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WO2011071164A1 - Composition de résine polycarbonate et article moulé - Google Patents

Composition de résine polycarbonate et article moulé Download PDF

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Publication number
WO2011071164A1
WO2011071164A1 PCT/JP2010/072284 JP2010072284W WO2011071164A1 WO 2011071164 A1 WO2011071164 A1 WO 2011071164A1 JP 2010072284 W JP2010072284 W JP 2010072284W WO 2011071164 A1 WO2011071164 A1 WO 2011071164A1
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WO
WIPO (PCT)
Prior art keywords
polycarbonate resin
weight
resin composition
less
dihydroxy compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2010/072284
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English (en)
Japanese (ja)
Inventor
一雄 佐々木
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009280865A external-priority patent/JP5716274B2/ja
Priority claimed from JP2009288107A external-priority patent/JP2011127037A/ja
Priority claimed from JP2010185054A external-priority patent/JP2012041467A/ja
Application filed by Mitsubishi Chemical Corp filed Critical Mitsubishi Chemical Corp
Priority to EP10836083.5A priority Critical patent/EP2511341A4/fr
Priority to CN2010800559078A priority patent/CN102712805A/zh
Publication of WO2011071164A1 publication Critical patent/WO2011071164A1/fr
Priority to US13/477,271 priority patent/US20120232198A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G64/02—Aliphatic polycarbonates
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and a molded product thereof.
  • Polycarbonate resins are generally composed of bisphenols as monomer components, taking advantage of transparency, heat resistance, mechanical strength, etc., and electrical / electronic parts, automotive parts, medical parts, building materials, films, sheets, bottles It is widely used as so-called engineering plastics in the fields of optical recording media and lenses.
  • conventional polycarbonate resins are limited in use outdoors or in the vicinity of lighting devices, because their hue, transparency, and mechanical strength deteriorate when used in places exposed to ultraviolet rays or visible light for a long time. .
  • Non-Patent Document 1 a method of adding a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, or a benzoxazine ultraviolet absorber to a polycarbonate resin is widely known (for example, Non-Patent Document 1).
  • HALS hindered amine
  • a cyclic dihydroxy compound monomer unit having an ether bond in the molecule such as a compound, an alicyclic dihydroxy compound, or isosorbide
  • light resistance is improved in principle.
  • polycarbonate resins using isosorbide as a monomer obtained from biomass resources are excellent in heat resistance and mechanical strength, so that many studies have been made in recent years (for example, Patent Documents 1 to 7). .
  • polycarbonate resin compositions that have an ether bond in the molecule, such as isosorbide, isomannide, isoitide, etc. that do not have a benzene ring structure in the molecular skeleton, benzotriazole, benzophenone, It is widely known to add a cyanoacrylate system (Patent Document 8).
  • Non-Patent Document 1 when an ultraviolet absorber as described in Non-Patent Document 1 is added, although the hue after ultraviolet irradiation is improved, the hue, heat resistance, and transparency of the resin are deteriorated in the first place. There were problems such as volatilization during molding and contamination of the mold.
  • a polycarbonate resin is obtained.
  • a polycarbonate resin obtained using a monomer having no phenolic hydroxyl group as described above is inferior in thermal stability to a polycarbonate resin obtained using a monomer having a phenolic hydroxyl group such as bisphenol A.
  • coloring occurs during polymerization or molding that is exposed to high temperatures, and as a result, ultraviolet light and visible light are absorbed, resulting in deterioration of light resistance.
  • the object of the present invention is to provide a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and a molded product thereof, which solves the above-mentioned conventional problems. There is to do.
  • the present inventor has obtained structural units and carbon numbers derived from the dihydroxy compound (a) having a site represented by the following general formula (1) in a part of the structure.
  • the present inventors have found that the resin composition has not only excellent light resistance but also excellent hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength, and has reached the present invention.
  • R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
  • Y represents a single bond or a divalent group.
  • the gist of the present invention resides in the following [1] to [8].
  • [1] Derived from a structural unit derived from a dihydroxy compound (a) having a site represented by the following general formula (1) as part of the structure and a dihydroxy compound (b) of an alicyclic hydrocarbon having 11 or less carbon atoms
  • R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
  • Y represents a single bond or a divalent group.
  • Polycarbonate resin composition [3] The polycarbonate resin composition according to [1] or [2], wherein the dihydroxy compound (a) is a dihydroxy compound represented by the following general formula (3).
  • a polycarbonate resin composition excellent in weather resistance, hue, transparency, heat resistance, thermal stability, moldability, and mechanical strength and a molded product thereof can be provided.
  • the polycarbonate resin (A) used in the present invention comprises a dihydroxy compound (a) having a part represented by the following general formula (1) in a part of the structure and a dihydroxy compound (b) having an alicyclic hydrocarbon having 11 or less carbon atoms. ) And a carbonic acid diester as raw materials and obtained by polycondensation by a transesterification reaction. That is, the polycarbonate resin (A) used in the present invention is composed of a structural unit derived from the dihydroxy compound (a) having a portion represented by the following general formula (1) in a part of the structure and an alicyclic group having 11 or less carbon atoms. And a structural unit derived from a hydrocarbon dihydroxy compound (b).
  • the dihydroxy compound used in the present invention includes a dihydroxy compound (a) having a portion represented by the general formula (1) in a part of the structure, and an alicyclic hydrocarbon dihydroxy compound (b) having 11 or less carbon atoms, If it contains, it will not specifically limit.
