue, heat resistance, thermal stability and mechanical strength, but also to have a specific birefringence. It is possible to obtain a stretched film useful for applications such as a phase difference film having a thickness of.
  • the method for producing a polycarbonate resin of the present invention it is possible to produce a polycarbonate resin having a small amount of foreign matter and suitably used for optical applications such as a retardation film with a high yield.
  • FIG. 1 is an overall process diagram showing an example of a method for producing a polycarbonate resin according to the present invention.
  • FIG. 2 is a perspective view of a biaxial glasses-type stirring blade.
  • FIG. 3 is a schematic plan view showing an example of a horizontal stirring reactor.
  • the method for producing a polycarbonate resin of the present invention is a method for producing a polycarbonate resin by continuously supplying a dihydroxy compound containing a dihydroxy compound having a fluorene structure, a carbonic acid diester, and a polymerization catalyst to a reactor and performing polycondensation.
  • a plurality of the reactors are connected in series, and the internal temperature of the reactor immediately before the final polymerization reactor is 200 ° C. or higher and lower than 225 ° C., and is one of the final polymerization reactors.
  • the melt viscosity of the reaction liquid at the outlet of the previous reactor is 20 Pa ⁇ s or more and 1000 Pa ⁇ s or less.
  • the production method of the polycarbonate resin of the present invention may be referred to as “the production method of the present invention”.
  • the first reactor is referred to as the first reactor
  • the second reactor is referred to as the second reactor
  • the third reactor is referred to as the third reactor, respectively.
  • the reactor is also called similarly.
  • the “reactor” is a device having a heating device for heating to a reaction temperature described later in a step after mixing a dihydroxy compound and a carbonic acid diester, and causing an intentional transesterification reaction.
  • the dissolution tank whose main purpose is to mix and dissolve the raw materials in advance, or the piping for transferring the reaction liquid, even if the reaction proceeds slightly, Not included in the reactor.
  • the “final polymerization reactor” is a reactor provided on the most downstream side, and the reduced viscosity of the reaction solution at the outlet of the reactor is the reaction preceding the reactor. That which is 1.5 times or more the reduced viscosity of the reaction solution in the vessel.
  • an extruder or the like is regarded as a final polymerization reactor.
  • the polymerization process is divided into two stages, a pre-stage reaction and a post-stage reaction.
  • the pre-reaction is preferably carried out at a temperature of 130 to 225 ° C., more preferably 150 to 220 ° C., preferably 0.1 to 10 hours, more preferably 0.5 to 3 hours.
  • a temperature of 130 to 225 ° C. more preferably 150 to 220 ° C., preferably 0.1 to 10 hours, more preferably 0.5 to 3 hours.
  • the pressure in the reaction system is gradually lowered from the previous stage reaction, the reaction temperature is gradually increased, and the monohydroxy compound generated at the same time is removed from the reaction system, and the pressure in the reaction system is preferably reduced to the final reaction.
  • the polycondensation reaction is performed under a temperature range of 2 kPa or less, preferably 200 to 260 ° C., more preferably 210 to 250 ° C., to produce a polycarbonate resin.
  • the pressure in this specification refers to what is called an absolute pressure expressed on the basis of a vacuum.
  • the reactor used in this polymerization step is one in which at least two reactors are connected in series, and the reaction product from the outlet of the first reactor enters the second reactor.
  • the number of reactors to be connected is not particularly limited, but is preferably 2 to 7, more preferably 3 to 5, and still more preferably 3 to 4.
  • the type of the reactor is not particularly limited, but the reactor for the first stage reaction preferably has one or more vertical stirring reactors, and the reactor for the second stage reaction preferably has one or more horizontal stirring reactors. .
  • the reaction conditions of the horizontal stirring reactor in the final stage can have an important influence not only from the quality of the resin obtained, but also from various viewpoints such as the production yield or the amount of foreign matter in the resin.
  • the connection between the reactor and the next reactor may be performed by direct piping only, or may be performed through a preheater or the like as necessary.
  • the pipe is preferably a double pipe type that can transfer the reaction liquid without cooling and solidifying, has no gas phase on the polymer side, and does not cause a dead space.
  • the temperature of the heating medium for heating each of the reactors is preferably 260 ° C. or higher, more preferably 255 ° C. or higher, and particularly preferably 250 ° C. or higher. If the temperature of the heating medium is too high, thermal deterioration on the reactor wall surface is promoted, which may lead to problems such as an increase in different structures or decomposition products, or deterioration in color tone.
  • the temperature of the heating medium in the reactor before the final polymerization reactor is preferably less than 230 ° C.
  • the lower limit of the temperature of the heating medium is not particularly limited as long as the reaction temperature can be maintained.
  • Any known reactor may be used in the present invention.
  • a jacket type reactor using hot oil or steam as a heating medium a reactor having a coiled heat transfer tube inside, and the like can be mentioned.
  • the reaction method of the production method according to the present invention is preferably a continuous method.
  • a plurality of vertical stirring reactors and then at least one horizontal stirring reactor are used as the reactor. These reactors are installed in series and processed continuously.
  • By continuously producing using a horizontal stirring reactor it becomes possible to efficiently produce a polycarbonate resin having a stable molecular weight and composition, and the orientation when producing a stretched film becomes uniform.
  • a stretched film having a stable retardation can be obtained.
  • the obtained polycarbonate resin is formed into pellets having a predetermined particle size. Further, a step of devolatilizing and removing an unreacted raw material or a reaction byproduct monohydroxy compound in the polycarbonate resin, a step of adding a heat stabilizer, a release agent, or the like may be appropriately added.
  • Monohydroxy compounds such as phenol generated in the reactor are collected in a tank and, after effective recovery from the viewpoint of effective resource utilization, recovered and reused as raw materials such as DPC or bisphenol A. It is preferable to do.
  • the purification method of the by-product monohydroxy compound is not particularly limited, but a distillation method is preferably used.
  • the production method of the present invention comprises a dihydroxy compound containing a dihydroxy compound having a fluorene structure (fluorene-based dihydroxy compound) such as 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BHEPF) as a raw material monomer; , Diphenyl carbonate (DPC) and other carbonic acid diesters are each melted to prepare a raw material mixed melt (raw material preparation step), and these compounds are melted in the presence of a polymerization catalyst in a plurality of reactors.
  • the polycondensation reaction is performed in multiple stages (polycondensation step).
  • the monohydroxy compound is removed from the reaction system to advance the reaction and produce a polycarbonate resin.
  • DPC is used as the carbonic acid diester
  • the monohydroxy compound becomes phenol, and the reaction proceeds by removing the phenol under reduced pressure.
  • the dihydroxy compound including the fluorene-based dihydroxy compound used as a raw material for the polycarbonate resin and the carbonic acid diester are a batch type, semi-batch type or continuous type stirring tank type apparatus in an atmosphere of an inert gas such as nitrogen or argon. Use to prepare as raw material mixed melt or drop them independently into the reactor.
  • the temperature of the melt mixing is 80 ° C. to 180 ° C. Preferably, it is selected from the range of 90 ° C to 130 ° C.
  • an antioxidant may be added to the raw material mixed melt.
  • a hindered phenolic antioxidant and / or a phosphorus-based antioxidant that is generally known, by improving the storage stability of the raw material in the raw material preparation step, and suppressing coloring during polymerization, The hue of the resulting resin can be improved.
  • the polymerization catalyst to be used is usually preferably prepared in advance as an aqueous solution.
  • concentration of the catalyst aqueous solution is not particularly limited, and is adjusted to an arbitrary concentration according to the solubility of the catalyst in water. Moreover, it can replace with water and can also select other solvents, such as acetone, alcohol, toluene, or phenol.
  • the property of water used for dissolving the polymerization catalyst is not particularly limited as long as the kind and concentration of impurities contained are constant, but usually distilled water or deionized water is preferably used.
  • Pre-stage reaction process First, the mixture of the dihydroxy compound and the carbonic acid diester is supplied to a vertical reactor while being melted, and a polycondensation reaction is performed at a temperature of 130 ° C. to 230 ° C.
  • the reaction is preferably carried out continuously in a multi-tank system of 1 tank or more, more preferably 2 to 6 tanks, and 40% to 95% of the theoretical amount of monohydroxy compound produced as a by-product is distilled off.
  • the reaction temperature is preferably 130 ° C. to 225 ° C., more preferably 150 ° C. to 220 ° C., and the pressure is preferably 40 kPa to 1 kPa.
  • the temperature of each tank is sequentially increased within the above range, and the pressure of each tank is sequentially decreased within the above range.
  • the average residence time is preferably from 0.1 to 10 hours, more preferably from 0.5 to 5 hours, still more preferably from 0.5 to 3 hours.
  • the temperature is too high, thermal decomposition is promoted, the generation of different structures or colored components increases, and the quality of the resin may be deteriorated.
  • the temperature is too low, the reaction rate is lowered, and thus productivity may be lowered.
  • the melt polycondensation reaction used in the present invention is an equilibrium reaction, the reaction is promoted by removing the by-product monohydroxy compound from the reaction system, and therefore it is preferable to use a reduced pressure.
  • the pressure is preferably 1 kPa or more and 40 kPa or less, more preferably 5 kPa or more and 30 kPa or less.
  • the pressure is too high, the monohydroxy compound will not be distilled and the reactivity will be lowered. If it is too low, raw materials such as unreacted dihydroxy compound and / or carbonic acid diester will be distilled, so that the molar ratio of the raw materials will be shifted and desired Control of the reaction becomes difficult, for example, the molecular weight is not reached, and the raw material basic unit may be deteriorated.
  • the oligomer obtained in the preceding polycondensation step is supplied to a horizontal stirring reactor, and a polycondensation reaction is performed at an internal temperature of 200 ° C. to 250 ° C. to obtain a polycarbonate resin.
  • This reaction is preferably carried out continuously in one or more horizontal stirring reactors, more preferably 1 to 3 horizontal stirring reactors.
  • the reaction temperature is preferably 210 to 260 ° C, more preferably 220 to 250 ° C.
  • the pressure is preferably 13.3 kPa to 10 Pa, more preferably 1 kPa to 20 Pa.
  • the pressure is preferably 2 kPa to 10 Pa, more preferably 1 kPa to 20 Pa.
  • the average residence time is preferably 0.1 to 10 hours, more preferably 0.5 to 5 hours, and further preferably 0.5 to 2 hours.
  • ⁇ Reactor> In the present invention in which the polycondensation process is performed in a multi-tank system using at least two reactors, a plurality of reactors including a vertical stirring reactor are provided to increase the average molecular weight (reduced viscosity) of the polycarbonate resin.
  • Examples of the reactor include a vertical stirring reactor and a horizontal stirring reactor.
  • Specific examples include a stirred tank reactor, a thin film reactor, a centrifugal thin film evaporation reactor, a surface renewal type biaxial kneading reactor, a biaxial horizontal type stirred reactor, a wet wall reactor, and polymerizing while freely dropping.
