WO2017000149A9 - 聚碳酸酯树脂组合物、其制造方法、成形体 - Google Patents

聚碳酸酯树脂组合物、其制造方法、成形体 Download PDF

Info

Publication number
WO2017000149A9
WO2017000149A9 PCT/CN2015/082743 CN2015082743W WO2017000149A9 WO 2017000149 A9 WO2017000149 A9 WO 2017000149A9 CN 2015082743 W CN2015082743 W CN 2015082743W WO 2017000149 A9 WO2017000149 A9 WO 2017000149A9
Authority
WO
WIPO (PCT)
Prior art keywords
polycarbonate resin
bis
compound
resin composition
weight
Prior art date
Application number
PCT/CN2015/082743
Other languages
English (en)
French (fr)
Other versions
WO2017000149A1 (zh
Inventor
田中智彦
吴国章
苏莉莉
赖文钦
Original Assignee
华东理工大学
三菱化学株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 华东理工大学, 三菱化学株式会社 filed Critical 华东理工大学
Priority to CN201580081281.0A priority Critical patent/CN107709458B/zh
Priority to PCT/CN2015/082743 priority patent/WO2017000149A1/zh
Publication of WO2017000149A1 publication Critical patent/WO2017000149A1/zh
Publication of WO2017000149A9 publication Critical patent/WO2017000149A9/zh

