WO2017000155A1 - Composition de résine de polycarbonate, son procédé de fabrication, et article moulé - Google Patents

Composition de résine de polycarbonate, son procédé de fabrication, et article moulé Download PDF

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Publication number
WO2017000155A1
WO2017000155A1 PCT/CN2015/082750 CN2015082750W WO2017000155A1 WO 2017000155 A1 WO2017000155 A1 WO 2017000155A1 CN 2015082750 W CN2015082750 W CN 2015082750W WO 2017000155 A1 WO2017000155 A1 WO 2017000155A1
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Prior art keywords
polycarbonate resin
compound
bis
resin composition
group
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PCT/CN2015/082750
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English (en)
Chinese (zh)
Inventor
田中智彦
吴国章
苏莉莉
赖文钦
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East China University of Science and Technology
Mitsubishi Chemical Corp
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East China University of Science and Technology
Mitsubishi Chemical Corp
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Priority to CN201580081298.6A priority Critical patent/CN107709459B/zh
Priority to PCT/CN2015/082750 priority patent/WO2017000155A1/fr
Publication of WO2017000155A1 publication Critical patent/WO2017000155A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C08K5/57—Organo-tin compounds
    • 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

Definitions

  • the present invention relates to a polycarbonate resin composition which is excellent in transparency and has a balance between biomass content, heat resistance and mechanical strength.
  • a conventional aromatic polycarbonate resin containing a chemical structure such as bisphenol A can be produced using a raw material derived from petroleum resources.
  • a raw material derived from petroleum resources due to fear of depletion of petroleum resources, it is required to provide polycarbonate having biomass resources such as plants as raw materials. Ester resin.
  • the global warming will cause problems such as climate change due to excessive carbon dioxide emissions, and it is also required to develop a polycarbonate resin which is carbon-neutral and uses plant-derived monomers as a raw material.
  • isosorbide a dihydroxy compound derived from biomass resources, is a monomer component, and is subjected to transesterification with a carbonic acid diester to distill off the side under reduced pressure.
  • a method for producing a polycarbonate resin is obtained by a monohydroxy compound produced by the reaction (see, for example, Patent Documents 1 to 7).
  • a dihydroxy compound such as ISB has a problem that the thermal stability is low, the polycondensation reaction at a high temperature, the molding, and the processing are caused, compared with the bisphenol compound used in the conventional aromatic polycarbonate resin. Thermal decomposition causes the resin to yellow.
  • the copolymers of ISB and bisphenol compound described in Patent Documents 3 to 6 have a high glass transition temperature, the ISB reactivity is different from that of the bisphenol compound, and the bisphenol compound is more likely to be a copolymer end group. .
  • the bisphenol compound when the polymerization reaction is carried out at a polymerization temperature lower than that of the aromatic polycarbonate resin in consideration of the color tone and the thermal stability of the ISB, the bisphenol compound may sometimes become a terminal group and the polymerization degree may not be sufficiently improved.
  • the product lacks impact toughness, which is more remarkable when the copolymerization amount of the bisphenol compound exceeds 20 mol%.
  • Patent Document 7 discloses a polycarbonate copolymer containing an ISB structural unit derived from an aliphatic dihydroxy compound structural unit and a structural unit derived from an aromatic bisphenol compound, although the polycarbonate copolymer Although it is excellent in heat resistance, moldability, and mechanical strength, since it contains a structural unit derived from a bisphenol compound, the degree of polymerization may not be sufficiently increased, and it may become a polymer which lacks impact toughness. Further, the biomass content rate is low, and it is not preferable from the viewpoint of environmental protection.
  • a polycarbonate resin containing a dihydroxy compound such as isosorbide (ISB) derived from a biomass-derived dihydroxy compound has high glass transition temperature and excellent heat resistance, but has the following disadvantages: in addition to molecular chain rigidity, during melt polymerization The viscosity is high, high molecular weight products cannot be obtained, and therefore, impact toughness is lacking. In order to improve the toughness, attempts have been made to copolymerize an aliphatic dihydroxy compound or an aromatic bisphenol compound.
  • ISB isosorbide
  • Patent Document 8 discloses a polycarbonate resin composition comprising ISB and an aliphatic group.
  • Patent Document 9 discloses a polycarbonate resin composition in which a polycarbonate resin containing a dihydroxy compound structural unit of ISB and an aliphatic hydrocarbon is mixed in an aromatic polycarbonate resin, whereby the pencil hardness is excellent .
  • Patent Document 1 International Publication No. 2004/111106
  • Patent Document 2 International Publication No. 2007/063823
  • Patent Document 3 International Publication No. 2005/066239
  • Patent Document 4 International Publication No. 2006/041190
  • Patent Document 5 Japanese Patent Laid-Open Publication No. 2009-062501
  • Patent Document 6 Japanese Laid-Open Patent Publication No. 2009-020963
  • Patent Document 7 Japanese Laid-Open Patent Publication No. 2011-127108
  • Patent Document 8 International Publication No. 2011/071162
  • Patent Document 9 International Publication No. 2012/1117212
  • the resin composition of the ISB copolymerized polycarbonate resin and the aromatic polycarbonate resin containing 45 mol% or more of the aliphatic dihydroxy compound as described in Patent Document 8 has transparency, hue, thermal stability, formability, and mechanical properties. Although the strength is excellent, if the glass transition temperature of the composition is increased to 120° C.
  • the content of the aromatic polycarbonate resin needs to be increased to 50% by weight or more. This inevitably lowers the biomass content rate, and therefore it is not preferable from the viewpoint of the environment.
  • a polycarbonate resin comprising two structural units of a dihydroxy compound of ISB and an aliphatic hydrocarbon is mixed in an aromatic polycarbonate resin, and the polycarbonate resin composition substantially has a full light transmission. The rate of passing rate is less than 20% and the transparency is poor.
  • the present invention has been made in view of the above circumstances, and provides a polycarbonate resin composition which is excellent in transparency and which has a high level of biomass content, heat resistance, and mechanical strength, a method for producing the same, and a poly A molded body of a carbonate resin composition.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a polycarbonate resin composition containing a specific polycarbonate resin (A) and an aromatic polycarbonate resin (B) has excellent transparency, and The present invention has been completed in a highly balanced manner in terms of biomass content, heat resistance and mechanical strength.
  • the gist of the present invention resides in the following [1] to [16].
  • a polycarbonate resin composition comprising a polycarbonate resin (A), an aromatic polycarbonate resin (B) and a lower portion containing a structural unit derived from a compound represented by the following formula (1) At least one or more compounds (C) of the tin compound and the basic nitrogen-containing compound represented by the formula (2) or (3), wherein the compound (C) is added in an amount relative to the polycarbonate-containing compound
  • the resin composition of the resin (A) and the aromatic polycarbonate resin (B) is contained in an amount of 0.001 part by weight or more and 5 parts by weight or less based on 100 parts by weight.
  • R represents an alkyl group or an aryl group having 1 to 15 carbon atoms
  • X1 to X4 represent an alkyl group having 1 to 15 carbon atoms, an aryl group, an allyloxy group, a cyclohexyl group, a hydroxyl group, a halogen or the like.
  • the monovalent group may be the same or different.
  • X5 represents a sulfur or an oxygen atom.
  • the polycarbonate resin composition according to claim 3 or 4 wherein the polycarbonate tree
  • the glass composition of the lipid composition as measured by differential scanning calorimetry has a glass transition temperature of 90 ° C or higher and 200 ° C or lower.
  • the polycarbonate resin composition of the present invention and the molded article thereof have excellent transparency and have a high balance of biomass content, heat resistance and mechanical strength.
  • the polycarbonate resin composition of the present invention is obtained from the above components by an addition step and a reaction step.
  • the polycarbonate resin (A) preferably contains a structural unit derived from a dihydroxy compound represented by the following formula (1) in a ratio of more than 50% by mole based on 100% by mole of the structural unit derived from all dihydroxy compounds (
  • the polycarbonate resin referred to as "structural unit (a)").