  • Examples thereof include a perforated plate reactor, and a perforated plate reactor with a wire that polymerizes while dropping along a wire.
  • it is preferable to use a vertical stirring reactor in the former reaction step and it is preferable to use a horizontal stirring reactor in the latter reaction step.
  • the parts constituting the reaction apparatus the parts contacting the raw material monomer or the polymerization liquid of the components such as piping (hereinafter referred to as “wetted part”)
  • the surface material of the wetted part is composed of the above-mentioned substance, and a bonding material composed of the above-described substance and another substance, or a material obtained by plating the substance on another substance is used as the surface material. Can be used.
  • the vertical stirring reactor is a reactor having a vertical rotating shaft and a stirring blade attached to the vertical rotating shaft.
  • types of the stirring blades include turbine blades, paddle blades, fiddler blades, anchor blades, full-zone blades (manufactured by Shinko Pantech Co., Ltd.), Sunmeler blades (manufactured by Mitsubishi Heavy Industries, Ltd.), Max blend blades (Sumitomo Shigeki). Machine Industries Co., Ltd.], helical ribbon blades and twisted lattice blades [manufactured by Hitachi, Ltd.].
  • the horizontal stirring reactor mentioned above has a plurality of stirring blades extending in a substantially vertical direction with respect to the rotation axis of a plurality of stirring blades provided in the horizontal direction (horizontal direction).
  • the stirring blades provided on the respective horizontal rotation shafts are preferably arranged so as to have self-cleaning properties.
  • a uniaxial stirring blade such as a disk type and a paddle type, HVR, SCR, N-SCR [manufactured by Mitsubishi Heavy Industries, Ltd.], Vivolak [manufactured by Sumitomo Heavy Industries, Ltd.] ],
  • a biaxial type stirring blade such as a spectacle blade and a lattice blade [manufactured by Hitachi, Ltd.].
  • stirring blades such as a wheel shape, a saddle shape, a rod shape, and a window frame shape may be mentioned.
  • Such stirring blades are installed in at least two or more stages per rotating shaft, and the reaction solution is scraped up or spread by the stirring blades to update the surface of the reaction solution. Further, when the length of the horizontal rotation axis of the horizontal reactor is L and the rotation diameter of the stirring blade is D, L / D is preferably 1 to 15, more preferably 2 to 14.
  • reaction conditions of the final polymerization reactor affect not only the quality of the polycarbonate resin but also the production yield, both the quality and the yield are taken into account based on the above conditions. It is preferable to set the reaction conditions in consideration.
  • the polycarbonate resin produced in the present invention also increases the viscosity of the reaction solution as the reaction proceeds, as in the case of ordinary polycarbonate resins. Therefore, in each multi-tank reactor, the by-product is produced as the polycondensation reaction proceeds. In order to more effectively remove the monohydroxy compound (which becomes phenol when DPC is used) out of the system and to ensure the fluidity of the reaction solution, the reaction conditions are increased stepwise. It is preferable to set a higher temperature and a higher vacuum.
  • the reaction temperature is lowered, the melt viscosity becomes high and the fluidity of the reaction liquid is lowered.
  • the reaction liquid may be entangled with the stirring shaft and may not sag.
  • the reaction liquid charged into the final polymerization reactor Is preferably as low as possible and has a high molecular weight (high viscosity).
  • the internal temperature of the reactor at the outlet of the reactor immediately before the final polymerization reactor is less than 225 ° C, preferably 220 ° C or less, more preferably 215 ° C or less.
  • the internal temperature of the reactor immediately before the final polymerization reactor is 200 ° C. or higher, preferably 210 ° C. or higher. .
  • the melt viscosity of the reaction liquid at the outlet of the reactor immediately before the final polymerization reactor is 20 Pa ⁇ s or more, preferably 50 Pa ⁇ s or more, more preferably 100 Pa ⁇ s or more. On the other hand, it is 1000 Pa ⁇ s or less, preferably 800 Pa ⁇ s or less.
  • the degree of vacuum of the final polymerization reactor is as high as possible.
  • the viscosity of the reaction solution is too low, the reaction solution foams violently and is ideal. The plug flow property cannot be obtained, and the molecular weight cannot be controlled.
  • the viscosity is too high, the fluidity in the final polymerization reactor is lowered, the residence time becomes excessive, and the quality of the obtained polycarbonate resin is deteriorated.
  • the melt viscosity of the reaction liquid at the outlet of the reactor immediately before the final polymerization reactor can be controlled to a desired viscosity by appropriately adjusting the temperature or pressure of the previous reaction, the amount of catalyst, or the like.
  • the melt viscosity means a melt viscosity at a shear rate of 91.2 s ⁇ 1 measured at a temperature equal to the temperature of the reaction solution using a capillary rheometer [manufactured by Toyo Seiki Co., Ltd.].
  • the temperature of the heating medium in the final polymerization reactor is preferably 260 ° C. or lower, more preferably 255 ° C. or lower, and further preferably 250 ° C. or lower.
  • the temperature of the heating medium is preferably 220 ° C or higher, more preferably 230 ° C or higher.
  • the amount of the compound is preferably 3 wt% or less, more preferably 2 wt% or less, and particularly preferably 1.5 wt% or less.
  • the amount of the monohydroxy compound contained is preferably as small as possible, it is impossible in practice, but it is ideally 0 wt%. However, it is impossible in practice, and it is usually preferably 500 ppm or more.
  • the melt viscosity of the reaction liquid at the outlet of the final polymerization reactor is 1800 Pa ⁇ s or more. More preferably, it is 2000 Pa ⁇ s or more, and particularly preferably 2200 Pa ⁇ s or more.
  • the melt viscosity is preferably 5000 Pa ⁇ s or less, and preferably 4000 Pa ⁇ s or less. It is more preferable.
  • the melt viscosity of the reaction liquid at the outlet of the final polymerization reactor should be controlled by adjusting the reaction conditions such as the temperature, pressure or residence time of the final polymerization reactor or the amount of catalyst, or adjusting the end group balance. Can do.
  • the end group balance is adjusted by controlling the charged molar ratio of the carbonic diester and the dihydroxy compound, or the amount of unreacted monomer distilled in the previous reaction.
  • Q / P is preferably 1.5 or more, more preferably 1.6 or more, still more preferably 1.7 or more, and on the other hand, it is preferably 3.0 or less, more preferably 2.9. Hereinafter, it is more preferably 2.8 or less.
  • Q / P When Q / P is 3.0 or less, it is possible to suppress an excessive heat history in the final polymerization reactor and to prevent the color tone of the resulting resin from deteriorating. Therefore, Q / P is preferably 2.5 or less, more preferably 2.2 or less, and particularly preferably 2.0 or less. Further, by setting Q / P to 1.5 or more, it is possible to suppress an excessive increase in the heat history before the final polymerization reactor, and to prevent deterioration of the color tone of the resin obtained in the same manner. Further, the molecular weight does not increase more than the target in the final polymerization reactor, and the reaction can be easily controlled. Therefore, Q / P is preferably 1.6 or more, more preferably 1.7 or more, and particularly preferably 1.8 or more.
  • Q and P can be adjusted by adjusting temperature, pressure, residence time, catalyst amount or end group balance, etc., and Q / P can be controlled by appropriately combining these conditions. can do.
  • the temperature is decreased, the pressure is increased, the residence time is shortened, P is decreased, and as it is, Q is simultaneously decreased.
  • the Q / P can be increased by decreasing the pressure in the reactor and keeping Q constant.
  • the amount of liquid in the reactor is increased / decreased according to the amount of reaction liquid processed (resin production volume) to control the appropriate residence time. To do.
  • the final polymerization reactor has a very high melt viscosity of the reaction liquid, it is difficult to control the amount of liquid in the reactor, so the final polymerization reactor is suitable for the throughput of the reaction liquid. It is preferable to set a large capacity.
  • the liquid volume is more easily decomposed than bisphenols used in a normal polycarbonate resin, so that the liquid volume is more severely adjusted.
  • V / A is preferably 2 or more, more preferably 3 or more, and on the other hand, it is preferably 13 or less, more preferably 10 or less.
  • V Horizontal reactor volume (L)
  • A Reaction liquid throughput (kg / hr)
  • V / A By setting V / A to 13 or less, it is possible to prevent the capacity of the reactor from becoming excessive with respect to the amount of the reaction solution, and to reduce the amount of solution in the reactor when shortening the residence time. It is possible to suppress the reaction liquid from flowing into the outlet of the reactor and improve the pelletization yield. In addition, if the amount of liquid is increased beyond an appropriate amount, the residence time becomes too long, the color tone of the resulting resin is deteriorated, and the molecular weight is excessively higher than the target, making it difficult to control the reaction. Tend to be.
  • V / A the residence time will not be too short, and the molecular weight can be improved to a desired level. Further, the surface renewability of the reaction solution is improved, residual low molecular components such as monohydroxy compounds (for example, phenol) can be reduced, and the quality of the resulting resin can be improved.
  • V / A is reduced by increasing the reaction solution throughput A, and V is reduced by reducing the reaction solution throughput A. / A increases.
  • the polycarbonate resin of the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester, phenol or substituted phenol as a monohydroxy compound is by-produced, and the polycarbonate resin It is inevitable that it remains.
  • a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate
  • the polycarbonate resin obtained by a normal batch reaction not the continuous type as in the present invention, contains a monohydroxy compound having an aromatic ring such as by-product phenol of 1500 ppm or more.
  • these monohydroxy compounds may have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
  • the aliphatic polycarbonate resin using the fluorene dihydroxy compound or the dihydroxy compound having a cyclic ether structure as a monomer has a larger reaction equilibrium constant than the conventional aromatic polycarbonate resin using bisphenol A as a monomer.
  • the molecular weight increase rate in the latter reaction is fast. For this reason, if the pressure is lowered too much, the reaction is promoted too much, so that the reaction tends to be difficult to control.
  • the reaction rate is usually maximized when the amount of the hydroxy terminal is equal to the amount of the phenyl carbonate terminal represented by the following structural formula (8).
  • the balance of such end groups can be controlled by the molar ratio of the total dihydroxy compound used in the reaction and the carbonic acid diester when charged to the first reactor.
  • the molar ratio of the carbonic acid diester is preferably 0.990 or more and 1.030 or less.
  • the molar ratio of the diester carbonate charge to the total dihydroxy compound is more preferably 0.995 or more, while more preferably 1.025 or less.
  • the pressure in the final polymerization reactor is preferably 2 kPa or less, more preferably 1.5 kPa or less, and still more preferably 1.0 kPa or less. In addition, although it is so preferable that it is low, in many cases, it will become the limit of pressure reduction substantially at 10 Pa.
  • the amount of hydroxy end groups of the polycarbonate resin obtained by polycondensation according to the present invention is preferably such that the amount of all hydroxy end groups in the reaction solution at the outlet of the final polymerization reactor is 1000 ppm or less. . More preferably, it is 900 ppm or less, Most preferably, it is 800 ppm or less.