  • dihydroxy compound (a) having a site represented by the general formula (1) in a part of the structure include oxyalkylene glycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol, -Bis (4- (2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -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- Butylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylsulfate Nyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-phenylpheny
  • anhydrosugar alcohol represented by the dihydroxy compound represented by the following formula (3) and a compound having a cyclic ether structure represented by the following formula (4) are preferable.
  • Anhydrosugar alcohols typified by dihydroxy compounds represented by formula (4) are preferred.
  • dihydroxy compound represented by the general formula (3) examples include isosorbide, isomannide, and isoidet, which have a stereoisomeric relationship, and these may be used alone or in combination of two or more. It may be used.
  • dihydroxy compounds it is preferable to use a dihydroxy compound having no aromatic ring structure from the viewpoint of the light resistance of the polycarbonate resin (A).
  • Isosorbide obtained by dehydrating condensation of sorbitol produced from starch is most preferable from the viewpoints of availability and production, light resistance, optical properties, moldability, heat resistance, and carbon neutral.
  • the alicyclic hydrocarbon dihydroxy compound (b) having 11 or less carbon atoms is a compound having a cyclic structure hydrocarbon skeleton and two hydroxy groups, and the hydroxy group may be directly bonded to the cyclic structure. , And may be bonded to the cyclic structure via a substituent.
  • the cyclic structure may be monocyclic or polycyclic.
  • hexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-methyl-1,4-cyclohexanediol, 4-cyclohexene-1,2- Cyclohexene diols such as diol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, cyclohexanedimethanol such as 1,4-cyclohexanedimethanol, 4-cyclohexene-1,2-diol
  • cyclohexene dimethanol, 2,3-norbornane dimethanol, norbornane dimethanol such as 2,5-norbornane dimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 1,3-adamantanediol, 2, 2-Adamantane All, and the like.
  • a dihydroxy compound containing a dihydroxy compound (a) having a site represented by the general formula (1) and a dihydroxy compound (b) of an alicyclic hydrocarbon having 11 or less carbon atoms in a part of the structure It is also possible to obtain effects such as improvement in flexibility of polycarbonate resin (A), improvement in heat resistance, improvement in moldability, and the number of carbon atoms of dihydroxy compound (b) of alicyclic hydrocarbon is a predetermined value. When it is below, it becomes possible to obtain a polycarbonate resin composition excellent in weather resistance and hue.
  • the carbon number of the alicyclic hydrocarbon dihydroxy compound (b) is usually 11 or less, preferably 10 or less, more preferably 8 or less.
  • the dihydroxy compound used in the present invention may contain a stabilizer such as a reducing agent, antioxidant, oxygen scavenger, light stabilizer, antacid, pH stabilizer, heat stabilizer, etc. Since the dihydroxy compound used in the invention is easily altered, it is preferable to include a basic stabilizer.
  • Basic stabilizers include group 1 or group 2 metal hydroxides, carbonates, phosphates, phosphites, hypophosphites in the long-period periodic table (Nomenclature of Organic Chemistry IUPAC Recommendations 2005).
  • the basic stabilizer when used as a raw material for producing polycarbonate resin, the basic stabilizer itself becomes a polymerization catalyst, and it becomes difficult to control the polymerization rate and quality. In order to deteriorate the initial hue and consequently deteriorate the light resistance of the molded product, it is preferable to remove the basic stabilizer by ion exchange resin or distillation before using it as a raw material for producing the polycarbonate resin.
  • the dihydroxy compound used in the present invention has a cyclic ether structure such as isosorbide, it is easily oxidized by oxygen. Therefore, during storage and production, in order to prevent decomposition by oxygen, water should not be mixed, It is important to use an oxygen scavenger or handle under a nitrogen atmosphere.
  • isosorbide is oxidized, decomposition products such as formic acid may be generated.
  • the resulting polycarbonate resin may be colored, and not only the physical properties may be significantly degraded, but also the polymerization reaction may be affected. In some cases, a high molecular weight polymer cannot be obtained.
  • distillation purification In order to obtain the dihydroxy compound used in the present invention which does not contain the above oxidative decomposition product, and in order to remove the above basic stabilizer, it is preferable to perform distillation purification.
  • the distillation in this case may be simple distillation or continuous distillation, and is not particularly limited.
  • distillation conditions it is preferable to carry out distillation under reduced pressure in an inert gas atmosphere such as argon or nitrogen.
  • inert gas atmosphere such as argon or nitrogen.
  • it is 250 ° C. or lower, preferably 200 ° C. or lower, particularly 180 °. It is preferable to carry out under the conditions of °C or less.
  • the dihydroxy compound used in the present invention is adjusted to a formic acid content in the dihydroxy compound used in the present invention of 20 ppm by weight or less, preferably 10 ppm by weight or less, particularly preferably 5 ppm by weight or less.
  • a dihydroxy compound containing is used as a raw material for producing a polycarbonate resin, it is possible to produce a polycarbonate resin (A) excellent in hue and thermal stability without impairing polymerization reactivity.
  • the formic acid content is measured by ion chromatography.
  • the polycarbonate resin (A) used in the present invention can be obtained by polycondensation by a transesterification reaction using the above-mentioned dihydroxy compound containing the dihydroxy compound used in the present invention and a carbonic acid diester as raw materials.