  • the polycarbonate resin (A) may be a homopolycarbonate resin of the structural unit (a), or may be a polycarbonate resin obtained by copolymerizing a structural unit other than the structural unit (a). From the viewpoint of optimizing impact toughness, a copolymerized polycarbonate resin is preferred.
  • dihydroxy compound represented by the above formula (1) examples include isosorbide (ISB), isomannide, and isoidide in a stereoisomer relationship. These dihydroxy compounds may be used alone or in combination of two or more.
  • the plant source is abundant in terms of availability, ease of production, weather resistance, optical properties, moldability, heat resistance, and carbon neutrality. Sorbitol which is easily converted from various starches is subjected to dehydration condensation to obtain isosorbide (ISB).
  • the dihydroxy compound represented by the above formula (1) is easily oxidized by oxygen. Therefore, in order to prevent oxidative decomposition during storage or use, it is preferred not to mix water and use a deoxidizing agent or under a nitrogen atmosphere.
  • the polycarbonate resin (A) is preferably a structural unit (a) containing a dihydroxy compound derived from the general formula (1), a dihydroxy compound of an aliphatic hydrocarbon, or a dihydroxy compound of an alicyclic hydrocarbon, Further, a copolymerized polycarbonate resin having a structural unit of one or more kinds of dihydroxy compounds (abbreviated as "structural unit (b)") is used as the dihydroxy compound containing an ether bond. Since these dihydroxy compounds have a soft molecular structure, the impact toughness of the polycarbonate resin can be improved by using these dihydroxy compounds as a raw material. Among these dihydroxy compounds, it is preferred to use an aliphatic group having a large effect of improving toughness.
  • dihydroxy compound of a hydrocarbon or a dihydroxy compound of an alicyclic hydrocarbon a dihydroxy compound of an alicyclic hydrocarbon is most preferably used.
  • Specific examples of the dihydroxy compound of the aliphatic hydrocarbon, the dihydroxy compound of the alicyclic hydrocarbon, and the dihydroxy compound containing the ether bond are as follows.
  • Dihydroxy compounds selected from aliphatic hydrocarbons include: ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, a linear aliphatic dihydroxy compound such as 1,9-nonanediol or 1,10-decanediol 1,12-dodecanediol; 1,3-butanediol, 1,2-butanediol, A branched aliphatic dihydroxy compound such as neopentyl glycol or hexanediol.
  • the dihydroxy compound selected from the alicyclic hydrocarbon includes: 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, and five rings.
  • the dihydroxy compound containing an ether bond may, for example, be an oxyalkylene glycol or a dihydroxy compound containing an acetal ring.
  • oxyalkylene glycol for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol or the like can be used.
  • dihydroxy compound containing an acetal ring for example, a spiro diol represented by the following structural formula (5) or a dioxane diol represented by the following structural formula (6) can be used.
  • the content ratio of the above structural unit (a) to 100 mol% of the structural unit derived from all dihydroxy compounds is preferably more than 50 mol%, more preferably 55 mol% or more and 95 mol%. % or less is more preferably 60% by mole or more and 90% by mole or less, and particularly preferably 65% by mole or more and 85% by mole or less.
  • the content ratio of the structural unit (a) is 50% by mole or less, the heat resistance is insufficient in addition to the low biomass content.
  • the structural unit (a) may be 100% by mole, but from the viewpoint of improving the molecular weight and impact resistance, it is preferred to carry out copolymerization.
  • the polycarbonate resin (A) may further contain a structural unit other than the structural unit (a) and the structural unit (b).
  • a structural unit (dihydroxy compound) for example, a dihydroxy compound having an aromatic group or the like can be used.
  • the content ratio of the structural unit derived from the aromatic group-containing dihydroxy compound is preferably 10% by mole or less, and more preferably 5% by mole or less based on 100% by mole of the structural unit derived from all the dihydroxy compounds.
  • dihydroxy compound containing an aromatic group for example, the following dihydroxy compounds can be used, but dihydroxy compounds other than these may be used.
  • the above other dihydroxy compound can be appropriately selected depending on the characteristics required for the polycarbonate resin. Further, the above other dihydroxy compounds may be used alone or in combination of two or more. By using the above-mentioned other dihydroxy compound in combination with the dihydroxy compound represented by the above formula (1), effects such as improvement in flexibility and mechanical properties of the polycarbonate resin (A) and improvement in moldability can be obtained.
  • the dihydroxy compound used as a raw material of the polycarbonate resin (A) may contain a reducing agent, an antioxidant, a deoxidizing agent, and light.
  • Stabilizers such as stabilizers, antacids, pH stabilizers and heat stabilizers.
  • the dihydroxy compound represented by the above formula (1) has a property of being easily deteriorated in an acidic state, and therefore, by using an alkali stabilizer in the synthesis of the polycarbonate resin (A), the above formula (1) can be suppressed.
  • the deterioration of the dihydroxy compound shown can further improve the quality of the obtained polycarbonate resin composition.
  • the alkaline stabilizer for example, the following compounds can be used. a hydroxide, carbonate, phosphate, phosphite, hypophosphite, borate and fatty acid salt of a Group IA or Group IIA metal in the Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005; Methyl ammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenyl hydroxide Ammonium, triethylmethylammonium hydroxide, triethylbenzylammonium hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenyl
  • the content of the above-mentioned basic stabilizer in the above-mentioned dihydroxy compound is not particularly limited, and since the dihydroxy compound represented by the above formula (1) is unstable in an acidic state, it is preferred to set the content of the alkaline stabilizer so as to contain The pH of the aqueous solution of the dihydroxy compound of the alkaline stabilizer is about 7.
  • the content of the alkaline stabilizer relative to the dihydroxy compound represented by the above formula (1) is preferably 0.0001 to 1% by mass, and more preferably 0.001 to 0.1% by mass.
  • carbonic acid diester used for the raw material of the polycarbonate resin [A] a compound represented by the following formula (9) can be usually used. 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 1 and A 2 a substituted or unsubstituted aromatic hydrocarbon group is preferably used, and an unsubstituted aromatic hydrocarbon group is more preferably used.
  • diphenyl carbonate such as diphenyl carbonate (DPC) or ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate
  • DPC diphenyl carbonate
  • ditolyl carbonate dimethyl carbonate
  • diethyl carbonate diethyl carbonate
  • di-tert-butyl carbonate diphenyl carbonate
  • Ester and the like diphenyl carbonate or substituted diphenyl carbonate is preferably used, and diphenyl carbonate is particularly preferably used.
  • the carbonic acid diester may contain an impurity such as a chloride ion, and the impurity may hinder the polycondensation reaction or the color tone of the obtained polycarbonate resin may be deteriorated. Therefore, it is preferable to use a carbonic acid diester which is purified by distillation or the like as needed.
  • the polycarbonate resin (A) can be synthesized by polycondensing the above-mentioned dihydroxy compound and carbonic acid diester by a transesterification reaction. More specifically, it can be obtained by removing a monohydroxy compound or the like produced by a side reaction in the transesterification reaction to the outside of the system while polycondensation.
  • transesterification reaction is carried out in the presence of a transesterification catalyst (hereinafter, a transesterification catalyst is referred to as a "polymerization catalyst").
  • a transesterification catalyst is referred to as a "polymerization catalyst”.
  • the kind of the polymerization catalyst can have a very large influence on the reaction rate of the transesterification reaction and the quality of the obtained polycarbonate resin (A).
  • the polymerization catalyst is not limited as long as it satisfies the transparency, color tone, heat resistance, weather resistance and mechanical strength of the obtained polycarbonate resin (A).
  • a metal compound of Group IA or Group IIA hereinafter referred to as "Group IA” or “Group IIA”
  • Group IA Group IA
  • Group IIA a metal compound of Group IA or Group IIA in the long-period periodic table
  • a basic compound such as a basic ammonium compound or an amine compound, and among them, a Group IA metal compound and/or a Group IIA metal compound is preferable.