  • the amount of all hydroxy end groups in the reaction solution at the outlet of the final polymerization reactor is preferably 50 ppm or more.
  • the amount of the monohydroxy compound contained in the polycarbonate resin obtained by polycondensation in the present invention is preferably 1500 ppm or less, more preferably 1000 ppm or less, at the reactor outlet immediately before the final polymerization reactor. Especially preferably, it is 500 ppm or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the monohydroxy compound is usually 1 ppm.
  • the amount of the monohydroxy compound contained in the polycarbonate resin is preferably 10 ppm or more and 3 wt% or less in the reaction solution at the outlet of the reactor immediately before the final polymerization reactor.
  • 1500 ppm or less is preferable at the exit of the final polymerization reactor, more preferably 1000 ppm or less, and particularly preferably 500 ppm or less.
  • the lower limit of the content of the monohydroxy compound is usually 1 ppm.
  • Monohydroxy compounds at the outlet of these reactors are removed by making the reactor pressure as low as possible. Furthermore, the monohydroxy compound in resin can further be reduced by supplying a reaction liquid to an extruder after a polymerization reaction and performing vacuum devolatilization.
  • the polycarbonate resin obtained by polycondensation of the dihydroxy compound containing the dihydroxy compound having the fluorene structure according to the present invention is lower in thermal stability than the conventional aromatic polycarbonate resin, so that the reaction temperature is as low as possible. Although it is necessary to set low, the viscosity of a reaction liquid becomes higher than the conventional polycarbonate resin for that purpose.
  • the reaction liquid may wrap around the stirring shaft and not sag.
  • the number of revolutions of the stirring blade is set according to the melt viscosity of the reaction solution. It is necessary to set appropriately, and it is preferable to set in the range of the following formula (3).
  • ⁇ is preferably 500 or more, on the other hand, preferably 20000 or less, more preferably 15000 or less.
  • ⁇ 20000 or less, it is possible to suppress the reaction liquid from being wound around the stirring shaft, to improve the yield in the pelletizing step, and to prevent an increase in foreign matters in the resin.
  • ⁇ 500 or more, the stirring efficiency becomes sufficient, the amount of residual low molecular components in the reaction solution is suppressed from increasing, and the reaction solution is prevented from staying on the reactor wall surface and deteriorating in color. be able to.
  • ⁇ can be kept within a preferable range by reducing the stirring blade rotational speed ⁇ with increasing molecular weight.
  • the stirring blade rotational speed ⁇ is preferably less than 5 rpm, more preferably less than 4 rpm, and particularly preferably 3. Less than 5 rpm, especially less than 3 rpm is optimal.
  • stirring blade rotational speed ⁇ is too small, the interface renewability is deteriorated, the increase in molecular weight is hindered, and a polycarbonate resin having a molecular weight suitable for a stretched film may not be obtained.
  • the polycarbonate resin obtained by polycondensation according to the present invention may be subjected to the polycondensation reaction described above, and then passed through a filter in a molten state to filter foreign matters.
  • the resin obtained by polycondensation is introduced into an extruder, and then the resin discharged from the extruder is It is preferable to filter using a filter.
  • examples of the method for filtering the polycarbonate resin obtained by polycondensation using a filter include the following methods.
  • the final polymerization reactor is extracted in a molten state using a gear pump or a screw, and filtered through a filter, and the final polymerization reactor is melted and uniaxially or biaxially extruded.
  • the resin is supplied to the machine, melt-extruded, filtered through a filter, cooled and solidified in the form of a strand, and pelletized with a rotary cutter, etc., uniaxial or biaxial in the molten state from the final polymerization reactor
  • the resin is supplied to the extruder and melt-extruded, it is once cooled and solidified in the form of strands, pelletized, the pellets are again introduced into the extruder, filtered through a filter, cooled and solidified in the form of strands, and pellets From the final polymerization reactor in a molten state, and cooled and solidified in the form of strands without passing through an extruder, and then once pellets
  • the resin is supplied from the final polymerization reactor to the uniaxial or biaxial extruder in the molten state.
  • a method of directly filtering with a filter, cooling and solidifying in the form of a strand, and pelletizing with a rotary cutter or the like is preferable. This will be specifically described below.
  • the form of the extruder is not limited, but it is usually preferable to use a single or twin screw extruder.
  • a twin screw extruder is preferable for improving the devolatilization performance described later or for uniform kneading of the additive.
  • the rotation direction of the shaft may be different or the same, but the same direction is preferable from the viewpoint of kneading performance.
  • the use of an extruder can stabilize the supply of polycarbonate resin to the filter.
  • the hue or heat stability, and further, the secondary monomer in the transesterification reaction which may adversely affect the product due to bleed out, etc.
  • the resulting monohydroxy compound or low molecular weight compound such as polycarbonate resin oligomer remains, but these are reduced by using an extruder having a vent port, preferably by reducing the pressure from the vent port using a vacuum pump or the like. It is also possible to devolatilize and remove. Moreover, volatile liquids, such as water, can be introduce
  • the number of vent ports may be one or plural, but preferably two or more.
  • a heat stabilizer a neutralizing agent, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, a lubricant, a lubricant, a plasticizer, a compatibilizing agent or Flame retardants can be added and kneaded.
  • the polycarbonate resin is extruded with the above extruder and then filtered with a filter. It is preferable.
  • Examples of the form of the filter include known ones such as a candle type, a pleat type, and a leaf disc type.
  • a leaf disk type that can provide a large filtration area with respect to the storage container of the filter is preferable, and a plurality of combinations are preferably used so that a large filtration area can be obtained.
  • the filter used in the present invention is configured by combining a holding member (also referred to as a retainer) with a filtering member (hereinafter sometimes referred to as a medium), and these filters are stored (in some cases, a plurality or plural). It is used in the form of a unit (sometimes called a filter unit) stored in a container.
  • a type in which a plurality of aperture media are overlapped so that the differential pressure (pressure loss) of the filter is small and the apertures become finer in order from the resin intrusion direction is preferable.
  • a type obtained by sintering metal powder it is also possible to use a type obtained by sintering metal powder.
  • the material of the filter medium is not limited as long as it has the strength and heat resistance necessary for filtration of the obtained polycarbonate resin, but stainless steel such as SUS316 or SUS316L with a low iron content is particularly preferable. .
  • a nonwoven fabric type can be used in addition to a regular weaving portion of the foreign matter, such as a plain weave, a twill weave, a plain tatami mat or a twill mat weave.
  • a non-woven fabric type having a high gel-capturing ability particularly a type in which steel wires constituting the non-woven fabric are sintered and fixed is preferable.
  • the opening of the filter is preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, still more preferably 20 ⁇ m or less, and 10 ⁇ m or less when it is particularly desired to reduce foreign matter, as 99% filtration accuracy.
  • the filtration accuracy of 99% is 1 ⁇ m or more. Preferably there is.
  • the aperture defined as 99% filtration accuracy is the value of ⁇ when the ⁇ value represented by the following formula (9) determined in accordance with ISO 16889 (2008) is 1000.
  • Passivation treatment includes, for example, a method in which a filter is immersed in an acid such as nitric acid or an acid is passed through the filter to form a passivated surface, and roasted (heated) in the presence of water vapor or oxygen. ) The method of processing, the method of using these together, etc. are mentioned. Among them, it is preferable to perform both nitric acid treatment and roasting.
  • the roasting temperature is preferably 350 ° C. to 500 ° C., more preferably 350 ° C. to 450 ° C., and the roasting time is preferably 3 hours to 200 hours, more preferably 5 hours to 100 hours. If the roasting temperature is too low or the time is too short, the formation of the passive state becomes insufficient, and the polycarbonate resin tends to deteriorate during filtration. On the other hand, if the temperature of roasting is too high or the time is too long, the filter media may be severely damaged and the required filtration accuracy may not be achieved.
  • the concentration of nitric acid in the treatment with nitric acid is preferably 5 to 50% by weight, more preferably 10 to 30% by weight, and the treatment temperature is preferably 5 to 100 ° C. More preferably, it is 50 ° C. to 90 ° C., and the treatment time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 60 minutes.
  • the concentration of nitric acid is too low, the processing temperature is too low, or the processing time is too short, the formation of passives will be insufficient, the concentration of nitric acid will be too high, the processing temperature will be too high, or the processing time will be If it is too long, the filter media will be severely damaged and the required filtration accuracy may not be achieved.
  • the material of the containment vessel of the filter used in the production method of the present invention is not limited as long as it has strength and heat resistance that can withstand resin filtration, but preferably SUS316 with a low iron content. Alternatively, it is a stainless steel such as SUS316L.
  • the storage container of the filter may be arranged such that the supply port and the discharge port of the polycarbonate resin are arranged substantially horizontally, arranged substantially vertically, or arranged obliquely.
  • the polycarbonate resin supply port is disposed at the bottom of the filter storage container and the discharge port is disposed at the top. .
  • a gear pump between the extruder and the filter in order to stabilize the supply amount of the polycarbonate resin to the filter.
  • a gear pump there is no restriction
  • sticker part is preferable from a viewpoint of foreign material reduction.
  • class 7 as defined in JIS B 9920 (2002), more preferably, in order to prevent foreign matter from being mixed from the outside air. It is preferable to carry out in a clean room with higher cleanliness than class 6.
  • the polycarbonate resin filtered by the filter is cooled and solidified and pelletized by a rotary cutter or the like, and it is preferable to use a cooling method such as air cooling or water cooling when pelletizing.
  • a cooling method such as air cooling or water cooling when pelletizing.
  • air cooling it is preferable to use air from which foreign matters in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign matters in the air.
  • the aperture of the water filter to be used is preferably 10 to 0.45 ⁇ m in terms of 99% removal filtration accuracy.
  • a raw material filter it is also effective to filter the raw material monomer through a filter before polycondensation in order to further reduce foreign matters.
  • this filter is referred to as a raw material filter.
  • the shape of the raw material filter at that time may be any type such as a basket type, a disc type, a leaf disc type, a tube type, a flat cylindrical type or a pleated cylindrical type.
  • a pleated type having a large filtration area is preferable.
  • the filter medium constituting the raw material filter may be any one of metal wind, laminated metal mesh, metal nonwoven fabric, porous metal plate, and the like. From the viewpoint of filtration accuracy, a laminated metal mesh or a metal nonwoven fabric is preferred, and among them, a type in which a metal nonwoven fabric is sintered and fixed is preferred.
  • metal or resin ceramics can be used.
  • a metal filter having an iron content of 80% or less is used.
  • stainless steel such as SUS304, SUS316, SUS316L, or SUS310S is preferable.
  • the opening of the filter in the upstream unit is preferably C ⁇ m.
  • the aperture of the filter in the downstream unit is D ⁇ m, C is preferably larger than D (C> D) in at least one combination.