  • a carbonic acid diester used what is normally represented by following General formula (6) is mentioned. These carbonic acid diesters may be used alone or in combination of two or more.
  • a 1 and A 2 are each independently a substituted or unsubstituted aliphatic group having 1 to 18 carbon atoms, or a substituted or unsubstituted aromatic group.
  • Examples of the carbonic acid diester represented by the general formula (6) include substituted diphenyl carbonates such as diphenyl carbonate and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate. Diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly preferable.
  • 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 (A) used in the present invention produces a polycarbonate resin by transesterifying the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester represented by the general formula (6) as described above. More specifically, it can be obtained by transesterification and removing by-product monohydroxy compounds and the like out of the system. In this case, polycondensation is usually carried out by transesterification in the presence of a transesterification catalyst.
  • the transesterification catalyst (hereinafter, sometimes simply referred to as “catalyst” or “polymerization catalyst”) that can be used in the production of the polycarbonate resin (A) used in the present invention is, in particular, a light transmittance at a wavelength of 350 nm or a yellow index. Can affect the value.
  • the catalyst used as long as the light resistance, transparency, hue, heat resistance, thermal stability, and mechanical strength of the manufactured polycarbonate resin (A) can satisfy the light resistance,
  • a metal compound, a basic boron compound, a basic phosphorus compound, or a basic ammonium of Group 1 or 2 (hereinafter also simply referred to as “Group 1” or “Group 2”) in the long-period periodic table
  • Examples thereof include basic compounds such as compounds and amine compounds.
  • at least one of a Group 1 metal compound and a Group 2 metal compound is used.
  • a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound in combination with the Group 1 metal compound and / or the Group 2 metal compound. It is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.
  • the group 1 metal compound and / or the group 2 metal compound are usually used in the form of a hydroxide or a salt such as a carbonate, a carboxylate, or a phenol salt. From the viewpoint of easiness, a hydroxide, carbonate, and acetate are preferable, and acetate is preferable from the viewpoint of hue and polymerization activity.
  • Group 1 metal compound examples 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, lithium carbonate, Cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride , Sodium borohydride, potassium borohydride, lithium phenide boron, cesium phenide boron, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, 2 sodium hydrogen phosphate , 2 potassium hydrogen phosphate, 2 lithium hydrogen phosphate, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium pheny
  • 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, magnesium carbonate, Examples include strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc. From the viewpoint of the hue of the polycarbonate resin obtained, a magnesium compound and / or a calcium compound is more preferable, and a calcium compound is most preferable.
  • Examples of basic boron compounds include tetramethylboron, tetraethylboron, tetrapropylboron, tetrabutylboron, trimethylethylboron, trimethylbenzylboron, trimethylphenylboron, triethylmethylboron, triethylbenzylboron, triethylphenylboron, tributylbenzyl.
  • Examples include sodium, potassium, lithium, calcium, barium, magnesium, or strontium salts such as boron, tributylphenylboron, tetraphenylboron, benzyltriphenylboron, methyltriphenylboron, butyltriphenylboron, etc. It is done.
  • Examples of the basic phosphorus compound include triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt, and the like.
  • 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 Sid, butyl triphenyl ammonium hydroxide, and the like.
  • amine compounds include 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2 -Dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline and the like.
  • the amount of the polymerization catalyst used is 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. Among them, lithium and two groups in the long-period periodic table are used.
  • the metal amount is preferably 0.1 ⁇ mol or more per 1 mol of the total dihydroxy compound. More preferably 0.5 ⁇ mol or more, particularly preferably 0.7 ⁇ mol or more.
  • the upper limit is preferably 20 ⁇ mol, more preferably 10 ⁇ mol, particularly preferably 3 ⁇ mol, most preferably 1.5 ⁇ mol, and most preferably 1.0 ⁇ mol.
  • the polycarbonate resin (A) used in the present invention is produced using a substituted diphenyl carbonate such as diphenyl carbonate or ditolyl carbonate as the carbonic acid diester represented by the general formula (6), phenol and substituted phenol are used.
  • By-product and remaining in the polycarbonate resin (A) are inevitable, but not only phenol and substituted phenol also have an aromatic ring, which absorbs ultraviolet rays and may cause deterioration of light resistance, May cause odor during molding.
  • the polycarbonate resin (A) contains an aromatic monohydroxy compound having an aromatic ring such as by-product phenol of 1000 ppm by weight or more after a normal batch reaction.
  • the content of this aromatic monohydroxy compound is preferably 700 ppm by weight or less, more preferably using a horizontal reactor excellent in devolatilization performance or an extruder with a vacuum vent. It is preferably 500 ppm by weight or less, particularly 300 ppm by weight or less. However, it is difficult to remove completely industrially, and the lower limit of the content of the aromatic monohydroxy compound is usually 1 ppm by weight or more.
  • aromatic monohydroxy compounds may naturally have a substituent depending on the raw material used, and may have, for example, an alkyl group having 5 or less carbon atoms.
  • Group 1 metals especially sodium, potassium, and cesium, especially lithium, sodium, potassium, and cesium, may have an adverse effect on the hue when contained in the polycarbonate resin (A) in large quantities.
  • the total amount of these in the polycarbonate resin (A) is usually 1 ppm by weight or less, preferably 0.8 ppm by weight or less as the amount of metal, because it may be mixed not only from the catalyst to be used, but also from raw materials and reactors. More preferably, it is 0.7 ppm by weight or less.