  • Group IA metal compound for example, the following compounds can be used.
  • a lithium compound is preferred from the viewpoint of polymerization activity and color tone of the obtained polycarbonate resin.
  • Group IIA metal compound for example, the following compounds can be used.
  • a magnesium compound, a calcium compound or a cerium compound is preferable, which is obtained from polymerization activity and From the viewpoint of the color tone of the polycarbonate resin, a magnesium compound and/or a calcium compound are more preferable, and a calcium compound is most preferable.
  • a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound or an amine compound may be used in combination with the above-mentioned Group IA metal compound and/or Group IIA metal compound, and it is particularly preferable to use only IA.
  • Group metal compounds and / or Group IIA metal compounds may be used in combination with the above-mentioned Group IA metal compound and/or Group IIA metal compound, and it is particularly preferable to use only IA.
  • Triethylphosphine tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts, and the like.
  • Tetramethylammonium hydroxide Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylhydrogen Ammonium Oxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide, Tributylphenylammonium Hydroxide, Tetraphenyl Examples of ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.
  • the following compounds can be used. 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, anthracene, and the like.
  • the amount of the polymerization catalyst used is preferably from 0.1 to 300 ⁇ mol, more preferably from 0.5 to 100 ⁇ mol, particularly preferably from 1 to 50 ⁇ mol per 1 mol of all dihydroxy compounds used for the reaction.
  • the amount of the polymerization catalyst to be used is preferably 0.1 ⁇ mol or more, more preferably 0.3 ⁇ mol or more, and particularly preferably 0.5 ⁇ mol or more per 1 mol of the total dihydroxy compound used for the reaction, based on the metal atomic weight of the compound containing the metal. Further, the upper limit is preferably 10 ⁇ mol or less, more preferably 5 ⁇ mol or less, and particularly preferably 3 ⁇ mol or less.
  • the polymerization temperature must be increased accordingly. Therefore, the obtained polycarbonate resin (A) may have a poor color tone, or the unreacted raw material may volatilize during the polymerization to cause the molar ratio of the dihydroxy compound and the carbonic acid diester to be destroyed, and the possibility may not be achieved. Molecular weight.
  • the amount of the polymerization catalyst used is too large, undesired side reactions may occur in combination, and the color tone of the obtained polycarbonate resin (A) may be deteriorated or the resin may be colored during molding.
  • the total amount of the compounds of these metals in the polycarbonate resin (A) is preferably 1 ppm by mass or less, and more preferably 0.5 ppm by mass or less based on the total content of sodium, potassium, cesium and iron.
  • the polycarbonate resin (A) can be obtained by polycondensation of a dihydroxy compound and a carbonic acid diester used as a raw material of a dihydroxy compound represented by the above formula (1) by a transesterification reaction in the presence of a polymerization catalyst.
  • the dihydroxy compound and the carbonic acid diester as raw materials are preferably uniformly mixed before the transesterification reaction.
  • the mixing temperature is usually 80 ° C or higher, preferably 90 ° C or higher, and usually 250 ° C or lower, preferably 200 ° C or lower, more preferably 150 ° C or lower, and preferably 100 ° C or higher and 120 ° C or lower. If the temperature of the mixture is too low, there is a possibility that the dissolution rate is slow or the solubility is insufficient, and the curing is often caused.
  • the temperature of the mixture is too high, thermal deterioration of the dihydroxy compound may occur, and as a result, the color tone of the obtained polycarbonate resin (A) may be deteriorated or the weather resistance may be adversely affected.
  • the operation of the dihydroxy compound and the carbonic acid diester of the mixed raw material is preferably 10 vol% or less, more preferably 0.0001 to 10 vol%, especially 0.0001 to 5 vol%, particularly 0.0001 to 1 vol, from the viewpoint of suppressing deterioration of color tone and reduction in reactivity. Under the atmosphere of %.
  • a carbonic acid diester in a molar ratio of from 0.90 to 1.20, more preferably a molar ratio of from 0.95 to 1.10, based on the total amount of the dihydroxy compound used for the reaction.
  • the molar ratio is small, there is a possibility that the amount of the hydroxyl terminal of the polycarbonate resin (A) to be produced is increased, whereby the thermal stability of the polymer is deteriorated, coloring is caused during molding, or the rate of the transesterification reaction is lowered, Or the desired high molecular weight body cannot be obtained.
  • the rate of the transesterification reaction may be lowered, or it may be difficult to produce the polycarbonate resin (A) having a desired molecular weight.
  • the decrease in the transesterification reaction rate leads to an increase in the heat-receiving process of the reaction, and thus it is possible to deteriorate the color tone and weather resistance of the obtained polycarbonate resin (A).
  • the molar ratio of the carbonic acid diester to the total dihydroxy compound increases, the amount of residual carbonic acid diester in the obtained polycarbonate resin (A) may increase, causing problems of contamination or odor during molding, and Preferably.
  • a method of polycondensing a dihydroxy compound and a carbonic acid diester is carried out in multiple stages using a plurality of reactors in the presence of the above catalyst.
  • the reaction may be in the form of a batch or a continuous process, or a combination of a batch process and a continuous process, preferably a polycarbonate resin which can be obtained in a less heated process, and the production efficiency is also preferably continuous.
  • the jacket temperature, the internal temperature, and the pressure in the reaction system in accordance with the reaction stage. Specifically, it is preferred to obtain a prepolymer at a relatively low temperature and a low vacuum in the initial stage of the reaction of the polycondensation reaction, and to raise the molecular weight to a predetermined value at a relatively high temperature and a high vacuum in the late stage of the reaction.
  • the unreacted monomer is distilled off, and the molar ratio of the dihydroxy compound to the carbonic acid diester may be deviated from the desired ratio. rate.
  • a decrease in the polymerization rate or a polymer having a desired molecular weight or terminal group cannot be obtained.
  • the rate of polymerization in the polycondensation reaction is controlled by the balance of the hydroxyl terminal and the carbonate terminal. Therefore, when the balance of the terminal group fluctuates due to the distillation of the unreacted monomer, it may be difficult to control the polymerization rate to be constant or the variation in the molecular weight of the obtained resin may be large. Since the molecular weight of the resin is related to the melt viscosity, the melt viscosity may fluctuate during melt processing, and it is difficult to maintain the quality of the molded article. This problem is particularly likely to occur when the polycondensation reaction is carried out in a continuous manner.
  • the temperature of the refrigerant introduced into the reflux condenser may be appropriately selected depending on the monomer to be used, and the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C, preferably 80 to 150 ° C at the inlet of the reflux condenser. It is particularly preferably 100 to 130 °C. When the temperature of the refrigerant is too high, the reflux flow rate is reduced, and the effect is lowered.
  • the distillation efficiency of the monohydroxy compound which should be distilled off may be lowered, and the reaction rate may be lowered and the obtained resin may be obtained.
  • Coloring As the refrigerant, warm water, steam, heat medium oil or the like can be used, and steam or heat medium oil is preferable.
  • the type and amount of the above-mentioned polymerization catalyst are important, without impairing the color tone of the obtained polycarbonate resin (A).
  • the polycarbonate resin (A) is produced by a process of two or more stages using a polymerization catalyst.
  • the polycondensation reaction can be carried out by using one polycondensation reactor and sequentially changing the conditions in two or more stages. However, from the viewpoint of production efficiency, it is preferred to use a plurality of reactors and change the respective conditions in multiple stages.
  • the preferred reaction conditions at the initial stage of the reaction and the preferred reaction conditions at the later stage of the reaction are usually different. Therefore, by using a plurality of reactors arranged in series, the respective conditions can be easily changed, and the production efficiency can be improved.
  • the polymerization reactor used in the production of the polycarbonate resin (A) may be at least two or more as described above, but it is preferably three or more, preferably from 3 to 5, from the viewpoint of production efficiency and the like, and particularly preferably 4.