  • the opening of the raw material filter is not particularly limited, but at least one filter preferably has a filtration accuracy of 99% of 10 ⁇ m or less, and is preferably on the most upstream side when a plurality of filters are arranged. Is 8 or more, more preferably 10 or more, and preferably 2 or less, more preferably 1 or less on the most downstream side.
  • the opening of the said raw material filter said here is also determined based on the above-mentioned ISO16889 (2008).
  • the temperature of the raw material fluid when the raw material is passed through the raw material filter is not limited. However, if the raw material is too low, the raw material is solidified. If the raw material is too high, there is a problem such as thermal decomposition.
  • the temperature is preferably 200 ° C, more preferably 100 ° C to 150 ° C.
  • any of the raw materials to be used may be filtered, or all of the raw materials may be filtered.
  • the method is not limited, and the dihydroxy compound and the carbonic acid diester are not limited.
  • the raw material mixture may be filtered, or may be mixed after separately filtering.
  • the reaction liquid in the middle of a polycondensation reaction can also be filtered with a filter.
  • FIG. 1 is a diagram showing an example of a manufacturing apparatus used in the manufacturing method of the present invention.
  • the polycarbonate resin of the present invention comprises a raw material preparation step for preparing the raw material dihydroxy compound and carbonic acid diester, and a polycondensation reaction of these raw materials in a molten state using a plurality of reactors. It is manufactured through a condensation process.
  • the distillate produced in the polycondensation step is liquefied by the condensers 12a, 12b, 12c and 12d and collected in the distillate collection tank 14a.
  • a step of devolatilizing and removing unreacted raw materials or reaction by-products in the polymerization reaction solution a step of adding a heat stabilizer, a release agent, a colorant, or the like, or a polycarbonate resin with pellets having a predetermined particle size
  • a step of forming a pellet of polycarbonate resin is formed.
  • BHEPF 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene
  • ISB specific dihydroxy compound
  • PEG1000 polyethylene glycol 1000
  • a DPC melt prepared at a predetermined temperature in a nitrogen gas atmosphere is supplied from the raw material supply port 1a to the raw material mixing tank 2a.
  • the powdered BHEPF is supplied from the raw material supply port 1b, and then the ISB melt and the PEG 1000 melt measured in a nitrogen gas atmosphere are supplied from the raw material supply ports 1c and 1d to the raw material mixing tank 2a. Continuously supplied. And these are mixed within the raw material mixing tank 2a, and a raw material mixing melt is obtained.
  • the obtained raw material mixed melt is continuously supplied to the first vertical stirring reactor 6a via the raw material supply pump 4a and the raw material filter 5a. Moreover, magnesium acetate aqueous solution is continuously supplied as a raw material catalyst from the catalyst supply port 1e in the middle of the transfer piping of the raw material mixed melt.
  • a first vertical stirring reactor 6a, a second vertical stirring reactor 6b, a third vertical stirring reactor 6c, and a fourth horizontal stirring reactor 6d are provided in series. It is done. In each reactor, the liquid level is kept constant and a polycondensation reaction is performed, and the polymerization reaction liquid discharged from the bottom of the first vertical stirring reactor 6a passes to the second vertical stirring reactor 6b. The third vertical stirring reactor 6c is successively supplied to the fourth horizontal stirring reactor 6d, and the polycondensation reaction proceeds.
  • the reaction conditions in each reactor are preferably set so that the high temperature, high vacuum, and low stirring speed are achieved as the polycondensation reaction proceeds.
  • the fourth horizontal stirring reactor 6d corresponds to the final polymerization reactor in the present invention
  • the third vertical stirring reactor 6c corresponds to the reactor immediately before the final polymerization reactor. To do.
  • the first vertical stirring reactor 6a, the second vertical stirring reactor 6b, and the third vertical stirring reactor 6c are provided with Max Blend blades 7a, 7b, 7c, respectively.
  • the fourth horizontal stirring reactor 6d is provided with a biaxial glasses-type stirring blade 7d.
  • a gear pump 4b is provided after the third vertical stirring reactor 6c because the transferred reaction liquid has a high viscosity.
  • the internal heat exchanger 8a may be used so that the temperature of the heating medium does not become excessively high. 8b is provided.
  • distilling tubes 11a, 11b, 11c, and 11d for discharging by-products generated by the polycondensation reaction are attached to these four reactors, respectively.
  • reflux condensers 9a and 9b and reflux pipes 10a and 10b are provided in order to return a part of the distillate to the reaction system.
  • the reflux ratio can be controlled by appropriately adjusting the pressure of the reactor and the temperature of the heating medium of the reflux condenser.
  • the distillation pipes 11a, 11b, 11c, and 11d are connected to condensers 12a, 12b, 12c, and 12d, respectively, and each reactor is in a predetermined depressurized state by a decompression device 13a, 13b, 13c, and 13d. To be kept.
  • by-products such as phenol (monohydroxy compound) are continuously liquefied and recovered from the condensers 12a, 12b, 12c, and 12d attached to each reactor.
  • a cold trap (not shown) is provided downstream of the condensers 12c and 12d attached to the third vertical stirring reactor 6c and the fourth horizontal stirring reactor 6d, respectively, so that by-products are continuously present. Solidified and recovered.
  • the reaction liquid raised to a predetermined molecular weight is extracted from the fourth horizontal stirring reactor 6d and transferred to the twin screw extruder 15a by the gear pump 4c.
  • the twin screw extruder is equipped with a vacuum vent to remove residual low molecular components in the polycarbonate resin. Further, an antioxidant, a light stabilizer, a colorant, a release agent, or the like is added as necessary.
  • Resin is supplied from the twin screw extruder 15a to the polymer filter 15b by the gear pump 4d, and foreign matter is filtered.
  • the resin that has passed through the filter is extracted in the form of a strand from the die head, cooled with water in the strand cooling tank 16a, and then pelletized by the strand cutter 16b.
  • the pellets are pneumatically transported by an air blower 16c and sent to a product hopper 16d. A predetermined amount of product is packed in a product bag by the measuring instrument 16e.
  • polycondensation based on a transesterification reaction between a dihydroxy compound and a carbonic acid diester is started according to the following procedure.
  • first vertical stirring reactor 6a second vertical stirring reactor 6b, third vertical stirring reactor 6c, The four horizontal stirring reactors 6d
  • the internal temperature of each reactor and the temperature and pressure of the heating medium are not particularly limited, but are preferably set as follows.
  • the dihydroxy compound and the carbonic acid diester are mixed at a predetermined molar ratio in a raw material mixing tank 2a in a nitrogen gas atmosphere to obtain a raw material mixed melt.
  • the raw material mixed melt prepared in the raw material mixing tank 2a is separately added to the first reactor. Continuously fed into the vertical stirring reactor 6a. Simultaneously with the start of the supply of the raw material mixed melt, the catalyst is continuously supplied from the catalyst supply port 1d into the first vertical stirring reactor 6a to start the transesterification reaction.
  • the liquid level of the polymerization reaction solution is kept constant so as to have a predetermined average residence time.
  • a valve (not shown) provided in a polymer discharge line at the bottom of the tank while detecting the liquid level with a liquid level gauge or the like.
  • a method for controlling the opening degree may be mentioned.
  • the polymerization reaction liquid is discharged from the tank bottom of the first vertical stirring reactor 6a, discharged to the second vertical stirring reactor 6b, and subsequently discharged from the tank bottom of the second vertical stirring reactor 6b, Sequentially and continuously supplied to the third vertical stirring reactor 6c.
  • 50% to 95% of the theoretical amount of phenol produced as a by-product is distilled off to produce oligomers.
  • the oligomer obtained in the preceding reaction step is transferred by the gear pump 4b, supplied to the fourth horizontal stirring reactor 6d, and under temperature and pressure conditions suitable for performing the latter reaction as described later,
  • the by-produced phenol and partially unreacted monomer are removed out of the system through the distillation pipe 11d to produce a polycarbonate resin.
  • the fourth horizontal stirring reactor 6d has one or more horizontal rotation shafts, and extends from the horizontal rotation shaft in the vertical direction, a disk shape, a wheel shape, a saddle shape, a rod shape, or a window frame shape.
  • One or two or more kinds of stirring blades such as those described above are combined, and at least two stages are installed in the horizontal direction per rotation axis.
  • the stirring blades provided on each horizontal rotation shaft are arranged to have self-cleaning properties. It is easy to stably obtain a polycarbonate resin having a reduced viscosity suitable for a stretched film by renewing the surface of the reaction solution by rolling up or spreading the reaction solution with such a stirring blade.
  • reaction solution surface renewal means that the reaction solution on the liquid surface is replaced with the reaction solution on the lower surface of the liquid surface.
  • FIG. 2 is a perspective view of the biaxial glasses-type stirring blade 7d
  • FIG. 3 is a schematic view of the horizontal stirring reactor 6d containing the same, as viewed from above.
  • the stirring blades 21A and 21B are in a phase difference of 90 degrees from each other, and the respective shafts 22A and 22B are rotated in reverse. As a result, the tip portions of the respective stirring blades 21A and 21B rotate while scraping off the resin adhered to the other stirring blades 21B and 21A.
  • a plurality of such stirring blades 21A, 21B are connected in the axial direction.
  • the reaction temperature in the latter reaction step is usually preferably 200 to 260 ° C., more preferably 210 to 250 ° C.
  • the reaction pressure is usually preferably 13.3 kPa to 10 Pa, more preferably. Is 2 kPa to 30 Pa, more preferably 1 kPa to 50 Pa.
  • the residence time of the reaction liquid can be appropriately set by using the fourth horizontal stirring reactor 6d having a larger hold-up than the twin-screw vent type extruder in terms of the device structure.
  • the temperature can be lowered, and it becomes possible to obtain a polycarbonate resin with improved color tone and excellent mechanical properties.
  • the horizontal stirring reactor is a device having a horizontal axis and mutually discontinuous stirring blades mounted substantially at right angles to the horizontal axis, and does not have a screw portion unlike an extruder. In the production method of the present invention, it is preferable to use at least one such horizontal stirring reactor.
  • the raw material mixed melt and the catalyst are continuously supplied to perform the transesterification reaction. Based melt polycondensation is started.
  • the average residence time of the polymerization reaction liquid in each reactor becomes equal to that in the steady operation immediately after the start of the melt polycondensation.
  • the polymerization reaction liquid does not receive an excessive heat history, and foreign matters such as gel or burns generated in the obtained polycarbonate resin are reduced. Also, the color tone is good.
  • the dihydroxy compound used for the production of the polycarbonate resin of the present invention includes a dihydroxy compound having a fluorene structure (fluorene-based dihydroxy compound). From the viewpoint of heat resistance, mechanical strength, optical properties, or polymerization reactivity of the obtained polycarbonate resin, those represented by the following formula (1) having a 9,9-diphenylfluorene structure are preferable.