  • the amount of metal in the polycarbonate resin (A) should be measured using a method such as atomic emission, atomic absorption, Inductive Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.
  • a method such as atomic emission, atomic absorption, Inductive Coupled Plasma (ICP) after recovering the metal in the polycarbonate resin by a method such as wet ashing. I can do it.
  • the polycarbonate resin (A) used in the present invention is obtained by polycondensation of the dihydroxy compound containing the dihydroxy compound used in the present invention and the carbonic acid diester of the general formula (6) by a transesterification reaction.
  • the compound and the carbonic acid diester are preferably mixed uniformly before the transesterification reaction.
  • the mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. Among these, 100 ° C. or higher and 120 ° C. or lower is preferable.
  • the lower limit of the mixing temperature is in the above range, the dissolution rate and solubility are good, and problems such as solidification are unlikely to occur.
  • the upper limit of the mixing temperature is within the above range, the dihydroxy compound is unlikely to be thermally deteriorated, resulting in a good hue of the polycarbonate resin and does not adversely affect light resistance.
  • the operation of mixing the dihydroxy compound containing the dihydroxy compound used in the present invention, which is the raw material of the polycarbonate resin (A) used in the present invention, and the carbonic acid diester represented by the general formula (6) is an oxygen concentration of 10 vol% or less, Is preferably carried out in an atmosphere of 0.0001 vol% to 10 vol%, especially 0.0001 vol% to 5 vol%, particularly 0.0001 vol% to 1 vol%, from the viewpoint of preventing hue deterioration.
  • the carbonic acid diester represented by the general formula (6) is 0.90 to less than the dihydroxy compound including the dihydroxy compound used in the present invention used in the reaction.
  • the molar ratio is preferably 1.20, and more preferably 0.95 to 1.10. If this molar ratio is at least the above lower limit, the terminal hydroxyl group of the produced polycarbonate resin does not increase, so that the thermal stability of the polymer can be obtained, coloring during molding, the rate of transesterification reaction can be reduced, It is difficult to cause a problem that a high molecular weight product cannot be obtained.
  • the molar ratio is not more than the above upper limit, there is no fear that the rate of transesterification will be reduced or it will be difficult to produce a polycarbonate resin (A) having a desired molecular weight.
  • the decrease in the transesterification reaction rate may increase the heat history during the polymerization reaction, and may deteriorate the hue and light resistance of the resulting polycarbonate resin.
  • the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) is increased. They increase, and these may absorb the ultraviolet rays and deteriorate the light resistance of the polycarbonate resin, which is not preferable.
  • the concentration of the carbonic acid diester remaining in the polycarbonate resin (A) used in the present invention is preferably 200 ppm by weight or less, more preferably 100 ppm by weight or less, particularly preferably 60 ppm by weight or less, and particularly preferably 30 ppm by weight or less. .
  • the polycarbonate resin (A) may contain unreacted carbonic acid diester, and the lower limit of the concentration is usually 1 ppm by weight or more.
  • the method of polycondensing a dihydroxy compound and a carbonic acid diester is usually carried out in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst.
  • the type of reaction may be any of batch type, continuous type, or a combination of batch type and continuous type.
  • the temperature of the refrigerant introduced into the reflux cooler can be appropriately selected according to the monomer used.
  • the temperature of the refrigerant introduced into the reflux cooler is 45 ° C. to 180 ° C. at the inlet of the reflux cooler.
  • it is 80 ° C to 150 ° C, and particularly preferably 100 ° C to 130 ° C. If the temperature of the refrigerant introduced into the reflux condenser is too high, the reflux amount is reduced and the effect is reduced. If it is too low, the distillation efficiency of the monohydroxy compound to be originally distilled tends to be reduced.
  • the refrigerant hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.
  • the polycarbonate resin (A) used in the present invention is preferably produced by polymerizing in a plurality of stages using a plurality of reactors using a catalyst.
  • the reason for carrying out the polymerization in a plurality of reactors is a polymerization reaction.
  • the initial stage since there are many monomers contained in the reaction solution, it is important to suppress the volatilization of the monomers while maintaining the necessary polymerization rate.
  • the equilibrium is shifted to the polymerization side. Therefore, it is important to sufficiently distill off the monohydroxy compound produced as a by-product.
  • the number of reactors used in the method of the present invention may be at least two or more. However, from the viewpoint of production efficiency, three or more, preferably 3 to 5, and particularly preferably 4 reactors are used. One. In the present invention, if there are two or more reactors, a plurality of reaction stages having different conditions may be provided in the reactor, or the temperature and pressure may be continuously changed.
  • the polymerization catalyst can be added to the raw material preparation tank, the raw material storage tank, or can be added directly to the polymerization tank. From the viewpoint of supply stability and polymerization control, the polymerization catalyst is supplied to the polymerization tank.
  • a catalyst supply line is installed in the middle of the raw material line before being fed, and preferably supplied as an aqueous solution. If the temperature of the polymerization reaction is too low, the productivity is lowered and the thermal history of the product is increased. If it is too high, not only the monomer is volatilized, but also the decomposition and coloring of the polycarbonate resin may be promoted.
  • the reaction in the first stage is carried out at 140 ° C. to 270 ° C., preferably 180 ° C. to 240 ° C., more preferably 200 ° C. to 230 ° C., and 110 kPa—
  • the generated monohydroxy compound is removed from the reaction system at a pressure of 1 kPa, preferably 70 kPa to 5 kPa, more preferably 30 kPa to 10 kPa (absolute pressure) for 0.1 hour to 10 hours, preferably 0.5 hour to 3 hours. Carried out while distilling.