Links

Classifications

    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings
    • 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.
  • 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 turn 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.
  • ISB isosorbide
  • Patent Document 8 discloses a polycarbonate resin composition comprising ISB and an aliphatic group.
  • a polycarbonate and an aromatic polycarbonate resin composed of two structural units of a hydrocarbon dihydroxy compound.
  • the structural unit content of the aliphatic hydrocarbon-derived dihydroxy compound in the former polycarbonate is 45 mol% or more.
  • 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 a pencil Excellent hardness.
  • 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 total light transmission. The rate is lower 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) derived from a structural unit derived from the following formula (1), an aromatic polycarbonate resin (B), and the following formula The compound (C) of one or more of (2), (3) and (4), wherein the compound (C) is added in an amount relative to the polycarbonate resin (A) and the aromatic polycarbonate.
  • the resin composition of the resin (B) is contained in an amount of 0.1 part by weight or more and 10 parts by weight or less per 100 parts by weight.
  • R 1 and R 2 each independently represent an alkyl group having 0 to 4 carbon atoms or an alkyl group having an amide bond having 0 to 4 carbon atoms;
  • X represents a sulfur atom; or has a group of R 1 or R 2
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 7 represents a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, and p represents an integer of 4 to 45.
  • R 8 represents an alkylene group having an aliphatic or aromatic ring having 1 to 18 carbon atoms.
  • R 9 represents a linear or cyclic carbonyl group or an aromatic carbonyl group having 1 to 20 carbon atoms. An integer from 2 to 3.
  • polycarbonate resin composition according to claim 3 or 4, wherein the polycarbonate resin composition has a glass transition temperature of 90 ° C or more and 200 ° C as measured by differential scanning calorimetry. the following.
  • 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 (abbreviation) "Structural unit (a)") polycarbonate resin.
  • 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 dihydroxy compound represented by the above formula (1) is most preferably rich in plants from the viewpoints of availability, ease of production, weather resistance, optical properties, moldability, heat resistance, and carbon neutrality. And 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).
  • dihydroxy compounds a dihydroxy compound of an aliphatic hydrocarbon having a large effect of improving toughness or a dihydroxy compound of an alicyclic hydrocarbon is preferably used, and 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 structural unit (a) is a structural single sheet derived from all dihydroxy compounds.
  • the content ratio of 100 mol% is preferably more than 50 mol%, more preferably 55 mol% or more and 95 mol% or less, further preferably 60 mol% or more and 90 mol% or less, particularly preferably 65 mol% or more and 85 mol%. the following.
  • 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 stabilizer such as a reducing agent, an antioxidant, a deoxidizing agent, a light stabilizer, an antacid, a pH stabilizer, and a heat stabilizer.
  • a stabilizer such as a reducing agent, an antioxidant, a deoxidizing agent, a light stabilizer, an antacid, a pH stabilizer, and a heat stabilizer.
  • 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.
  • the Group IIA metal compound is preferably a magnesium compound, a calcium compound or a cerium compound. From the viewpoint of polymerization activity and color tone of the obtained 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, there is The side reaction which is not preferable is not preferable, and the color tone of the polycarbonate resin (A) obtained is deteriorated or the resin at the time of a shaping process is colored.
  • the Group IA metal if sodium, potassium or cesium is contained in a large amount in the polycarbonate resin, there is a possibility that the color tone is adversely affected. Further, if iron is contained in a large amount in the polycarbonate resin, it is also likely to adversely affect the color tone. Moreover, these metals not only come from the catalyst used but also from the raw materials or the reaction device.
  • 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 amount of the dihydroxy compound is increased, the amount of the residual carbonic acid diester in the polycarbonate resin (A) may increase, which may cause a problem of contamination or odor during molding, which is not preferable.
  • 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 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. If the polymerization reactor is When two or more are used, 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.
  • the polymerization rate becomes high, and the molecular weight change is too high, so one side
  • the 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 at a temperature of 240 ° C and a shear rate of 91.2 sec -1 measured using 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.
  • phosphonic acid for example, the following compounds can be used. Phosphonic acid (phosphite), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylene diphosphonic acid, 1-Hydroxyethane-1,1-diphosphonic acid, 4-methoxyphenylphosphonic acid, nitrotrimethylene (methylene phosphonic acid), propylphosphonic anhydride, and the like.
  • Phosphonic acid phosphite
  • methylphosphonic acid methylphosphonic acid
  • ethylphosphonic acid vinylphosphonic acid
  • decylphosphonic acid methylphosphonic acid
  • phenylphosphonic acid benzylphosphonic acid
  • aminomethylphosphonic acid methylene diphosphonic acid
  • 1-Hydroxyethane-1,1-diphosphonic acid 4-methoxyphenylphosphonic 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 be more reliably obtained by adjusting the content according to the amount of the polymerization catalyst.
  • 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 (2).
  • the content ratio of the structural unit derived from the dihydroxy compound represented by the above formula (2) 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 a 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 hydroxyl group derived from a dihydroxy compound.
  • the structural unit of the hydrogen atom is removed from the group.
  • 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-methylphenyl)methane, 2,2- 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 formulas (2), (3) and (4).
  • the compound represented by the formula (2) is a compound represented by the following formula (2).
  • R 1 and R 2 each independently represent an alkyl group having 0 to 4 carbon atoms or an alkyl group having an amide bond having 0 to 4 carbon atoms;
  • X represents a sulfur atom; or has a group of R 1 or R 2