  • the number of the polymerization reactors is two or more, a plurality of reaction stages having different conditions may be further carried out in each polymerization reactor, or the temperature and pressure may be continuously changed.
  • the polymerization catalyst may be added to the raw material preparation tank or the raw material storage tank, or may be directly added to the polymerization reactor. From the viewpoint of the stability of the supply and the control of the polycondensation reaction, it is preferred to provide a catalyst supply line in the middle of the raw material line before being supplied to the polymerization reactor and supply the polymerization catalyst as an aqueous solution.
  • the productivity is lowered or the heating process applied to the product is increased. If the temperature is too high, not only the volatilization of the monomer but also the decomposition of the polycarbonate resin (A) may be promoted. Or coloring.
  • the reaction conditions in the first-stage reaction the following conditions can be employed. That is, the maximum temperature of the internal temperature of the polymerization reactor is usually set to be in the range of 150 to 250 ° C, preferably 160 to 240 ° C, and more preferably 170 to 230 ° C.
  • the pressure of the polymerization reactor (hereinafter, the pressure represents the absolute pressure) is usually set in the range of 1 to 110 kPa, preferably 5 to 70 kPa, and more preferably 7 to 30 kPa.
  • the reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 3 hours. The first stage reaction is carried out while distilling off the produced monohydroxy compound to the outside of the reaction system.
  • the pressure of the reaction system is gradually lowered from the pressure in the first stage, and the generated monohydroxy compound is continuously removed from the reaction system while the pressure (absolute pressure) of the final reaction system is 1 kPa or less.
  • the maximum temperature of the internal temperature of the polymerization reactor is usually set in the range of 200 to 260 ° C, preferably 210 to 250 ° C.
  • the reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.3 to 6 hours, particularly preferably 0.5 to 3 hours.
  • the color tone of the obtained polycarbonate resin (A) tends to be deteriorated.
  • the polymerization rate is changed by the ratio of the hydroxyl group terminal and the carbonate group terminal as described above, it is possible to intentionally reduce one terminal group, suppress the polymerization rate, and accordingly maintain the pressure of the polymerization reactor in the final stage as The high vacuum allows the residual low molecular component in the resin represented by the monohydroxy compound to be reduced.
  • the polycarbonate resin (A) obtained in the polymerization reactor of the final stage preferably contains 10 mol/ton or more of both the hydroxyl terminal and the carbonate terminal.
  • one terminal group is preferably 60 mol/ton or less.
  • the residual amount of the monohydroxy compound in the resin can be reduced at the outlet of the polymerization reactor.
  • the residual amount of the monohydroxy compound in the resin in the outlet of the polymerization reactor is preferably 2,000 ppm by mass or less, more preferably 1,500 ppm by mass or less, still more preferably 1,000 ppm by mass or less.
  • the residual amount of the monohydroxy compound is preferably small, but if it is reduced to less than 100 ppm by mass, it is necessary to employ an operation condition in which the amount of one terminal group is extremely reduced and the pressure of the polymerization reactor is maintained at a high vacuum. At this time, as described above, it is difficult to maintain the molecular weight of the obtained polycarbonate resin (A) at a certain level. Therefore, it is usually 100 ppm by mass or more, and preferably 150 ppm by mass or more.
  • the monohydroxy compound produced by the side reaction is preferably reused as a raw material of another compound after being purified as necessary.
  • the monohydroxy compound is phenol
  • it can be used as a raw material of diphenyl carbonate or bisphenol A.
  • the glass transition temperature of the polycarbonate resin (A) is preferably 90 ° C or higher. When the glass transition temperature is lower than 90 ° C, the resin composition may have difficulty in achieving a balance between heat resistance and biomass content.
  • the glass transition temperature of the polycarbonate resin (A) is more preferably 100 ° C or more, further preferably 110 ° C or more, and particularly preferably 120 ° C or more, from the viewpoint of further improving the balance between the heat resistance and the biomass content.
  • the glass transition temperature of the polycarbonate resin (A) is preferably 170 ° C or lower.
  • the glass transition temperature of the polycarbonate resin (A) is more preferably 165 ° C or less, further preferably 160 ° C or less, and particularly preferably 150 ° C or less from the viewpoint of improving the molecular weight and preventing the balance of coloring.
  • the molecular weight of the polycarbonate resin (A) can be expressed by reduced viscosity, and the higher the reduction viscosity, the larger the molecular weight.
  • the reduced viscosity of the polycarbonate resin (A) is usually 0.30 dL/g or more, preferably 0.33 dL/g or more.
  • the reduction viscosity is too large, the fluidity at the time of molding is lowered, and the productivity or the workability tends to be lowered.
  • the reduced viscosity is usually 1.20 dL/g or less, preferably 1.00 dL/g or less, and more preferably 0.80 dL/g or less.
  • the reduced viscosity of the polycarbonate resin (A) was a solution in which the concentration of the resin composition was precisely adjusted to 0.6 g/dL using dichloromethane as a solvent, and the temperature was 20.0 ° C ⁇ 0.1 ° C using an Ubbelohde viscosity tube. The measured value under the conditions. The details of the method for measuring the reduced viscosity will be described in the examples.
  • the melt viscosity of the polycarbonate resin (A) is preferably 400 Pa ⁇ s or more and 3,000 Pa ⁇ s or less, more preferably 600 Pa ⁇ s or more and 2500 Pa ⁇ s or less, and particularly preferably 800 Pa ⁇ s or more and 2000 Pa ⁇ s or less.
  • the melt viscosity of the polycarbonate resin (A) is less than the above range, the molded article of the resin composition may become brittle and may not be a material having sufficient mechanical properties.
  • the melt viscosity is higher than the above range, there is a possibility that the flow is insufficient during the molding process to impair the appearance of the molded article, or the dimensional accuracy is deteriorated.
  • the melt viscosity is a melt viscosity measured at a temperature of 240 ° C and a shear rate of 91.2 sec -1 measured by a capillary rheometer [manufactured by Toyo Seiki Co., Ltd.]. The details of the method for measuring the melt viscosity will be described in Examples to be described later.
  • the polycarbonate resin (A) preferably contains a catalyst deactivator.
  • the catalyst deactivator is not particularly limited as long as it is an acidic substance and has a deactivation function of a polymerization catalyst, and examples thereof include phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, and tetrabutyl octylsulfonate.
  • Anthracene salt tetramethyl phosphonium benzenesulfonate, tetrabutylphosphonium sulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium p-toluenesulfonate; Ammonium salt such as tetramethylammonium sulfonate or tetrabutylammonium dodecylbenzenesulfonate; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, and p-toluenesulfonic acid An alkyl ester such as an ester or ethyl hexadecylsulfonate.
  • the catalyst deactivator preferably contains a phosphorus-based compound (hereinafter referred to as "specific phosphorus-based compound”) containing any of the partial structures represented by the following structural formula (10) or the following structural formula (11).
  • a phosphorus-based compound hereinafter referred to as "specific phosphorus-based compound”
  • the polymerization catalyst described later is deactivated, and the subsequent polycondensation reaction can be suppressed from proceeding unnecessarily.
  • coloring of the polycarbonate resin (A) at a high temperature can be suppressed.
  • phosphoric acid As the specific phosphorus-based compound containing the partial structure represented by the above structural formula (10) or structural formula (11), phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate, acid phosphate or the like can be used.
  • phosphoric acid, phosphonic acid, and phosphonic acid esters are more excellent in the effects of catalyst deactivation and coloring inhibition, and phosphorous acid is particularly preferable.
  • the following compounds can be used. Phosphonic acid (phosphite), methylphosphonic acid, ethylphosphonic acid, ethylene Phosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylene diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 4-methoxy Phenylphosphonic acid, nitrogen tris(methylene phosphonic acid), propylphosphonic anhydride, and the like.