  • the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system.
  • the maximum internal temperature in all reaction stages is less than 250 ° C., particularly from 225 ° C. It is preferable that it is 245 degreeC.
  • it is necessary to use a horizontal reactor with excellent plug flow and interface renewability at the final stage of polymerization. preferable.
  • the monohydroxy compound produced as a by-product is preferably reused as a raw material for diphenyl carbonate, bisphenol A, etc. after purification as necessary from the viewpoint of effective utilization of resources.
  • the polycarbonate resin (A) used in the present invention is usually cooled and solidified after polycondensation as described above, and pelletized with a rotary cutter or the like.
  • the method of pelletization is not limited, but it is extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of a strand, and pelletized, or from the final polymerization reactor in a molten state, uniaxial or biaxial extrusion.
  • the resin is supplied to the machine, melt-extruded, cooled and solidified into pellets, or extracted from the final polymerization reactor in a molten state, cooled and solidified in the form of strands, once pelletized, and then uniaxially again
  • a method may be mentioned in which resin is supplied to a biaxial extruder, melt-extruded, cooled and solidified, and pelletized.
  • the residual monomer under reduced pressure devolatilization and generally known heat stabilizers, neutralizers, UV absorbers, mold release agents, colorants, antistatic agents, lubricants, lubricants, A plasticizer, a compatibilizer, a flame retardant, etc. can be added and kneaded.
  • the melt kneading temperature in the extruder depends on the glass transition temperature and molecular weight of the polycarbonate resin (A), but is usually 150 ° C. to 300 ° C., preferably 200 ° C. to 270 ° C., more preferably 230 ° C. to 260 ° C. is there.
  • melt kneading temperature is lower than 150 ° C.
  • melt viscosity of the polycarbonate resin (A) is high, the load on the extruder is increased, and the productivity is lowered.
  • temperature is higher than 300 ° C., the thermal deterioration of the polycarbonate becomes severe, resulting in a decrease in mechanical strength due to a decrease in molecular weight, coloring, and gas generation.
  • the filter installation position is preferably on the downstream side of the extruder, and the foreign matter removal size (opening) of the filter is preferably 100 ⁇ m or less as the filtration accuracy for 99% removal. In particular, in the case of disagreeing with the entry of minute foreign matters for film use etc., it is preferably 40 ⁇ m or less, more preferably 10 ⁇ m or less.
  • Extrusion of the polycarbonate resin (A) used in the present invention is preferably a clean room having a higher degree of cleanliness than Class 7 as defined in JIS B 9920 (2002), more preferably a clean room in order to prevent foreign matter from being mixed after extrusion. It is desirable to implement in. Moreover, when cooling the extruded polycarbonate resin into chips, it is preferable to use a cooling method such as air cooling or water cooling. As the air used for air cooling, it is desirable to use air from which foreign substances in the air have been removed in advance with a hepa filter or the like to prevent reattachment of foreign substances in the air.
  • the opening of the filter to be used is preferably 10 ⁇ m to 0.45 ⁇ m as 99% removal filtration accuracy.
  • the molecular weight of the polycarbonate resin (A) used in the present invention thus obtained can be represented by a reduced viscosity, and the reduced viscosity is usually 0.30 dL / g or more, preferably 0.35 dL / g or more.
  • the upper limit of the reduced viscosity is more preferably 1.20 dL / g or less and 1.00 dL / g or less, and still more preferably 0.80 dL / g or less.
  • the reduced viscosity of the polycarbonate resin (A) is not less than the above lower limit, the mechanical strength of the molded product can be sufficiently obtained, and if it is not more than the above upper limit, the fluidity at the time of molding does not decrease, and productivity and molding Improves.
  • the reduced viscosity is measured using a Ubbelohde viscometer at a temperature of 20.0 ° C. ⁇ 0.1 ° C., using methylene chloride as a solvent, precisely preparing a polycarbonate concentration of 0.6 g / dL.
  • the lower limit of the concentration of the terminal group represented by the following general formula (7) in the polycarbonate resin (A) used in the present invention is usually 20 ⁇ eq / g or more, preferably 40 ⁇ eq / g or more, particularly preferably 50 ⁇ eq / g.
  • the upper limit is usually 160 ⁇ eq / g or less, preferably 140 ⁇ eq / g or less, particularly preferably 100 ⁇ eq / g or less.
  • the concentration of the end group represented by the following general formula (7) is too high, even if the hue at the time of polymerization or molding is good, the hue after exposure to ultraviolet rays may be deteriorated. Thermal stability may be reduced.
  • the concentration of the terminal group represented by the following general formula (7) In order to control the concentration of the terminal group represented by the following general formula (7), the molar ratio of the dihydroxy compound containing the dihydroxy compound used in the present invention as a raw material and the carbonic acid diester represented by the general formula (6) is set. In addition to controlling, a method for controlling the kind and amount of the catalyst at the time of the transesterification reaction, the polymerization pressure and the polymerization temperature can be used.
  • C the number of moles of H bonded to the aromatic ring in the polycarbonate resin (A) used in the present invention is (C) and the number of moles of H bonded to other than the aromatic ring is (D), it is bonded to the aromatic ring.
  • the ratio of the number of moles of H to the number of moles of total H is expressed as C / (C + D).