  • R 1 to R 4 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon group having 6 to 20 carbon atoms. It represents a cycloalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and the same or different groups are arranged as each of the four substituents on each benzene ring.
  • X is a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 6 to 20 carbon atoms.
  • m and n are each independently an integer of 0 to 5.
  • R 1 to R 4 are each independently a hydrogen atom or an unsubstituted or ester group, an ether group, a carboxylic acid, an amide group, or a halogen substituted alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a carbon number More preferred are 1 to 6 alkyl groups.
  • X is unsubstituted or substituted by an ester group, an ether group, a carboxylic acid, an amide group, or a halogen-substituted alkylene group having 2 to 10 carbon atoms, unsubstituted or an ester group, an ether group, a carboxylic acid, an amide group, or a halogen.
  • a cycloalkylene group having 6 to 20 carbon atoms, an unsubstituted or ester group, an ether group, a carboxylic acid, an amide group, or an arylene group having 6 to 20 carbon atoms substituted with halogen is preferable. More preferably, it is an alkylene group of ⁇ 6.
  • M and n are each independently preferably an integer of 0 to 2, with 0 or 1 being particularly preferred.
  • 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-2-) Methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, 9,9-bis [4- (2 -Hydroxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxypropoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3 -Isopropylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isobutylphenyl] fluorene, 9,9-bis 4- (2-hydroxyethoxy) -3-tert-butylphen
  • 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis [4- (2) is preferable from the viewpoint of optical performance, handling, availability, and the like.
  • the polycarbonate resin of the present invention is preferably obtained by using 18 mol% or more of a fluorene-based dihydroxy compound having a structural unit represented by the above general formula (1) as a raw material monomer, based on the total dihydroxy compound, More preferably, it is 20 mol% or more, Most preferably, it is 25 mol% or more. Moreover, it is preferably 90 mol% or less, more preferably 70 mol% or less, and particularly preferably 50 mol% or less.
  • the obtained polycarbonate resin may not exhibit the desired optical performance. If the amount is too large, the melt viscosity of the obtained polycarbonate resin becomes excessively high, and it may not be able to be stably discharged due to wrapping around the stirring blade of the horizontal stirring reactor. May cause deterioration of the polycarbonate resin. Moreover, the fluidity
  • the polycarbonate resin of the present invention preferably contains a structural unit derived from a dihydroxy compound other than the fluorene-based dihydroxy compound in order to adjust the desired optical properties.
  • a dihydroxy compound (specific dihydroxy compound) having a portion represented by the above formula (5) in a part of the structure is provided. preferable.
  • Specific examples include oxyalkylene glycols, dihydroxy compounds having an ether group bonded to an aromatic group in the main chain, and dihydroxy compounds having a cyclic ether structure.
  • Specific examples of the specific dihydroxy compound having a site represented by the above formula (5) in a part of the structure include, for example, oxyalkylene glycols and dihydroxy compounds having an ether group bonded to an aromatic group in the main chain. And dihydroxy compounds having a cyclic ether structure.
  • Examples of the oxyalkylene glycols include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.
  • Examples of the dihydroxy compound having an ether group bonded to an aromatic group in the main chain include 2,2-bis [4- (2-hydroxyethoxy) phenyl] propane and 2,2-bis [4- (2 -Hydroxypropoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) biphenyl, bis [4- (2-hydroxyethoxy) phenyl] sulfone, etc. Can be mentioned.
  • dihydroxy compound having the cyclic ether structure examples include a dihydroxy compound represented by the following formula (10) and a spiro glycol represented by the following formula (11) or the following formula (12).
  • cyclic ether structure of the “dihydroxy compound having a cyclic ether structure” means an organic compound having an ether group in the cyclic structure and a structure in which the carbon constituting the cyclic chain is an aliphatic carbon. To do.
  • examples of the dihydroxy compound represented by the formula (10) include isosorbide (ISB), isomannide and isoidet which are in a stereoisomeric relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.
  • the hydroxy compounds represented by the formula (10), (11) or (12) are preferred from the viewpoints of availability, handling, reactivity during polymerization, and hue of the obtained polycarbonate resin.
  • a representative dihydroxy compound having a cyclic ether structure is preferable, and a dihydroxy compound represented by the above formula (10) or a dihydroxy compound having two cyclic ether structures such as spiroglycol represented by the following formula (11) is further included.
  • an anhydrous sugar alcohol which is a dihydroxy compound having two sugar-derived cyclic ether structures, such as a dihydroxy compound represented by the following formula (10), is particularly preferable.
  • dihydroxy compounds having no aromatic ring structure are preferably used from the viewpoint of optical properties of the polycarbonate resin.
  • anhydrous sugar alcohols such as dihydroxy compounds represented by the above formula (10) obtained by dehydrating condensation of sorbitol produced from various starches that are abundant as plant-derived resources are available. And most preferable from the viewpoints of ease of production, light resistance, optical properties, moldability, heat resistance and carbon neutral.
  • the dihydroxy compound represented by the above formula (10), (11) or (12) when used as a raw material monomer, it is preferably used in an amount of 10 mol% or more, more preferably 30 mol% or more, especially with respect to the total dihydroxy compound. Preferably it is 40 mol% or more.
  • the upper limit is preferably 80 mol% or less, more preferably 60 mol% or less, and particularly preferably 50 mol% or less. If the amount of the dihydroxy compound used is too small or too large, the obtained polycarbonate resin may not exhibit the desired optical performance.
  • These specific dihydroxy compounds may be used alone or in combination of two or more depending on the required performance of the polycarbonate resin to be obtained.
  • the dihydroxy compound having the bond structure of the formula (2) may contain a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer or a heat stabilizer. .
  • a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer or a heat stabilizer.
  • a basic stabilizer since the specific dihydroxy compound of the present invention is easily altered under acidic conditions, it is preferable to include a basic stabilizer.
  • Examples of the basic stabilizer include hydroxides, carbonates, phosphates, phosphites, and hypophosphites of group 1 or group 2 metals in the long-period periodic table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005).
  • Acid salts, borates and fatty acid salts tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, Triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenyl Basic ammonium compounds such as ammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide, diethylamine , Dibutylamine,
  • the content of these basic stabilizers in the dihydroxy compound is not particularly limited.
  • the dihydroxy compound having the structure represented by the formula (2) used in the present invention is unstable in an acidic state, and thus the above-mentioned stability. It is preferable to add a stabilizer so that the pH of the aqueous solution of the dihydroxy compound containing the agent is 7 or more.
  • the amount is usually preferably 0.0001% by weight to 1% by weight, more preferably 0.001% by weight to 0.1% by weight, based on each dihydroxy compound used in the present invention.
  • the specific dihydroxy compound having the structure represented by the formula (2) is apt to be gradually oxidized by oxygen, moisture is not mixed to prevent decomposition by oxygen during storage or handling during manufacture.
  • an oxygen scavenger it is preferable to use an oxygen scavenger or to have a nitrogen atmosphere.
  • the polycarbonate resin of the present invention may contain a structural unit derived from a dihydroxy compound other than the fluorene-based dihydroxy compound and the specific dihydroxy compound (hereinafter may be referred to as “other dihydroxy compound”).
  • Examples of the other dihydroxy compounds include linear aliphatic hydrocarbon dihydroxy compounds, linear branched aliphatic hydrocarbon dihydroxy compounds, alicyclic hydrocarbon dihydroxy compounds, and aromatic bisphenols.
  • straight-chain aliphatic hydrocarbon dihydroxy compound examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2 -Butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
  • dihydroxy compound of the linear branched aliphatic hydrocarbon examples include neopentyl glycol and hexylene glycol.
  • Examples of the alicyclic hydrocarbon dihydroxy compound include 1,2-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and tricyclodecanedi.
  • aromatic bisphenols examples include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, and 2,2-bis (4 -Hydroxy-3,5-diethylphenyl) propane, 2,2-bis (4-hydroxy- (3,5-diphenyl) phenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) Propane, 2,2-bis (4-hydroxyphenyl) pentane, 2,4'-dihydroxy-diphenylmethane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-5-nitrophenyl) methane, 1,1- Bis (4-hydroxyphenyl) ethane, 3,3-bis (4-hydroxyphenyl) pentane, 1,1-bis (4-hydroxy) Enyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4′-dihydroxydiphenylsulfone, bis (4-hydroxyphen
  • dihydroxy compounds may be used alone or in combination with the specific dihydroxy compound depending on the required performance of the polycarbonate resin to be obtained, and after combining two or more kinds, the fluorene-based dihydroxy compound or the specific dihydroxy compound. You may use together with a compound. Above all, in order to obtain the desired optical performance, to stabilize production, and to obtain a polycarbonate resin having characteristics suitable for a stretched film, two or more kinds of dihydroxy compounds are copolymerized in addition to the fluorene-based dihydroxy compound. Is preferred.
  • a dihydroxy compound having no aromatic ring structure in the molecular structure that is, an aliphatic hydrocarbon dihydroxy compound or an alicyclic hydrocarbon dihydroxy compound is preferable. May be.
  • the aliphatic hydrocarbon dihydroxy compounds suitable for the polycarbonate resin of the present invention include 1,3-propanediol, 1,4-butanediol, 1,5-heptanediol, and 1,6-hexanediol.
  • a straight-chain aliphatic hydrocarbon dihydroxy compound having 3 to 6 carbon atoms and having hydroxy groups at both ends is preferred.
  • 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or tricyclodecane dimethanol is particularly preferable, and 1,2-cyclohexanedimethanol is more preferable.
  • It is a dihydroxy compound having a cyclohexane structure such as 2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol or 1,4-cyclohexanedimethanol.
  • the polycarbonate resin of the present invention can be obtained by polycondensation by a transesterification reaction using a dihydroxy compound containing the fluorene-based dihydroxy compound and a carbonic acid diester as raw materials.
  • Examples of the carbonic acid diester used usually include those represented by the following formula (13). These carbonic acid diesters may be used alone or in combination of two or more.
  • a 1 and A 2 are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A 1 and A 2 May be the same or different.
  • a preferable example of A 1 and A 2 is a substituted or unsubstituted aromatic hydrocarbon group, and a more preferable example is an unsubstituted aromatic hydrocarbon group.
  • Examples of the carbonic acid diester represented by the formula (13) include substituted diphenyl carbonate such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Among them, preferred is diphenyl carbonate or substituted diphenyl carbonate, and particularly preferred is diphenyl carbonate.
  • DPC diphenyl carbonate
  • ditolyl carbonate dimethyl carbonate
  • diethyl carbonate diethyl carbonate
  • di-t-butyl carbonate diphenyl carbonate
  • Carbonic acid diesters may contain impurities such as chloride ions, which may hinder the polymerization reaction or worsen the hue of the resulting polycarbonate resin. It is preferable to use what was done.
  • the polycarbonate resin of the present invention is produced by transesterifying the dihydroxy compound containing the specific dihydroxy compound and the carbonic acid diester represented by the formula (13) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system.