  • Phosphonic acid phosphite
  • methylphosphonic acid methylphosphonic acid
  • ethylphosphonic acid ethylene Phosphonic acid
  • decylphosphonic acid decylphosphonic acid
  • phenylphosphonic acid phenylphosphonic acid
  • benzylphosphonic acid aminomethylphosphonic acid
  • methylene diphosphonic acid 1-hydroxyethane-1,1-diphosphonic acid
  • the following compounds can be used. Dimethyl phosphonate, diethyl phosphonate, bis(2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, A Dimethyl phosphinate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, phenylphosphine Dipropyl acrylate, diethyl (methoxymethyl)phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl)phosphonate, para Diethyl benzylphosphonate, diethylphosphonoacetic acid, ethyl diethylphosphonoacetate
  • the acidic phosphate for example, the following compounds can be used. Dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, bis(2-ethylhexyl) phosphate, diisophosphate Phosphate diesters such as tridecyl ester, dioleyl phosphate, distearyl phosphate, diphenyl phosphate, dibenzyl phosphate, or a mixture of diester and monoester, diethyl chlorophosphate, stearyl phosphate Zinc salts, etc.
  • Dimethyl phosphate diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis(butoxyethyl) phosphate, bis(2-ethylhexyl) phosphate, diisophosphate Phosphate diesters such as
  • the above specific phosphorus-based compounds may be used singly or in combination of two or more kinds in any combination and in any ratio.
  • the content of the specific phosphorus-based compound in the polycarbonate resin (A) is preferably 0.1 ppm by mass or more and 5 ppm by mass or less in terms of phosphorus atom.
  • the content of the specific phosphorus-based compound is too small, the effect of catalyst deactivation and coloring inhibition may be insufficient.
  • the polycarbonate resin (A) may be colored instead. Further, at this time, in particular, in the durability test of high temperature and high humidity, the polycarbonate resin (A) is easily colored.
  • the specific phosphorus-based compound can more reliably obtain the effects of catalyst deactivation and coloring inhibition.
  • the content of the specific phosphorus-based compound is preferably 0.5 times mol or more and 5 times mol or less, more preferably 0.7 times mol or more and 4 times mol or less, based on 1 mol of the metal atom of the polymerization catalyst, and particularly preferably 0.8 times mol or more and 3 times mol or less.
  • the aromatic polycarbonate resin (B) is a polycarbonate resin having a structural unit derived from an aromatic dihydroxy compound represented by the following formula (12) as a main structural unit.
  • R 1 to R 8 in the above formula (12) each independently represent a hydrogen atom or a substituent.
  • Y represents a single bond or a divalent group.
  • the substituent of R 1 to R 8 in the formula (12) represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, and a halogen. a group, a halogenated alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 20 carbon atoms which may have a substituent.
  • the divalent group of Y in the formula (12) includes an alkylene group having a chain structure of 1 to 6 carbon atoms which may have a substituent, and a carbon number of 1 to 6 which may have a substituent.
  • an alkylidene group having a chain structure an alkylene group having a cyclic structure of 3 to 6 carbon atoms which may have a substituent
  • an alkylidene group having a cyclic structure of 3 to 6 carbon atoms which may have a substituent O-, -S-, -CO- or -SO 2 -.
  • the substituent is not particularly limited as long as the effect of the present invention is not inhibited, and the molecular weight is usually 200 or less.
  • the substituent of the alkylene group having a chain structure of 1 to 6 carbon atoms is preferably an aryl group, and particularly preferably a phenyl group.
  • the aromatic polycarbonate resin (B) may be a homopolymer or a copolymer. In the case of a copolymer, it is preferred that the total structural unit derived from the dihydroxy compound is derived from the general formula (12).
  • the content ratio of the structural unit derived from the dihydroxy compound represented by the above formula (12) to 100 mol% of the total structural unit derived from all dihydroxy compounds is more preferably 50.
  • the mole% or more is more preferably 70% by mole or more, and particularly preferably 90% by mole 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. Further, the aromatic polycarbonate resin (B) may contain a structural unit derived from a dihydroxy compound having a moiety represented by the above formula (1). However, in the case of a structural unit containing a dihydroxy compound derived from the moiety represented by the above formula (1), a polycarbonate resin having a structural unit different from that of the polycarbonate resin (A) can be used.
  • the structural unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) is a structural unit in which a hydrogen atom is removed from the hydroxyl group of the dihydroxy compound.
  • Specific examples of the equivalent dihydroxy compound include the following dihydroxy compounds.
  • a halogenated bisphenol compound such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane or 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane.
  • dihydroxy compound examples include bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxyphenyl)methane, and bis(4-hydroxy-3-methyl group).
  • Phenyl)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, 1,1-bis(4-hydroxyl) -3,3,5-trimethylphenyl)cyclohexane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1 , 1-bis(4-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane
  • bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5-A) are particularly preferred.
  • any conventionally known method such as a phosgene method, a transesterification method, or a pyridine method can be used.
  • a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described as an example.
  • the transesterification method is a production method in which a dihydroxy compound, a carbonic acid diester, a basic catalyst, and an acidic substance neutralizing the basic catalyst are subjected to melt transesterification polycondensation.
  • the dihydroxy compound may, for example, be a biphenyl compound or a bisphenol compound exemplified above.
  • Typical examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate, and carbonic acid. Diethyl ester, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Among them, diphenyl carbonate is particularly preferably used.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (B) is usually 8,000 or more and 30,000 or less, and preferably 10,000 or more and 25,000 or less, from the balance between mechanical properties and moldability. Further, the reduced viscosity of the aromatic polycarbonate resin (B) was measured by using dichloromethane as a solvent, and the polycarbonate concentration was precisely adjusted to 0.60 g/dl, and the measurement was carried out at a temperature of 20.0 ° C ⁇ 0.1 ° C, usually 0.23 dl. /g or more and 0.72 dl / g or less, preferably in the range of 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 compound (C) is one or more compounds selected from the group consisting of the following formula (2) or (3) and a basic nitrogen-containing compound.
  • the compound represented by the formula (2) is a compound represented by the following formula (2) or (3).
  • R represents an alkyl group or an aryl group having 1 to 15 carbon atoms
  • X1 to X4 represent an alkyl group having 1 to 15 carbon atoms, an aryl group, an allyloxy group, a cyclohexyl group, a hydroxyl group, a halogen or the like.
  • the monovalent group may be the same or different.
  • X5 represents a sulfur or an oxygen atom.
  • dibutyltin oxide (818-08-6), methylphenyltin oxide, tetraethyltin oxide, hexaethyltin oxide, cyclohexahexyltin oxide, and di(12.
  • Alkyl) tin oxide triethyltin hydroxide (994-32-1), triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate (1067-33-0), dibutyl Bisodium laurate (77-58-7), dioctyltin dilaurate (3648-18-8), diphenyltin dilaurate, monobutyltin trichloride (1118-46-3) Dibutyltin dichloride (683-18-1), tributyltin chloride (1461-22-9), dibutyltin sulfide and monobutyl hydroxytin oxide (2273-43-0, MBTO_MCC )Wait.
  • dibutyltin dilaurate is mentioned.
  • stannic acid may be used as the other compound (C).
  • an alkyl stannic acid such as methyl stannic acid, ethyl stannic acid or butyl stannic acid may be mentioned.
  • Examples of the basic nitrogen-containing compound include a basic ammonium compound and an amine compound.
  • the basic ammonium compound for example, the following compounds can be used. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylhydrogen Ammonium Oxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide, Tributylphenylammonium Hydroxide, Tetraphenyl Examples of ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammoni
  • the following compounds can be used. 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, anthracene, and the like.
  • the amount of the compound (C) to be added is 0.001 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the resin composition containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). It is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. Further, it is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less.
  • the amount is less than 0.001 part by weight, the effect of the transparency is insufficient.
  • the amount is more than 5 parts by weight, the coloring is remarkable, but the coloring is remarkable, the molecular weight is lowered, and the mechanical strength is insufficient.