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the compound represented by the formula (3) is a compound represented by the following formula (3).
  • R 7 represents a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, and p represents an integer of 4 to 45.
  • R 7 represents a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, and p represents an integer of 4 to 45.
  • the compound represented by the formula (3) is preferably a polyethylene glycol having a molecular weight of 200 to 2,000, and particularly preferably a polyethylene glycol having a molecular weight of 600 to 1,500. These may be used alone or in combination of two or more.
  • the compound represented by the formula (4) is a compound represented by the following formula (4).
  • R 8 represents an alkylene group having an aliphatic or aromatic ring having 1 to 18 carbon atoms.
  • R 9 represents a linear or cyclic carbonyl group or an aromatic carbonyl group having 1 to 20 carbon atoms. An integer from 2 to 3.
  • the amount of the compound (C) to be added is 0.1 parts by weight or more and 10 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 0.5 parts by weight or more, and more preferably 1 part by weight or more. Further, it is preferably 8 parts by weight or less, and more preferably 5 parts by weight or less. Add amount When the amount is less than 0.1 part by weight, the effect of the transparency is insufficient. When the amount is more than 10 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 in the method of adding the above compound (C), can be supplied in a solid state, and the compound soluble in water or a solvent can be supplied as an aqueous solution or a 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 2 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 total light 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-based dyes; azo-based, thioindole-based, pirinone-based, guanidine-based, quinophthalone-based, and dioxazines.
  • Condensed polycyclic dyes such as phthalic acid, isoindolinone, and quinophthalone; lanthanide, perhexanone, anthraquinone, methine, quinoline, heterocyclic, methyl dye Wait.
  • 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 antioxidant examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and phosphorous acid triphosphate.
  • tridecyl phenyl phosphite tris(2,4-di-tert-butylphenyl) phosphite, and bis (2,4-di-tertiary) Butylphenyl) pentaerythritol diphosphite, bis(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)benzo Triazole, 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-but
  • triazine-based compound examples include 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-isooctyloxyphenyl ---Triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol (manufactured by BASF Japan, Tinuvin 1577FF )Wait.
  • 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) of 1000 ppm by weight or less; and then, the polycarbonate resin (A) and the aromatic polymer are polymerized.
  • the carbonate resin (B) is subjected to a reaction step of 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 same polycarbonate resin (A) and aromatic polycarbonate resin (B) as described above can be used as described above.
  • 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.
  • ⁇ ISB isosorbide [made by Roquette Freres]: bio-sourced raw materials
  • ⁇ 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".
  • a resin was produced in the same manner as in Production Example 1 except that the amount of the aqueous solution was changed to 1.5 ⁇ mol per 1 mol of the dihydroxy compound, and the reduced viscosity of the obtained polycarbonate resin was changed from 0.60 dL/g to 0.63 dL/g.
  • a polycarbonate resin having a molar ratio of ISB/CHDM of 50/50 mol% was obtained.
  • 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
  • PC-B2 Iupilon S2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.: 100% by mole of aromatic polycarbonate resin of bisphenol A structural unit, interfacial polymerization product, reduced viscosity 0.50 dl/g): raw materials derived from fossil fuels
  • ⁇ C-1 4,4'-thiobis(2-tert-butyl-5-methylphenyl), z300 manufactured by Zibo Debaiyi Industry and Trade Co., Ltd.
  • ⁇ C-3 Polyethylene glycol (molecular weight: 2000, PEG 2000 manufactured by Sinopharm Chemical Reagent Co., Ltd.)
  • ⁇ C-4 bisphenol A epoxy resin (CYD-011 manufactured by Yueyang Baling Petrochemical Co., Ltd.)
  • 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 PC-A2 in Example 1 was changed to 50 parts by weight, PC-B1 was changed to 50 parts by weight, C-1 was changed to 2.5 parts by weight, and the kneading time was changed to 8 minutes. 1 is carried out in the same manner. 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 changed to 5 parts by weight. The results are shown in Table 1.
  • Example 3 The same procedure as in Example 3 was carried out except that PC-B1 in Example 3 was changed to PC-B2. 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.
  • the PC-A2 in the first embodiment was changed to 90 parts by weight, the PC-B1 was changed to 10 parts by weight, the C-1 was changed to 0.5 part by weight, and the kneading time was changed to 8 minutes. 1 is carried out in the same manner. The results are shown in Table 2.
  • Example 5 The same procedure as in Example 5 was carried out except that C-1 in Example 5 was changed to 2.5 parts by weight. The results are shown in Table 2.
  • Example 2 The same procedure as in Example 2 was carried out except that PC-A2 in Example 2 was changed to 75 parts by weight, PC-B3 was changed to 25 parts by weight, and C-1 was changed to 5 parts by weight. The results are shown in Table 2.
  • Example 2 The same procedure as in Example 2 was carried out except that PC-A2 in the second embodiment was changed to PC-A1 and PC-B1 was changed to PC-B2 and C-1 was changed to 10 parts by weight. The results are shown in Table 2.
  • Example 3 The same procedure as in Example 3 was carried out except that C-1 in Example 3 was changed to C-1. The results are shown in Table 2.
  • Example 3 The same procedure as in Example 3 was carried out except that 5 to 5 parts by weight of C-1 in Example 3 was changed to 10 parts by weight of C-2. The results are shown in Table 2.
  • Example 11 The same procedure as in Example 11 was carried out except that PC-A2 in Example 11 was changed to PC-A1. The results are shown in Table 2.
  • Example 3 The same procedure as in Example 2 was carried out except that 2.5 parts by weight of C-1 in Example 2 was changed to 1.25 parts by weight of C-3. The results are shown in Table 3.
  • Example 13 In the same manner as in Example 13, except that 1.25 parts by weight of C-3 in Example 13 was changed to 2.5 parts by weight. The results are shown in Table 3.
  • Example 2 The same procedure as in Example 2 was carried out except that 2.5 parts by weight of C-1 in Example 2 was changed to 7 parts by weight of C-4. The results are shown in Table 3.
  • Such a polycarbonate resin composition is excellent in transparency and has a high level of balance, and preferably has a biomass content, heat resistance, and mechanical strength.