  • C / (C + D) is preferably 0.1 or less, and more preferably 0.05 or less. Particularly preferably, it is 0.02 or less, preferably 0.01 or less.
  • C / (C + D) can be quantified by 1 H-NMR.
  • the polycarbonate resin used in the present invention can be formed into a molded product by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method.
  • the polycarbonate resin (A) used in the present invention is, as necessary, a heat stabilizer, a neutralizer, an ultraviolet absorber, a release agent, a colorant, an antistatic agent, and a lubricant before performing various moldings.
  • Additives such as lubricants, plasticizers, compatibilizers, and flame retardants can also be mixed with a tumbler, super mixer, floater, V-type blender, nauter mixer, Banbury mixer, extruder or the like.
  • the glass transition temperature of the polycarbonate resin (A) is preferably 75 ° C. or higher and 105 ° C. or lower, more preferably 80 ° C. or higher and 105 ° C. or lower, and more preferably 85 ° C. or higher and 105 ° C. or lower. preferable.
  • the aromatic polycarbonate resin (B) used in the present invention is a polycarbonate resin in which structural units derived from a dihydroxy compound are linked by a carbonate bond, and is represented by the following general formula (2) as a structural unit derived from a dihydroxy compound. It has a structural unit.
  • R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
  • Y represents a single bond or a divalent group.
  • substituent of R 1 to R 8 in the general formula (2) include an alkyl group having 1 to 10 carbon atoms which may have a substituent, and 1 to carbon atoms which may have a substituent. 10 alkoxy groups, halogen groups, halogenated alkyl groups having 1 to 10 carbon atoms, or aromatic groups having 6 to 20 carbon atoms which may have a substituent. Among these, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aromatic group having 6 to 20 carbon atoms which may have a substituent is preferable.
  • the divalent group represented by Y is an alkylene group having a chain structure having 1 to 6 carbon atoms which may have a substituent, and an optionally substituted carbon group having 1 carbon atom.
  • the substituent is not particularly limited as long as the effects of the present invention are not inhibited, but usually has a molecular weight of 200 or less.
  • an aryl group is preferable, and a phenyl group is particularly preferable.
  • the aromatic polycarbonate resin (B) used in the present invention may be a homopolymer or a copolymer.
  • the aromatic polycarbonate resin (B) is a copolymer
  • all the structural units derived from the dihydroxy compound are A polycarbonate resin having the largest number of structural units derived from the dihydroxy compound represented by the formula (1), more preferably the dihydroxy compound represented by the general formula (1) with respect to all the structural units derived from the dihydroxy compound.
  • a polycarbonate resin having a structure derived from is used in an amount of 50 mol% or more, more preferably 70 mol% or more, particularly preferably 90 mol% or more.
  • the aromatic polycarbonate resin (B) may have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure. Furthermore, the aromatic polycarbonate resin (B) used in the present invention may contain a structural unit derived from a dihydroxy compound having a site represented by the general formula (1). However, a polycarbonate resin having a structure different from that of the polycarbonate resin (A) is used when it contains a structural unit derived from a dihydroxy compound having a site represented by the general formula (1).
  • the structural unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) used in the present invention is obtained by removing a hydrogen atom from the hydroxyl group of the dihydroxy compound.
  • Specific examples of the corresponding dihydroxy compound include the following. 4,4′-biphenol, 2,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-dimethyl-2,4′-dihydroxy-1 , 1′-biphenyl, 3,3′-di- (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′ -Dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra- (t-butyl) -4,4'-dihydroxy-1,1'-biphenyl, 2,2', 3,3 Biphenyl compounds such as'
  • Halogenated bisphenol compounds such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane.
  • preferred dihydroxy compounds are bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1 , 1-bis- (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis -(4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4-hydroxy Phenyl) -1-phenylethane, 1,1-bis- (4-hydroxyphenyl) -1-phenylpropan
  • bis- (4-hydroxyphenyl) methane bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis -(4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -Bis- (4-hydroxyphenyl) cyclohexane is preferred.
  • the production method of the aromatic polycarbonate resin (B) used in the present invention may be any conventionally known method such as a phosgene method, a transesterification method, or a pyridine method.
  • a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described below.
  • the transesterification method is a production method in which a dihydroxy compound and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added, and melt transesterification condensation polymerization is performed.
  • the dihydroxy compound include the biphenyl compounds and bisphenol compounds exemplified above.
  • carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (B) used in the present invention is usually 8,000 or more and 30,000 or less, preferably 10,000 or more and 25,000, from the balance of mechanical properties and molding processability.
  • the range is as follows.
  • the reduced viscosity of the aromatic polycarbonate resin (B) was measured at a temperature of 20.0 ° C. ⁇ 0.1 ° C. using methylene chloride as a solvent and the polycarbonate concentration was precisely adjusted to 0.60 g / dl. Usually, it is 0.23 dl / g or more and 0.72 dl / g or less, preferably 0.27 dl / g or more and 0.61 dl / g or less.
  • the aromatic polycarbonate resin (B) may be used alone or in combination of two or more.
  • the polycarbonate resin composition in the present invention preferably has a single glass transition temperature from the viewpoint of maintaining the transparency of the polycarbonate resin composition and the polycarbonate resin molded product.
  • the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the polycarbonate resin composition only need to be different types, and the polycarbonate resin (A) preferably has a ring structure, Among these, those containing isosorbide as a dihydroxy compound having a site represented by the general formula (1) in a part of the structure are particularly preferable.