  • the solid compound can be supplied in a solid state and can be dissolved in
  • the water or solvent compound can be supplied as an aqueous solution or solution. Further, it may be added to the polycarbonate resin raw material, and in the case of an aqueous solution or a solution, it may be supplied from a raw material input port of the extruder, or a liquid may be added from the cylinder using a pump or the like.
  • the polycarbonate resin composition preferably has a total light transmittance of 80% or more in the thickness direction of the molded body having a thickness of 1 mm.
  • the total light transmittance is more preferably 85% or more, further preferably 88% or more, and particularly preferably 90% or more.
  • the method of measuring the total light transmittance will be described in the examples to be described later.
  • the haze can also be measured by the same method as the full line transmittance.
  • the glass transition temperature of the polycarbonate resin composition is preferably 100 ° C or more and 200 ° C or less. In the case where the glass transition temperature is lower than 100 ° C, it is possible to undergo deformation in the heat resistance test or the weather resistance test. On the other hand, when the glass transition temperature exceeds 200 ° C, the polycarbonate resin (A) component is easily thermally decomposed, and if it is retained for a long period of time during molding, appearance defects such as silver streaks or foaming may occur. When the resin composition is produced, the polycarbonate resin (A) may be thermally deteriorated to cause a decrease in impact resistance.
  • the glass transition temperature of the polycarbonate resin is more preferably 110° C. or higher and 190° C. or lower, and still more preferably 120° C. or higher and 180° C. or lower.
  • the polycarbonate resin composition which exhibits the total light transmittance and the glass transition temperature specified above includes a polycarbonate resin (A) containing a structural unit derived from the compound represented by the above formula (1), and an aromatic polycarbonate.
  • the ester resin (B) and the above specific compound (C) can be obtained by adjusting the content of the compound (C) to the above-mentioned predetermined range.
  • the compounding ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the polycarbonate resin composition can be arbitrarily selected depending on the desired physical properties.
  • the weight ratio (A/B) of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is preferably 95/5 to 50/50, and more preferably 90/%, from the viewpoint of increasing the biomass content. 10 to 60/40. If it deviates from the above range, it may be difficult to better balance heat resistance, impact resistance, and biomass content.
  • additives can be added to the above polycarbonate resin composition.
  • additives there are dyes, antioxidants, UV absorbers, light stabilizers, mold release agents, heat stabilizers, flame retardants, flame retardant aids, inorganic fillers, impact modifiers, hydrolysis inhibitors, foaming
  • an additive which is usually used in a polycarbonate resin can be used.
  • the dyeing pigment examples include organic dyes such as inorganic pigments, organic pigments, and organic dyes.
  • the inorganic pigment include carbon black; titanium oxide, zinc oxide, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron. It is a black oxide-based pigment or the like.
  • organic dyes such as organic pigments and organic dyes include phthalocyanine dyes;
  • a condensed polycyclic dye such as an azo system, a thioindole system, a purple ketone ketone, an anthraquinone, a quinacridone, a dioxazine, an isoindolinone or a quinophthalone; Ketone, oxime, methine, quinoline, heterocyclic, methyl dyes, and the like.
  • These dyes may be used singly or in combination of two or more.
  • an inorganic pigment is preferable, and the inorganic pigment is used as a coloring agent, and the molded article can be used for outdoor use or the like for a long period of time.
  • the amount of the dye is 0.05 parts by weight or more and 5 parts by weight or less based on 100 parts by weight of the total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). It is more preferably 0.05 parts by weight or more and 3 parts by weight or less, still more preferably 0.1 parts by weight or more and 2 parts by weight or less.
  • the amount of the colorant is less than 0.05 part by weight, it is difficult to obtain a dyed article having clear reflection properties.
  • it is more than 5 parts by weight the surface roughness of the molded article becomes large, and it is difficult to obtain a dyed molded article having clear reflection properties.
  • the antioxidant a general antioxidant used in the resin can be used. From the viewpoint of oxidative stability and thermal stability, a phosphite-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant are preferable.
  • the amount of the antioxidant added is usually preferably 0.001 part by weight or more, more preferably 0.002 part by weight or more, and still more preferably 0.005, based on 100 parts by weight of the total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). More than the weight.
  • the amount of the antioxidant added is usually preferably 5 parts by weight or less, more preferably 3 parts by weight or less, and still more preferably 2 parts by weight or less, based on 100 parts by total of the total amount.
  • the amount of the antioxidant added is more than 5 parts by weight, the mold may be contaminated during molding, and a molded article having an excellent surface appearance may not be obtained.
  • it is less than 0.001 part by weight, there is a tendency that a sufficient improvement effect with respect to the molding stability cannot be obtained.
  • phosphite-based antioxidant examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and trisphosphonium phosphite.
  • trioctyl phosphite tris(octadecyl) 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 II Phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di Tert-butylphenyl) pentaerythritol diphosphite
  • tridecyl phenyl phosphite tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and double (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • These compounds may be used alone or in combination of two or more.
  • sulfur-based antioxidant examples include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and dimyristyl.
  • pentaerythritol tetrakis(3-laurylthiopropionate) is preferred.
  • phenolic antioxidant examples include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and trisole.
  • one or more aromatic monohydroxy compounds are preferably substituted with an alkyl group having 5 or more carbon atoms, and specifically, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyl is preferred.
  • Phenyl)propionate pentaerythritol-tetra ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ⁇ , 1,6-hexanediol-bis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Phenylene or the like is further preferably pentaerythritol-tetra ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. These compounds may be used alone or in combination of two or more.
  • Examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, a benzoate-based compound, a hindered amine-based compound, a phenyl salicylate-based compound, and a cyano group.
  • An acrylate type compound, a malonate type compound, an oxalic acid aniline type compound, etc. may be used alone or in combination of two or more.
  • benzotriazole-based compound examples include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole and 2-(2'-hydroxyl group). -3'-tert-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3'-methyl-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-dodecylphenyl)benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-tert-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, Methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert
  • the triazine-based compound may, for example, be 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isoxin Oxyphenyl)-s-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (BASF ⁇ Japan Company system, Tinuvin1577FF) and so on.
  • hydroxybenzophenone-based compound examples include 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-octyloxy Benzophenone and the like.
  • cyanoacrylate compound examples include ethyl-2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylic acid. Ester and the like.
  • malonic ester-based compound examples include 2-(1-arylalkylene)malonates. Among them, [(4-methoxyphenyl)-methylene]-dimethyl malonate (manufactured by Clariant, Hostavin PR-25), 2-(p-methoxybenzylidene)malonic acid is preferred. Dimethyl ester.
  • the oxalic acid anilide compound may, for example, be 2-ethyl-2'-ethoxy-oxaloanilide (made by Clariant Co., Ltd., Sanduvor VSU).
  • 2-(2'-hydroxy-3'-tert-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriene is preferred.
  • the light stabilizer is a hindered amine light stabilizer, and its molecular weight is preferably 1,000 or less, and more preferably 900 or less. When the molecular weight exceeds 1,000, there is a possibility that the weather resistance cannot be sufficiently obtained when the molded article is formed. Further, the molecular weight is preferably 300 or more, and more preferably 400 or more. When the molecular weight is less than 300, heat resistance may be lacking, and the mold may be contaminated during molding, and a molded article having an excellent surface appearance may not be obtained. Further, a compound having a piperidine structure is preferred.
  • the piperidine structure defined herein may be an amine structure having a saturated six-membered ring, and further includes a structure in which a part of the piperidine structure is substituted with a substituent.
  • the substituent is an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable.
  • a compound having a plurality of piperidine structures is particularly preferred, and those having a plurality of piperidine structures linked by an ester structure are preferred.
  • the content of the light stabilizer is preferably 0.001 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). It is more preferably 0.005 parts by weight or more and 3 parts by weight or less, and still more preferably 0.01 parts by weight or more and 1 part by weight or less.
  • the amount of the hindered amine light stabilizer added is more than 5 parts by weight, coloring tends to occur, and even if a coloring agent is added, it is difficult to obtain a darkness having a depth and a clear feeling.