  • transesterification reaction polycondensation is performed in the presence of a transesterification reaction catalyst.
  • the transesterification reaction catalyst (hereinafter simply referred to as a catalyst or a polymerization catalyst) that can be used in the production of the polycarbonate resin of the present invention may be used. ) Can greatly affect the reaction rate or the color tone of the polycarbonate resin obtained by polycondensation.
  • the catalyst used is not limited as long as it can satisfy the transparency, hue, heat resistance, thermal stability, and mechanical strength of the produced polycarbonate resin.
  • metal compounds of Group 1 or Group 2 (hereinafter simply referred to as “Group 1” or “Group 2”) in the long-period periodic table, as well as basic boron compounds, basic phosphorus compounds, and basic ammonium compounds And basic compounds such as amine compounds.
  • Group 1 metal compounds and / or Group 2 metal compounds are used.
  • Examples of the Group 1 metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, potassium carbonate, and carbonic acid. Lithium, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, hydrogenated Cesium boron, sodium borohydride, potassium phenyl boronate, lithium phenyl boronide, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, hydrogen phosphate Sodium, 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium
  • Examples of the Group 2 metal compound include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, carbonic acid.
  • Examples thereof include magnesium, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, and strontium stearate.
  • magnesium compounds, calcium compounds, and barium compounds are preferred, and magnesium compounds and / or calcium compounds are more preferred from the viewpoint of polymerization activity and the hue of the polycarbonate resin obtained.
  • a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound can be used in combination with the aforementioned Group 1 metal compound and / or Group 2 metal compound.
  • a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound
  • Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts.
  • Examples of the basic ammonium compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide.
  • Triethylmethylammonium hydroxide triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium Hydroxide and butyltriphenyl ammonium hydroxide, and the like.
  • Examples of the amine compound include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, and 4-methoxypyridine.
  • the amount of the polymerization catalyst used is generally preferably 0.1 ⁇ mol to 300 ⁇ mol, more preferably 0.5 ⁇ mol to 100 ⁇ mol, per 1 mol of all dihydroxy compounds used in the polymerization.
  • the amount of metal is The amount is preferably 0.1 ⁇ mol or more, more preferably 0.3 ⁇ mol or more, particularly preferably 0.5 ⁇ mol or more per 1 mol of the dihydroxy compound.
  • 40 micromol or less is preferable, More preferably, it is 30 micromol or less, More preferably, it is 20 micromol or less.
  • the specific dihydroxy compound having a fluorene moiety used in the present invention may contain sulfur impurities derived from the catalyst used in the synthesis, and has the effect of deactivating the polymerization catalyst.
  • the polymerization catalyst to be added is preferably used in excess of the above range by the amount deactivated.
  • the polymerization temperature must be increased by that much. Therefore, there is a high possibility that the hue of the resulting polycarbonate resin will deteriorate, and the unreacted raw material may volatilize during the polymerization, causing the molar ratio of the dihydroxy compound and the carbonic acid diester to collapse and not reaching the desired molecular weight. There is.
  • the amount of the polymerization catalyst used is too large, undesirable side reactions may occur, and the hue of the resulting polycarbonate resin may be deteriorated or the resin may be colored during molding.
  • Group 1 metals sodium, potassium, and cesium may adversely affect the hue if they are contained in a large amount in the polycarbonate resin. And these metals may mix not only from the catalyst to be used but from a raw material or a reaction apparatus.
  • the total amount of the compound of the metal in the polycarbonate resin is preferably 2 ⁇ mol or less, more preferably 1 ⁇ mol or less, still more preferably 0.5 ⁇ mol or less, per 1 mol of the total dihydroxy compound as the metal amount.
  • the molecular weight of the polycarbonate resin of the present invention obtained by polycondensation in this way can be expressed by reduced viscosity, preferably 0.20 dL / g or more, more preferably 0.30 dL / g or more. Preferably, it is 0.35 dL / g or more, more preferably 0.40 or more. On the other hand, it is preferably 1.20 dL / g or less, more preferably 0.80 dL / g or less, further preferably 0.60 dL / g or less, and 0.50 dL / g or less. Particularly preferred, most preferred is 0.45 dL / g or less.
  • the reduced viscosity is a value measured using an Ubbelohde viscometer at a temperature of 20.0 ° C. ⁇ 0.1 ° C., prepared precisely using a methylene chloride as a solvent and a polycarbonate resin concentration of 0.6 g / dL. It is.
  • the glass transition temperature of the polycarbonate resin in the present invention is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher, and particularly preferably 125 ° C. or higher. If the glass transition temperature is excessively low, after the polycarbonate resin of the present invention is formed into a film, it tends to deteriorate the heat resistance when stretched into a retardation film, etc. There is a possibility that the phase difference changes with time. On the other hand, the glass transition temperature is preferably 160 ° C. or less, more preferably 150 ° C. or less, still more preferably 140 ° C. or less, and particularly preferably 135 ° C. or less.
  • the melt viscosity during the production of the polycarbonate resin becomes high, and there is a possibility that it will not be able to be discharged stably by wrapping around the stirring blade of the horizontal stirring reactor. As a result, it tends to be difficult to increase the molecular weight (reduced viscosity) which greatly affects the fracture at the time of stretching. Furthermore, when molding into a film, the molding stability may be deteriorated, such as uneven thickness. If the molding temperature is set high in order to suppress this, the resin will be deteriorated and the film may be stretched or machined. Strength may be reduced.
  • a resin with little coloring and less foreign matter can be obtained while being a polycarbonate resin having the structure of the above formula (1).
  • a foreign matter having a maximum length of 20 ⁇ m or more contained in a film having a thickness of 30 ⁇ m ⁇ 5 ⁇ m formed from the polycarbonate resin of the present invention is preferably 1000 / m 2 or less, more preferably 500 / m 2.
  • it can be most preferably 200 pieces / m 2 or less.
  • the polycarbonate resin of the present invention is optionally provided with a heat stabilizer, a neutralizing agent, an ultraviolet absorber, a release agent, an antistatic agent, a lubricant, a lubricant, a plasticizer, or a compatibilizing agent.
  • Additives such as agents can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer or extruder.
  • melt extrusion method As a method for producing a film using the polycarbonate resin of the present invention, a melt extrusion method is preferable from the viewpoint of productivity.
  • a method of extruding a resin using a T die and sending it to a cooling roll is preferably used.
  • the melting temperature at this time is determined from the molecular weight of the polycarbonate resin, Tg, melt flow characteristics, etc., but is preferably in the range of 150 ° C. to 300 ° C., more preferably in the range of 170 ° C. to 280 ° C.
  • the retardation value of the formed film is preferably 20 nm or less, more preferably 10 nm or less.
  • the retardation value of the film is larger than this, it is not preferable because when the film is stretched to obtain a retardation film, the dispersion of the retardation value in the film surface increases.
  • the solution casting method can also be used as a method for producing the film.
  • the solvent for example, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, dioxolane, dioxane, tetrahydrofuran, toluene, methyl ethyl ketone and the like are preferable.
  • the amount of residual solvent in the film obtained by the solution casting method is preferably 2% by weight or less, more preferably 1% by weight or less. By setting it to 2% by weight or less, it is possible to prevent a decrease in the glass transition temperature of the film due to a large amount of residual solvent, which is preferable in terms of heat resistance.
  • the thickness of the unstretched film is preferably in the range of 20 ⁇ m to 400 ⁇ m, more preferably 30 ⁇ m to 300 ⁇ m, still more preferably 50 ⁇ m to 200 ⁇ m, and particularly preferably 80 ⁇ m to 150 ⁇ m.
  • the film may be appropriately determined within the above range in consideration of a desired retardation value and thickness of the retardation film.
  • the polycarbonate resin of the present invention was molded into an unstretched film having a thickness of 100 ⁇ m ⁇ 10 ⁇ m, and the elongation (tension) until breaking when a tensile test was conducted at a glass transition temperature of + 6 ° C. and a tensile speed of 625% / min. (Elongation at break) is preferably 120% or more, more preferably 150% or more, still more preferably 200% or more, and particularly preferably 220% or more.
  • the upper limit is Usually, it is 400% or less, preferably 300% or less.
  • Polycarbonate resins made from dihydroxy compounds having a fluorene structure have a rigid fluorene structure, so if the molecular structure is copolymerized with a flexible dihydroxy compound or the molecular weight is increased, the tensile elongation at break tends to increase.
  • the dihydroxy compound having a fluorene structure is excessively reduced, the desired optical performance will not be exhibited, and attempts to increase the reduced viscosity may lead to degradation of the polycarbonate resin and manufacturing problems as described above. It is not easy to satisfy all of the plurality of performances.
  • a retardation film can be obtained by stretching and orienting the unstretched film thus obtained.
  • the stretching method include known methods such as longitudinal uniaxial stretching and lateral uniaxial stretching using a tenter, and simultaneous biaxial stretching and sequential biaxial stretching in combination thereof.
  • Stretching may be performed batchwise, but it is preferable in terms of productivity to be performed continuously. Further, a continuous retardation film with less variation in retardation within the film surface can be obtained compared to a batch system.
  • the stretching temperature is preferably in the range of (Tg ⁇ 20 ° C.) to (Tg + 30 ° C.), more preferably in the range of (Tg ⁇ 10 ° C.) to (Tg + 20 ° C.) with respect to the glass transition temperature of the polycarbonate resin. It is. If the stretching temperature is excessively low, the film may be broken at the time of stretching, and if it is excessively high, the birefringence of the stretched film may be reduced and a desired phase difference may not be obtained.
  • the draw ratio is determined by the target retardation value, but is preferably 1.05 to 4 times, more preferably 1.1 to 3 times, still more preferably 1.5 to 2.5 times. It is.
  • the stretching direction may be the longitudinal direction (longitudinal stretching) of the unstretched film, or may be the perpendicular direction (lateral stretching).
  • the birefringence when the film formed by molding the polycarbonate resin in the present invention is stretched is usually 0.0010 or more, preferably 0.0014 or more, more preferably 0.0016 or more, still more preferably 0.0018 or more, Particularly preferred is 0.0020.
  • 0.0010 or more preferably 0.0014 or more, more preferably 0.0016 or more, still more preferably 0.0018 or more, Particularly preferred is 0.0020.
  • the birefringence is excessively increased, it is necessary to set the stretching ratio high and the stretching temperature low, and orientation relaxation after stretching tends to occur, and the change in phase difference may increase.
  • it is 0.0060 or less, preferably 0.0050 or less, more preferably 0.0040 or less, and particularly preferably 0.0035 or less.
  • the thickness of the stretched film according to the present invention is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably 20 ⁇ m to 150 ⁇ m, still more preferably 30 ⁇ m to 100 ⁇ m, and particularly preferably 40 ⁇ m to 80 ⁇ m.