  • the polycarbonate resin composition in the present invention includes a structural unit derived from a dihydroxy compound (a) having a site represented by the following general formula (1) in a part of the structure and a dihydroxy compound (b) of an alicyclic hydrocarbon. It is a polycarbonate resin composition containing a polycarbonate resin (A) containing a derived structural unit and an aromatic polycarbonate resin (B).
  • R 1 to R 8 in the general formula (2) each independently represent a hydrogen atom or a substituent.
  • Y represents a single bond or a divalent group.
  • the proportion of the structural unit derived from the alicyclic hydrocarbon dihydroxy compound (b) in the polycarbonate resin (A) is usually 35 mol% or more, preferably 40 mol% or more. Preferably it is 50 mol% or more, Most preferably, it is 55 mol% or more. On the other hand, it is preferably 90 mol% or less, more preferably 80 mol% or less, and particularly preferably 70 mol% or less.
  • the ratio of the aromatic polycarbonate resin (B) in the polycarbonate resin composition comprising the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is preferably 20% by weight or more, preferably 30% by weight. More preferably, it is 50% by weight or more, particularly preferably 55% by weight or more. On the other hand, it is preferably 90% by weight or less, more preferably 80% by weight or less, and particularly preferably 70% by weight or less.
  • the polycarbonate resin composition and the polycarbonate resin molded article of the present invention can be blended with resins other than polycarbonate resins and additives other than resins.
  • resins other than polycarbonate resins that are compounded for the purpose of further improving and adjusting molding processability and various physical properties include resins such as polyester resins, polyethers, polyamides, polyolefins, polymethyl methacrylates, and core-shell types. And rubber-like modifiers such as graft-type or linear random and block copolymers.
  • the amount of the resin other than the polycarbonate resin is 1 part by weight or more and 30 parts by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix
  • a heat stabilizer can be blended in order to prevent a decrease in molecular weight and a deterioration in hue during molding.
  • the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
  • triphenyl phosphite tris (nonylphenyl) phosphite, tris (2 , 4-Di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl Phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylene bis (4,6-di-) tert -Butylphenyl)
  • heat stabilizers may be used alone or in combination of two or more.
  • the amount of the heat stabilizer is 0.0001 parts by weight or more and 1 part by weight or less based on 100% by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention.
  • By blending the heat stabilizer within such a range it is possible to prevent a decrease in molecular weight or discoloration of the resin without causing bleeding of the additive.
  • antioxidants generally known for the purpose of antioxidant can be mix
  • antioxidants include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl)
  • the amount of the antioxidant is 0.0001 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. Is preferably blended at a ratio of 0.0005 parts by weight or more and 0.5 parts by weight or less, more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. Further preferred. By blending the antioxidant in such a range, the oxidation deterioration of the resin can be prevented without causing the bleeding of the antioxidant on the surface of the molded body and the deterioration of the mechanical properties of various molded products.
  • an ultraviolet absorber can be blended.
  • examples of such an ultraviolet absorber include 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzo Triazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′- And methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one), and the like.
  • the melting point of the ultraviolet absorber is particularly preferably in the range of 120 to 250 ° C.
  • an ultraviolet absorber having a melting point of 120 ° C. or higher is used, fogging due to gas on the surface of the molded article is reduced and improved.
  • the blending amount of the ultraviolet absorber is a ratio of 0.0001 part by weight or more and 1 part by weight or less with respect to 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. Is preferably blended at a ratio of 0.0005 parts by weight or more and 0.5 parts by weight or less, more preferably 0.001 parts by weight or more and 0.2 parts by weight or less. Further preferred. Within such a range, the weather resistance of the resin composition and the molded article can be improved without causing bleeding of the ultraviolet absorbent on the surface of the molded article of the ultraviolet absorbent and deterioration of mechanical properties of various molded articles.
  • a hindered amine light stabilizer can be mix
  • Such hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, poly [[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]], N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidylamin
  • the amount of the hindered amine light stabilizer is 0.001 part by weight or more and 1 part by weight or less based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. It is preferable to mix
  • the polycarbonate resin composition of the present invention can be molded without causing bleeding of the hindered amine light stabilizer on the surface of the polycarbonate resin composition and deterioration of mechanical properties of various molded products.
  • the weather resistance of the molded product formed can be improved.
  • the polycarbonate resin composition of the present invention preferably further contains a release agent in order to further improve the releasability from the mold during melt molding.
  • Release agents include higher fatty acids, higher fatty acid esters of mono- or polyhydric alcohols, natural animal waxes such as beeswax, natural plant waxes such as carnauba wax, natural petroleum waxes such as paraffin wax, and montan wax. Natural coal wax, olefin wax, silicone oil, organopolysiloxane and the like can be mentioned, and higher fatty acid and higher fatty acid ester of monohydric or polyhydric alcohol are particularly preferable.
  • a partial ester or a total ester of a substituted or unsubstituted monovalent or polyhydric alcohol having 1 to 20 carbon atoms and a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms is preferable.
  • Such partial esters or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbite, stearyl stearate, behenic acid monoglyceride, behenyl behenate, Pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, isopropyl palmitate, biphenyl biphenate Sorbitan monostearate, 2-ethylhexyl stearate and the like.
  • the higher fatty acid is preferably a substituted or unsubstituted saturated fatty acid having 10 to 30 carbon atoms.
  • saturated fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.