  • the amount of the aromatic polycarbonate resin (B) is preferably set cautiously. The amount added.
  • the release agent for imparting mold release property during molding may be contained in an amount of 0.0001 part by weight or more and 2 parts by weight or less based on 100 parts by weight of the polycarbonate resin.
  • Fatty acid esters Fatty acid esters.
  • the content of the fatty acid ester of the polyol is less than 0.0001 part by weight, the effect of addition may not be sufficiently obtained, and the mold may be cracked due to mold release failure during mold release during molding.
  • the resin composition is white turbid or the adhering matter adhering to the mold during the forming process is increased.
  • the content of the fatty acid ester of the polyol is more preferably 0.01 parts by weight or more and 1.5 parts by weight or less, and still more preferably 0.1 parts by weight or more and 1 part by weight or less.
  • the fatty acid ester of the polyhydric alcohol is preferably a partial ester or a full ester of a polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms.
  • Examples of the partial ester or the full ester of the polyhydric alcohol and the saturated fatty acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, and behenic acid.
  • stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used.
  • a full ester is more preferable as the fatty acid ester of the polyol.
  • fatty acid a higher fatty acid is preferable, and a saturated fatty acid having 10 to 30 carbon atoms is more preferable.
  • a fatty acid include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.
  • the polyhydric alcohol is preferably ethylene glycol.
  • the fatty acid ester of the above polyol is preferably a fatty acid diester of a glycol.
  • the addition timing and the addition method of the release agent to be blended in the polycarbonate resin composition are not particularly limited.
  • the addition period is, for example, a case where the polymerization reaction is completed in the case of producing a polycarbonate resin by a transesterification method, and further, in the course of the mixing of the polycarbonate resin composition and other compounding agents, regardless of the polymerization method.
  • the polycarbonate resin composition is melted, it is blended and kneaded with a polycarbonate resin composition in a solid state such as granules or powder using an extruder or the like.
  • Examples of the method of addition include a method of directly mixing or kneading a release agent in a polycarbonate resin composition, and a high concentration produced by using a small amount of a polycarbonate resin composition or other resin and a release agent. The method of adding the form of the masterbatch.
  • the above polycarbonate resin composition may be, for example, an aromatic polyester, an aliphatic polyester, a polyamide, a polystyrene, a polyolefin, an acrylic, an amorphous polyolefin, or the like, within a range not impairing the effects of the present invention.
  • One or two or more kinds of synthetic resins such as ABS and AS, such as synthetic resins, polylactic acid, and polybutylene succinate, are kneaded and used as a polymer alloy.
  • glass fiber, glass ground fiber, glass flake, glass beads, silica, alumina, titania, calcium sulfate powder, gypsum may be added within a range in which design can be maintained.
  • gypsum whiskers barium sulfate, talc, mica, wollastonite and other calcium silicate; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber , inorganic fillers such as brass fiber, stainless steel fiber, potassium titanate fiber, and their whiskers; and powdered organic fillers such as wood powder, bamboo powder, coconut starch, softwood powder, pulp powder; crosslinked polyester, poly A capsular-spherical organic filler such as styrene, styrene-acrylic acid copolymer or urea resin; or a fibrous organic filler such as carbon fiber, synthetic fiber
  • the above-mentioned polycarbonate resin composition can be produced by the following steps: in the above-mentioned specific polycarbonate resin (A) and aromatic polycarbonate resin (B), 0.5 ppm by weight in terms of metal amount is added.
  • the above specific compound (C) in an amount of 1000 ppm by weight or less; and then a reaction step of subjecting the polycarbonate resin (A) and the aromatic polycarbonate resin (B) to a melting reaction.
  • the compound (C) is present to promote the transesterification reaction between the polycarbonate resin (A) and the aromatic polycarbonate resin (B), thereby obtaining a resin composition having high compatibility.
  • the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the compound (C) the same polycarbonate resin (A) and aromatic polycarbonate resin (B) as described above can be used.
  • Compound (C) Compound (C).
  • the polycarbonate resin composition can be produced by passing the above components in a specific ratio simultaneously or in any order through a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a kneading roller or A mixer such as an extruder is mixed to manufacture.
  • a tumbler mixer a V-type mixer, a Nauta mixer, a Banbury mixer, a kneading roller or A mixer such as an extruder is mixed to manufacture.
  • a mixer such as an extruder is more preferable.
  • the polycarbonate resin composition can be formed by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method.
  • the molded article obtained by the molding is excellent in color tone, transparency, heat resistance, weather resistance, optical properties, and mechanical strength, and has low residual molecular components and foreign matter, and is therefore suitable for interior parts for vehicles.
  • a sample of the polycarbonate resin (A) or the aromatic polycarbonate resin (B) was dissolved in dichloromethane to prepare a polycarbonate resin solution having a concentration of 0.6 g/dL.
  • the relative viscosity ⁇ rel was calculated based on the following formula (i) by measuring the passage time t 0 of the solvent and the passage time t of the solution under the conditions of a temperature of 20.0 ° C ⁇ 0.1 ° C using an Ubbel-type viscosity tube manufactured by Senyou Chemical Industry Co., Ltd.
  • the specific viscosity ⁇ sp is obtained from the relative viscosity ⁇ rel based on the following formula (ii).
  • the obtained specific viscosity ⁇ sp was divided by the concentration c (g/dL) of the solution, whereby the reduced viscosity ( ⁇ sp /c) was determined.
  • the glass transition temperature was measured at a temperature elevation rate of 10 ° C/min under a nitrogen atmosphere using a differential scanning calorimeter (DSC: Modulate DSC 2910, TA America). The case where the single transition temperature is set to ⁇ , and the case where there are two or more transition temperatures is ⁇ , and the total glass transition temperature is described.
  • DSC differential scanning calorimeter
  • the total light transmittance was measured with a standard C light source using a hot-pressed sheet having a thickness of 1 mm to be described later and using a haze meter (manufactured by Shanghai Shinko Co., Ltd., WGW). By visual inspection, the case of apparent opacity is described as opaque.
  • the elongation at break was determined in accordance with the ASTM D638 standard.
  • Radiocarbon 14 is generated at a certain speed by cosmic rays in the atmosphere and disappears at a certain speed (half-life: 5370 years), so there is a certain amount in nature.
  • a plant that absorbs carbon dioxide in the atmosphere contains a certain amount of the C14. When it does not cause carbonation assimilation, such as felling, it disappears at a certain speed. Therefore, the radiocarbon dating method is established by using this property. Since fossil fuels were not affected by cosmic rays for a long time, C14 disappeared. On the other hand, since the bio-derived chemical has only passed a short time after the supply of C14 is stopped, it can be said that the content of C14 is a substantially constant value.
  • the method for calculating the biomass content will also be specifically described using the above method.
  • the biomass content when the polycarbonate resin (A) and the aromatic polycarbonate resin (B) are blended is because the aromatic polycarbonate resin (B) is derived from fossil fuels.
  • the polymer produced from the raw material has a biomass content of 0%.
  • the examples were blended in a weight ratio, and therefore, the molar mass (unit: g/mol) of each of the polycarbonate resins was calculated, and the weight was divided by the molar mass, respectively, thereby being converted into a molar fraction.
  • the blended biomass content was calculated by the product of the biomass content of the above polycarbonate resin (A) and its molar fraction.
  • the calculation of biomass is calculated only from the resin component, and components such as the compound (C), the heat stabilizer, and the release agent are not considered.
  • ⁇ CHDM 1,4-cyclohexanedimethanol [made by SK Chemical Co., Ltd.]: raw materials derived from fossil fuels
  • DPC Diphenyl carbonate [Mitsubishi Chemical Co., Ltd.]: Raw materials derived from fossil fuels
  • Irganox 1010 pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Corporation]
  • E-275 Ethylene glycol distearate [Nippon Oil Co., Ltd.]