  • the stretched film is excessively thick, the thickness when assembled as a retardation plate is increased, and a display having a desired thickness cannot be obtained. On the other hand, if it is too small, it may cause breakage during stretching or assembly.
  • the retardation of the stretched film (retardation film) according to the present invention is represented by the product of in-plane birefringence and the film thickness, and is usually 30 nm to 400 nm as a value when measured at a measurement wavelength of 590 nm.
  • the thickness is preferably 50 nm to 300 nm, particularly preferably 100 nm to 200 nm. If the retardation is excessively small, the performance as a retardation film tends to be inferior. If the retardation is excessively large, it is necessary to increase the thickness of the film, so that the retardation plate cannot be reduced in weight and size.
  • the stretched film (retardation film) according to the present invention is laminated and bonded via a known iodine-based or dye-based polarizing plate and an adhesive, thereby being used for various liquid crystal display devices or organic EL display devices. It can be used as a phase difference plate.
  • the ratio (Re450 / Re550) of the retardation (Re450) measured at a wavelength of 450 nm to the retardation (Re550) measured at a wavelength of 550 nm is preferably 0.5 or more and 1.0 or less. 0.70 or more and 1.0 or less is more preferable, 0.80 or more and 0.95 or less is further preferable, and 0.85 or more and 0.93 or less is particularly preferable.
  • phase difference characteristics can be obtained at each wavelength in the visible region.
  • a retardation film having such wavelength dependency is prepared as a quarter wavelength plate, and a circularly polarizing plate or the like can be manufactured by laminating with a polarizing plate, and polarization with less hue wavelength dependency.
  • a board and a display device can be realized.
  • film refers to a thin and flat product whose thickness is extremely small compared to the length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll.
  • sheet refers to a product that is thin by definition in JIS and whose thickness is small and flat for the length and width.
  • the boundary between the “sheet” and the “film” is not clear and it is not necessary to distinguish the two in terms of the present invention, even if the term “film” is used in this specification, the “sheet” As a concept including “
  • the transparent film according to the present invention preferably has a photoelastic coefficient of 50 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, and more preferably 40 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less.
  • a photoelastic coefficient of 50 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less, and more preferably 40 ⁇ 10 ⁇ 12 Pa ⁇ 1 or less.
  • the stretched film of the present invention is used as a retardation film for viewing angle compensation of various displays (for example, liquid crystal display devices, organic EL display devices, plasma display devices, FED field emission display devices, SED surface electric field display devices), and reflection of external light. It can be used for prevention, color compensation, or conversion of linearly polarized light into circularly polarized light. Especially, it can use suitably in the organic electroluminescence display which plays the role of a reflecting plate with a back electrode being a metal.
  • a reflective liquid crystal display device including a reflective liquid crystal panel is preferable.
  • a reflective liquid crystal display device comprising a polarizing film, a quarter-wave plate, and a liquid crystal cell including a liquid crystal layer between two substrates having transparent electrodes in this order.
  • a display device with excellent image quality can be obtained by using it for a display device, particularly a polarizing film single-reflection type liquid crystal display device.
  • a polarizing film, a retardation film, a substrate with a transparent electrode, a liquid crystal layer and a substrate with a scattering reflection electrode, a polarizing film, a scattering plate, a retardation film, and a transparent electrode A substrate, a liquid crystal layer, and a substrate with a specular reflective electrode, a polarizing film, a retardation film, a substrate with a transparent electrode, a liquid crystal layer, a substrate with a transparent electrode, and a reflective layer.
  • the quarter-wave plate can be used in a liquid crystal display device having both a transmission type and a reflection type.
  • Examples of the configuration of the liquid crystal display device include a polarizing film, a retardation film, a substrate with a transparent electrode, a liquid crystal layer, a substrate with a reflection / transmission electrode, a retardation film, a polarizing film, and a backlight system.
  • a reflective polarizing film made of cholesteric liquid crystal that reflects only the left or right circularly polarized light if it is used as an element for converting circularly polarized light into linearly polarized light, good linearly polarized light can be obtained in a wide band.
  • the polycarbonate resin according to the present invention is excellent in heat resistance and moldability, and further has little transparency and high transparency. Therefore, it can be used for other optical films, optical discs, optical prisms, pickup lenses, and the like.
  • the present invention will be described in more detail with reference to examples.
  • the present invention is not limited to the following examples unless it exceeds the gist.
  • the value of various manufacturing conditions and evaluation results in the following examples has a meaning as a preferable value of the upper limit or the lower limit in the embodiment of the present invention, and the preferable range is the above-described upper limit or lower limit value.
  • a range defined by a combination of values of the following examples or values of the examples may be used.
  • Hydroxy terminal group amount [ppm] ( ⁇ ) integral value ⁇ 17.01 / ⁇ ( ⁇ integral value / 2 ⁇ 464.51 + ( ⁇ ) /3 ⁇ 172.14+ ( ⁇ ) /82.3 ⁇ 1025.99 ⁇ ⁇ 1000000
  • Glass transition temperature (Tg) Using a differential scanning calorimeter (DSC220, manufactured by SII Nanotechnology Inc.), about 10 mg of polycarbonate resin was heated at a temperature increase rate of 20 ° C./min, and measured according to JIS-K7121 (1987). Extrapolated glass transition start temperature, which is the temperature at the intersection of the straight line that extends the low-temperature base line to the high-temperature side and the tangent line drawn at the point where the slope of the step change portion of the glass transition is maximized was determined as the glass transition temperature.
  • L * is 99.40 ⁇ 0.05, a * is 0.03 ⁇ 0.01, b * is ⁇ 0.43 ⁇ 0.01, YI is ⁇ It was confirmed to be 0.58 ⁇ 0.01.
  • the pellets were measured by packing them into a cylindrical glass container having an inner diameter of 30 mm and a height of 50 mm to a depth of about 40 mm. The operation of taking out the pellet from the glass container and then performing the measurement again was repeated twice, and the average value of the measurement values of three times in total was used. The smaller the YI value, the less yellow the resin is, and the better the color tone.
  • the sample was uniaxially stretched by a batch type biaxial stretching apparatus [manufactured by Toyo Seiki Sangyo Co., Ltd.] at a stretching speed of 720 mm / min (strain speed of 1200% / min) at a stretching ratio of 2.0 times. At this time, it extended
  • the stretching temperature is gradually lowered from the glass transition temperature of the polycarbonate resin + 20 ° C., the stretched film is made 3 times, and a stretched film is created at a temperature 2 ° C. higher than the temperature at which the breakage occurs three times. Used for measurement.
  • Example preparation> A polycarbonate resin sample (4.0 g), which was vacuum-dried at 80 ° C. for 5 hours, was heated with a hot press at a hot press temperature of 250 ° C. using a spacer having a width of 8 cm, a length of 8 cm, and a thickness of 0.5 mm. After pressurizing under the condition of 20 MPa for 1 minute, the entire spacer was taken out and cooled with a water tube cooling press at a pressure of 20 MPa for 3 minutes, and a sample having a width of 5 mm and a length of 20 mm was cut out.
  • the cut sample was fixed to a viscoelasticity measuring apparatus, and the storage elastic modulus E ′ was measured at a frequency of 96 Hz at a room temperature of 25 ° C.
  • the emitted laser light is passed through the polarizer, sample, compensator, and analyzer in this order, picked up by a photodetector (photodiode), and passed through a lock-in amplifier with respect to the amplitude and distortion of the waveform of angular frequency ⁇ or 2 ⁇ .
  • the phase difference was determined, and the strain optical coefficient 0 ′ was determined.
  • the directions of the polarizer and the analyzer were orthogonal to each other, and each was adjusted so as to form an angle of ⁇ / 4 with respect to the extending direction of the sample.
  • Example 1-1 As shown in FIG. 1 described above, a polycarbonate resin was produced under the following conditions using a continuous production apparatus having three vertical stirring reactors and one horizontal stirring reactor.
  • each reactor was previously set to an internal temperature and pressure according to the reaction conditions.
  • this raw material mixed melt is continuously supplied into the first vertical stirring reactor 6a controlled within the range of ⁇ 5% of the above-mentioned predetermined temperature and pressure through the raw material introduction pipe heated to 140 ° C. And the liquid level was kept constant, controlling the opening degree of the valve
  • a magnesium acetate aqueous solution as a catalyst was continuously supplied into the first vertical stirring reactor 6a from the catalyst supply port 1d at a ratio of 19 ⁇ mol with respect to 1 mol of all dihydroxy components.
  • the capacity of the fourth horizontal stirring reactor 6d was 250 L, the temperature of the heating medium was 240 ° C., and the reaction solution was supplied at a treatment rate of 40 kg / hr.
  • the third vertical stirring reactor 6c corresponds to the reactor immediately before the final polymerization reactor. That is, the internal temperature of the reactor immediately before the final polymerization reactor is 220 ° C.
  • the reaction liquid extracted from the fourth horizontal stirring reactor 6d was transferred to the extruder 15a by the gear pump 4c.
  • a gear pump 4c is arranged on the resin discharge side of the extruder 16d, and further downstream, a leaf disk filter (made by Nippon Pole Co., Ltd.) having an outer diameter of 112 mm, an inner diameter of 38 mm, and a filtration accuracy of 99% within the containment vessel.
  • the polymer filter 15b equipped with 10 sheets) was disposed.
  • a die for forming a strand was attached to the discharge side of the polymer filter.
  • the discharged resin was cooled with water in the form of a strand and solidified, and then pelletized with a rotary cutter. The process from stranding to pelletization was performed in a clean room. Subsequently, the pellets were sent to the product hopper 16d by pneumatic transfer.
  • the reaction solution corresponding to the outlet of the reactor immediately before the final polymerization reactor from the valve attached after the gear pump 4b is sent from the valve attached after the gear pump 4c to the final polymerization reactor outlet.
  • the polycarbonate resin pellets were sampled after the strand cutter 16b, and various analyzes were performed by the above-described analysis methods.
  • Example 1-2 The pressure in the third vertical stirring reactor 6c was 22 kPa, and the molecular weight and melt viscosity at the outlet of the third vertical stirring reactor 6c were lower than in Example 1-1.
  • Example 1-1 when the conditions of the fourth horizontal stirring reactor 6d were adjusted so that the reduced viscosity at the outlet of the fourth horizontal stirring reactor 6d was in the range of 0.39 to 0.41, the pressure was The average residence time was 0.6 kPa and 120 minutes. Items not mentioned were the same as in Example 1-1.
  • the pressure was 1.5 kPa and the average residence time was 100 minutes. Items not mentioned were the same as in Example 1-1.
  • Example 1-4 The same operation as in Example 1-1 was performed except that the stirring rotation speed of the fourth horizontal stirring reactor 6d was changed to 6 rpm. The reaction liquid was entangled with the stirring shaft and it was difficult for the reaction liquid to sag to the outlet of the reactor, and the pelletization process was stopped 12 times during the 24-hour operation. The amount of foreign matter in the obtained polycarbonate resin pellets was remarkably increased. The monohydroxy compound content was lower than in Example 1-1, and the color tone was good.