  • One of these release agents may be used alone, or two or more thereof may be mixed and used.
  • the content of the releasing agent is preferably 0.0001 parts by weight or more, more preferably 0.001 parts by weight, based on 100 parts by weight of the mixture of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) used in the present invention. 01 parts by weight or more, particularly preferably 0.1 parts by weight or more, on the other hand, preferably 2 parts by weight or less, more preferably 1 part by weight or less, particularly preferably 0.5 parts by weight or less.
  • the timing and method of adding the release agent to be blended with the polycarbonate resin composition there are no particular limitations on the timing and method of adding the release agent to be blended with the polycarbonate resin composition.
  • the polycarbonate resin is produced by the transesterification method, when the polymerization reaction is completed; the polycarbonate resin melted during mixing of the polycarbonate resin and other compounding agents regardless of the polymerization method.
  • a method of directly mixing or kneading the release agent with a polycarbonate resin; a high-concentration masterbatch prepared using a small amount of a polycarbonate resin or other resin and the release agent can also be added. .
  • a polycarbonate resin molded product obtained by molding the above-described polycarbonate resin composition is obtained.
  • the molding method of the polycarbonate resin molded product is not particularly limited, but the polycarbonate resin (A), the aromatic polycarbonate resin (B) and, if necessary, other raw materials such as resins and additives are directly mixed, and an extruder or an injection. Either put into a molding machine and mold, or melt and mix the raw materials using a twin-screw extruder, extrude into a strand shape to produce pellets, and then put these pellets into an extruder or injection molding machine Can be mentioned.
  • the polycarbonate resin molded article of the present invention is excellent in light resistance and transparency, it can be used for road sound insulation walls, arcade ceiling sheets, arcade ceiling plates, facility roofs, facility wall materials, and the like.
  • a specific device is used and a specific filter or the like is used to mainly emit light having a wavelength of 300 nm or more and 1100 nm or less, a black panel temperature of 63 ° C., and a relative humidity of 50.
  • a sample is irradiated for 500 hours at a discharge voltage of 50 V and a discharge current of 60 A using a sunshine carbon arc in an environment where the rainfall spraying time per hour is 12 minutes.
  • the difference from the YI) value is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less.
  • Example 1 After dry blending PC1 and PC3 at a weight ratio of 80:20, the mixture was extruded at a resin temperature of 250 ° C. using a twin screw extruder (TEX30HSS-32) manufactured by Nippon Steel Works, and cooled and solidified with water. Then, it pelletized with the rotary cutter. After the pellets were dried at 80 ° C. for 10 hours in a nitrogen atmosphere, the pellets were supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.) under the conditions of a resin temperature of 250 ° C., a mold temperature of 60 ° C., and a molding cycle of 40 seconds. An injection-molded plate (width 60 mm ⁇ length 60 mm ⁇ thickness 3 mm) was molded. Table 1 shows the results of measuring the total light transmittance and YI of the obtained sample.
  • TEX30HSS-32 twin screw extruder manufactured by Nippon Steel Works
  • Example 2 Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC3 were mixed at a mixing weight ratio of 60:40. The results are shown in Table 1.
  • Example 3 Samples were prepared and evaluated in the same manner as in Example 1 except that PC1 and PC3 were mixed at a mixing weight ratio of 40:60. The results are shown in Table 1.
  • Example 1 Samples were prepared and evaluated in the same manner as in Example 1 except that PC2 and PC3 were mixed at a mixing weight ratio of 80:20. The results are shown in Table 1.

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Abstract

La présente invention concerne : une composition de résine polycarbonate ayant d'excellentes résistance aux intempéries, transparence, couleur, résistance à la chaleur, stabilité thermique, moulabilité et résistance mécanique ; et un article moulé produit à partir de la composition de résine polycarbonate. La présente invention concerne spécifiquement : une composition de résine polycarbonate comprenant une résine polycarbonate (A) qui contient un motif structural dérivé d'un composé dihydroxy (a) ayant, en tant que partie de la structure de celui-ci, un fragment représenté par la formule générale (1) et un motif structural dérivé d'un composé dihydroxy (b) d'un hydrocarbure alicyclique ayant 11 atomes de carbone ou moins et une résine polycarbonate aromatique (B) représentée par la formule générale (2) ; et un article moulé produit à partir de la composition de résine polycarbonate. (Dans la composition, le fragment représenté par la formule générale (1) n'est pas une partie de -CH2-O-H. Dans la formule générale (2), R1 à R8 représentent indépendamment un atome d'hydrogène ou un substituant ; et Y représente une simple liaison ou un groupe bivalent.)
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CN105713366B (zh) * 2009-12-10 2018-08-28 三菱化学株式会社 聚碳酸酯树脂组合物和成型品
JP5966251B2 (ja) * 2010-03-26 2016-08-10 三菱化学株式会社 ポリカーボネート樹脂組成物及び成形品
EP2692797A4 (fr) 2011-03-31 2014-09-10 Mitsubishi Chem Corp Composition de résine polycarbonate et article moulé obtenu à partir de ladite composition
KR101940339B1 (ko) 2011-03-31 2019-01-18 미쯔비시 케미컬 주식회사 폴리카보네이트 수지 조성물 및 그 성형품
CN103597009B (zh) 2011-04-19 2016-01-20 帝人株式会社 共聚聚碳酸酯及由它们形成的透明成型品
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EP2511341A4 (fr) 2015-07-08

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