  • an aqueous solution of calcium acetate monohydrate as a catalyst was supplied to the first vertical stirring reactor so as to be 1.5 ⁇ mol based on 1 mol of all the dihydroxy compounds.
  • the reaction temperature, internal pressure, and residence time of each reactor were respectively referred to as a first vertical stirred reactor: 190 ° C, 25 kPa, and 90 minutes, and a second vertical stirred reactor: 195 ° C, 10 kPa, 45 minutes, third standing Stirred reactor: 210 ° C, 3 kPa, 45 minutes, 4th horizontal stirred reactor: 225 ° C, 0.5 kPa, 90 minutes.
  • the operation was carried out while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the obtained polycarbonate resin was 0.41 dL/g to 0.43 dL/g.
  • the polycarbonate resin was taken out from the fourth horizontally stirred reactor in an amount of 60 kg/hr, and the resin was directly supplied to a vented twin-screw extruder (manufactured by Nippon Steel Co., Ltd., TEX30 ⁇ , in a molten state). L/D: 42].
  • the polycarbonate resin that passed through the extruder was continuously passed through a 10 ⁇ m mesh candle type filter (manufactured by SUS316) in a molten state to filter foreign matter.
  • the polycarbonate resin was discharged from the mold in a strip shape, cooled by water, and then granulated using a rotary cutter to obtain particles of a copolymerized polycarbonate resin having a ISB/CHDM molar ratio of 70/30 mol%.
  • the extruder has three vacuum exhaust ports, and the remaining low molecular components in the resin are removed by volatility. 2,000 ppm by mass of water was added to the resin in front of the second exhaust port to perform water injection and devolatilization. 0.1 mass part, 0.05 mass part, and 0.3 part by mass of Irganox 1010, AS 2112, and E-275 were added to the front surface of the third exhaust port with respect to 100 parts by mass of the polycarbonate resin. Through the above operation, an ISB/CHDM copolymer polycarbonate resin was obtained.
  • the polycarbonate resin (A) obtained in Production Example 1 is referred to as "PC-A1".
  • the polycarbonate resin (A) obtained in Production Example 2 is referred to as "PC-A2".
  • ISB/CHDM/DPC/calcium acetate monohydrate 0.27/0.73/1.00/6.5 ⁇ 10 -7 was charged in a molar ratio, and ISB was loaded.
  • the DPC and the calcium acetate monohydrate having a chloride ion concentration of 10 ppb or less were distilled and purified, and the nitrogen substitution was sufficiently performed.
  • the mixture was heated by a heating medium, and stirring was started at an internal temperature of 100 ° C, and the contents were melted and made uniform while controlling the internal temperature to 100 ° C.
  • the temperature was raised, the internal temperature was 210 ° C over 40 minutes, and the internal temperature was 210 ° C to control the temperature to maintain the temperature, and the pressure was reduced. After reaching 210 ° C, the pressure was 13.3 kPa (absolute pressure) after 90 minutes. The same as the following), while maintaining this pressure, it is further maintained for 30 minutes.
  • the phenol vapor generated by the side reaction together with the polymerization reaction is introduced into a reflux condenser using a vapor having an inlet temperature of 100 ° C as a reflux condenser as a refrigerant, and the phenol vapor contains a certain amount of monomer components in the polymerization reactor.
  • the uncondensed phenol vapor was then introduced into a condenser using warm water of 45 ° C as a refrigerant.
  • the mixture was transferred to another polymerization apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above, and the temperature was raised and decompressed, and the mixture was allowed to stand for 60 minutes.
  • the internal temperature was 210 ° C and the pressure was 200 Pa.
  • the internal temperature was 220 ° C and the pressure was 133 Pa or less over 20 minutes, and the pressure was recompressed at the time when the predetermined stirring power was reached, and the molten polycarbonate resin was granulated from the outlet of the polymerization reactor by a granulator to obtain granules. .
  • the reduced viscosity was 0.63 dl/g.
  • PC-A3 The polycarbonate resin (A) obtained in Production Example 3 is referred to as "PC-A3".
  • PC-B1 Iupilon S3000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.: 100 mol% aromatic polycarbonate resin of bisphenol A structural unit, interfacial polymerization product, reduced viscosity 0.46 dl/g): raw materials derived from fossil fuels
  • ⁇ C-1 Dibutyltin dilaurate (made by Aladdin)
  • ⁇ C-2 tetramethylammonium hydroxide (made by Aladdin)
  • PC-A2 50 parts by weight of PC-A2 obtained in Production Example 2, 50 parts by weight of PC-B1 as the aromatic polycarbonate resin (B), and 0.03 parts by weight of C-1 as the compound (C) were put together.
  • the mixture was kneaded in a small kneader (Rheocord 300P manufactured by Hakke Co., Ltd.).
  • the mixture was kneaded at 80 rpm and a set temperature of 250 ° C for 8 minutes to obtain a pelletized resin.
  • the obtained pellets were dried at 80 ° C for 12 hours in a vacuum dryer, and then pressed at a set temperature of 250 ° C and a pressure of 10 MPa for 10 minutes using a hot press apparatus (manufactured by Shanghai Xima Weili Rubber Machinery Co., Ltd.), and then passed. The mixture was cooled and pressed to obtain a test piece of 50 mm ⁇ 50 mm ⁇ 1 mmt. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that C-1 in Example 1 was changed to 0.2 part by weight. Will result Shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that PC-A2 obtained in Production Example 2 in Example 1 was changed to PC-A1 obtained in Production Example 1. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that the case of using C-1 in Example 1 was changed to use 0.05 to 0.05 parts by weight. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that the case of using C-1 in Example 3 was changed to use C-30.2 parts by weight. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that the case of using C-1 in Example 1 was changed to use 0.05 to 5 parts by weight of C-4. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that the case of using C-1 in Example 3 was changed to use C-40.2 parts by weight. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was carried out except that C-1 in Example 1 was 0 parts by weight. The results are shown in Table 1.
  • Example 2 The same procedure as in Example 2 was carried out except that C-1 in Example 2 was 0 parts by weight. The results are shown in Table 1.
  • such a polycarbonate resin composition is excellent in transparency, and has a biomass ratio, heat resistance, and mechanical strength in a highly balanced manner.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de polycarbonate, son procédé de fabrication, et un corps moulé. La composition de résine de polycarbonate contient une résine de polycarbonate spécifique (A) et une résine de polycarbonate aromatique (B), et présente une excellente transparence, ainsi qu'une teneur en biomasse, une résistance à la chaleur et une résistance mécanique fortement équilibrées.
PCT/CN2015/082750 2015-06-30 2015-06-30 Composition de résine de polycarbonate, son procédé de fabrication, et article moulé Ceased WO2017000155A1 (fr)

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JPH01275655A (ja) * 1988-04-27 1989-11-06 Mitsubishi Gas Chem Co Inc 色相の改良された樹脂組成物
CN101466788A (zh) * 2006-05-19 2009-06-24 沙伯基础创新塑料知识产权有限公司 高热聚碳酸酯组合物，其制备方法及其制品
CN102656231A (zh) * 2009-12-10 2012-09-05 三菱化学株式会社 聚碳酸酯树脂组合物以及将其成型而得到的成型体、膜、板和注射成型品

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JP6108651B2 (ja) * 2008-11-28 2017-04-05 三菱化学株式会社 ポリカーボネート樹脂組成物、光学フィルム及びポリカーボネート樹脂成形品
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JPH01275655A (ja) * 1988-04-27 1989-11-06 Mitsubishi Gas Chem Co Inc 色相の改良された樹脂組成物
CN101466788A (zh) * 2006-05-19 2009-06-24 沙伯基础创新塑料知识产权有限公司 高热聚碳酸酯组合物，其制备方法及其制品
CN102656231A (zh) * 2009-12-10 2012-09-05 三菱化学株式会社 聚碳酸酯树脂组合物以及将其成型而得到的成型体、膜、板和注射成型品

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