  • Example 1-5 The same operation as in Example 1-1 was performed, except that the stirring rotation speed of the fourth horizontal stirring reactor 6d was changed to 0.5 rpm. Although the operation could be continued stably, compared with Example 1-1, the stirring efficiency was lowered, and therefore the phenol content in the obtained polycarbonate resin was increased. The amount of foreign matter has become very small. Moreover, the color tone of the pellet YI was also favorable.
  • the raw materials were continuously supplied to the reactor so that the throughput of the final polymerization reactor was 50 kg / hr.
  • the reaction conditions were adjusted so that the reduced viscosity at the outlet of the fourth horizontal stirring reactor 6d was in the range of 0.41 to 0.44, and the conditions of each reactor were also adjusted appropriately according to the progress of the reaction. Unless otherwise specified, the same procedure as in Example 1-1 was performed. A polycarbonate resin having a good color tone and a very small content of monohydroxy compound in the polycarbonate resin and foreign matter was obtained.
  • the raw materials were continuously supplied to the reactor so that the throughput of the final polymerization reactor was 50 kg / hr.
  • the reaction conditions were adjusted so that the reduced viscosity at the outlet of the fourth horizontal stirring reactor 6d was in the range of 0.57 to 0.60, and the conditions of each reactor were also adjusted appropriately according to the progress of the reaction. Unless otherwise specified, the same procedure as in Example 1-1 was performed. A polycarbonate resin having a good color tone and a very small content of monohydroxy compound in the polycarbonate resin and foreign matter was obtained.
  • Example 1-1 The internal temperature of the third vertical stirring reactor 6c was raised to 230 ° C.
  • the pressure was 1.1 kPa and the average residence time was 100 minutes. Items not mentioned were the same as in Example 1-1.
  • the obtained polycarbonate resin deteriorated in color tone and the monohydroxy compound content also increased.
  • Example 1-6 the internal temperature of the third vertical stirring reactor 6c was raised to 230 ° C.
  • the pressure was 0.9 kPa, and the average residence time was 100 minutes. Items not mentioned were the same as in Example 1-6.
  • the obtained polycarbonate resin deteriorated in color tone and the monohydroxy compound content also increased.
  • Example 1-7 the internal temperature of the third vertical stirring reactor 6c was raised to 230 ° C.
  • the pressure was 0.8 kPa and the average residence time was 100 minutes. Items not mentioned were the same as in Example 1-7.
  • the obtained polycarbonate resin deteriorated in color tone and the monohydroxy compound content also increased.
  • Table 2 shows the results of Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-3.
  • Example 2-1 As shown in FIG. 1 described above, a polycarbonate resin was produced under the following conditions using a continuous production apparatus having three vertical stirring reactors and one horizontal stirring reactor.
  • this raw material mixed melt is continuously supplied into the first vertical stirring reactor 6a controlled within the range of ⁇ 5% of the above-mentioned predetermined temperature and pressure through the raw material introduction pipe heated to 140 ° C. And the liquid level was kept constant, controlling the opening degree of the valve
  • a magnesium acetate aqueous solution as a catalyst was continuously supplied into the first vertical stirring reactor 6a from the catalyst supply port 1d at a ratio of 10 ⁇ mol with respect to 1 mol of all dihydroxy components.
  • the capacity of the fourth horizontal stirring reactor 6d was 250 L, the temperature of the heating medium was 242 ° C., the stirring rotation speed was 2 rpm, and the reaction solution was supplied at a throughput of 60 kg / hr.
  • the reaction liquid extracted from the fourth horizontal stirring reactor 6d was transferred to the extruder 15a by the gear pump 4c.
  • a gear pump 4c is arranged on the resin discharge side of the extruder 16d, and further downstream, a leaf disk filter (made by Nippon Pole Co., Ltd.) having an outer diameter of 112 mm, an inner diameter of 38 mm, and a filtration accuracy of 99% within the containment vessel.
  • the polymer filter 15b equipped with 10 sheets) was disposed.
  • a die for forming a strand was attached to the discharge side of the polymer filter.
  • the discharged resin was cooled with water in the form of a strand and solidified, and then pelletized with a rotary cutter. The process from stranding to pelletization was performed in a clean room. Subsequently, the pellets were sent to the product hopper 16d by pneumatic transfer.
  • Example 2-2 A polycarbonate resin having a higher molecular weight than that of Example 2-1 was produced by lowering the pressure in the fourth horizontal stirring reactor 6d.
  • the fluidity of the molten resin has decreased, and it has stopped dripping down to the outlet at the bottom of the tank, so that the molten resin can be stably extracted by lowering the rotation speed of stirring to 1 rpm.
  • Became When a film was prepared from the obtained polycarbonate resin and stretched, stretching was possible at a stretching temperature lower than that of Example 2-1, and higher in-plane birefringence was obtained.
  • the stretched film had a wavelength difference (Re450 / Re550) of retardation of 0.892, which was stronger than that of Example 2-1. It is possible to obtain desired wavelength dispersion by appropriately adjusting the copolymer composition.
  • Example 2-5 BHEPF, ISB, and PEG # 1000 were used as dihydroxy compounds.
  • BHEPF / ISB / PEG # 1000 / DPC 0.357 / 0.632 / 0.011 / 1.010 Went to.
  • the glass transition temperature was improved as compared with the polycarbonate resins of Example 2-1 and Example 2-6, the glass transition temperature was easily broken during stretching, and the film could be stretched only at a high temperature. The in-plane retardation of the stretched film was 0.0009, which was a low value.
  • Example 2-8 BHEPF and ISB were used as dihydroxy compounds.
  • the glass transition temperature was improved as compared with the polycarbonate resins of Example 2-1 and Example 2-6, the glass transition temperature was easily broken during stretching, and the film could be stretched only at a high temperature.
  • the in-plane retardation of the stretched film was 0.0008, which was a low value.
  • the reduced viscosity of the obtained polycarbonate resin was 0.356 dL / g, and the molecular weight was lower than that of Example 2-1.
  • the various analysis was implemented for the obtained polycarbonate resin by the above-mentioned analysis method. Compared to Examples 2-1 and 2-2, the tensile elongation at break was low, and stretching could not be performed unless the stretching temperature was high. The in-plane birefringence of the obtained stretched film was 0.0012, which was a low value.
  • Comparative Example 2-2 Polymerization was performed using a batch polymerization apparatus in the same manner as in Comparative Example 2-1. The same operation as in Comparative Example 2-1 was performed except that the temperature of the second reactor was changed to 255 ° C. The reduced viscosity, tensile elongation at break, and in-plane birefringence of the stretched film of the obtained polycarbonate resin were almost the same as those of Example 2-1, but the color tone of the polycarbonate resin deteriorated because the reaction temperature was increased.
  • the polycarbonate resin of the present invention allows the reaction to proceed to a high molecular weight by using a continuous polymerization method, and the tensile breaking elongation is higher than that of the polycarbonate resin obtained by batch polymerization. The degree improved. Therefore, it was possible to perform stretching at a lower temperature, and high in-plane birefringence can be obtained.

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Abstract

La présente invention concerne un procédé pour la préparation d'une résine de polycarbonate par alimentation continue d'un diester d'acide carbonique et d'un composé dihydroxy contenant un composé dihydroxy présentant une structure fluorène, en présence d'un catalyseur de polymérisation, dans des récipients de réaction et réalisation d'une polycondensation. Ce procédé pour la préparation d'une résine de polycarbonate est caractérisé en ce que : les récipients de réaction sont constitués d'au moins une pluralité de récipients raccordés en série ; la température dans l'avant-dernier récipient de réaction de polymérisation est de 200°C à 225°C ; et la viscosité de masse fondue de la solution de réaction à la sortie de l'avant-dernier récipient de réaction de polymérisation est de 20 Pa.s à 1000 Pa.s.
PCT/JP2012/058748 2011-03-31 2012-03-30 Procédé pour la préparation d'une résine de polycarbonate, pellets de résine de polycarbonate et film étiré WO2012133856A1 (fr)

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EP2708568B1 (fr) * 2011-05-09 2018-08-01 Mitsubishi Chemical Corporation Résine polycarbonate et film transparent comprenant celle-ci
JP5445652B1 (ja) * 2012-10-03 2014-03-19 三菱化学株式会社 ポリカーボネート樹脂の製造方法
JP6146151B2 (ja) * 2013-06-14 2017-06-14 三菱化学株式会社 ポリカーボネート樹脂の製造方法
JP6861569B2 (ja) * 2016-04-28 2021-04-21 三井化学株式会社 ポリカーボネート樹脂、その製造方法および光学成形体
TW202426537A (zh) 2017-12-28 2024-07-01 日商帝人股份有限公司 聚（酯）碳酸酯
JP7436927B2 (ja) 2020-10-27 2024-02-22 新日本理化株式会社 環式ジオール化合物、該化合物の製造方法及び該化合物の用途
WO2022163684A1 (fr) 2021-01-27 2022-08-04 新日本理化株式会社 Composé diol cyclique, son procédé de production et son utilisation

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JP2003167121A (ja) * 2001-11-30 2003-06-13 Fuji Photo Film Co Ltd ポリカーボネート系位相差フィルムおよびその製造方法
WO2006041190A1 (fr) * 2004-10-14 2006-04-20 Teijin Limited Polycarbonate de faible constante photoélastique et film fabriqué à partir dudit polycarbonate
WO2009075305A1 (fr) * 2007-12-13 2009-06-18 Mitsubishi Chemical Corporation Procédé de production de polycarbonate
JP2012031369A (ja) * 2009-11-17 2012-02-16 Mitsubishi Chemicals Corp ポリカーボネート樹脂
JP2012031370A (ja) * 2009-11-19 2012-02-16 Mitsubishi Chemicals Corp ポリカーボネート樹脂フィルム並びに透明フィルム及びその製造方法

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JP5532531B2 (ja) * 2006-06-19 2014-06-25 三菱化学株式会社 ポリカーボネート共重合体及びその製造方法
JP5875747B2 (ja) * 2008-11-28 2016-03-02 三菱化学株式会社 ポリカーボネート原料用ジヒドロキシ化合物の保存方法

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JP2003167121A (ja) * 2001-11-30 2003-06-13 Fuji Photo Film Co Ltd ポリカーボネート系位相差フィルムおよびその製造方法
WO2006041190A1 (fr) * 2004-10-14 2006-04-20 Teijin Limited Polycarbonate de faible constante photoélastique et film fabriqué à partir dudit polycarbonate
WO2009075305A1 (fr) * 2007-12-13 2009-06-18 Mitsubishi Chemical Corporation Procédé de production de polycarbonate
JP2012031369A (ja) * 2009-11-17 2012-02-16 Mitsubishi Chemicals Corp ポリカーボネート樹脂
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