Landscapes

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

Abstract

本发明涉及聚碳酸酯树脂组合物、其制造方法、成形体。该聚碳酸酯树脂组合物含有特定的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)，具有优异的透明性，并且高度均衡地兼备生物质含有率、耐热性及机械强度。

Description

聚碳酸酯树脂组合物、其制造方法、成形体 技术领域
本发明涉及一种透明性优异、生物质含有率、耐热性及机械强度可获得平衡的聚碳酸酯树脂组合物。
背景技术
含双酚A等化学结构的现有的芳香族聚碳酸酯树脂可使用由石油资源衍生的原料制造，但是，近年来由于担心石油资源枯竭，要求提供以植物等生物质资源为原料的聚碳酸酯树脂。另外，由于担心二氧化碳过量排放导致地球变暖会带来气候变化等问题，也要求开发废弃处理也呈碳中性的以植物来源单体为原料的聚碳酸酯树脂。
在这种情况下，已经有文献提出源自生物质资源二羟基化合物即异山梨醇(ISB)为单体成分，通过与碳酸二酯的酯交换反应，在减压条件下一边蒸馏除去副反应产生的单羟基化合物，一边得到聚碳酸酯树脂的制造方法(例如参照专利文献1～7)。
可是，ISB这样的二羟基化合物存在以下问题：与现有的芳香族聚碳酸酯树脂中所使用的双酚化合物相比，热稳定性低、在高温下进行的缩聚反应、成形、加工时因热分解导致树脂变黄。虽然专利文献3～6中所记载的ISB和双酚化合物的共聚物具有较高的玻璃化转变温度，但是ISB反应活性与双酚化合物的反应活性存在不同，双酚化合物更易成为共聚物端基。此时，若考虑色调、ISB的热稳定性而选择低于芳香族聚碳酸酯树脂的聚合温度下实施聚合反应，那么这种双酚化合物有时可成为一种封端基，无法充分提高聚合度，产物缺乏冲击韧性，这种情况在双酚化合物共聚量超过20摩尔％时较为显著。
进而，专利文献7公开了一种含有源自ISB结构单元、源自脂肪族二羟基化合物结构单元及源自芳香族双酚化合物结构单元的聚碳酸酯共聚物，但该聚碳酸酯共聚物虽然耐热性、成形性及机械强度优异，但由于含有源自双酚化合物的结构单元，因此，有时聚合度也未充分上升，成为缺乏冲击韧性的聚合物。另外，生物质含有率低，从环境保护方面考虑也不优选。
包含源自生物质二羟基化合物即异山梨醇(ISB)等二羟基化合物的聚碳酸酯树脂虽然玻璃化温度高且耐热性优异，但存在以下缺点：除分子链刚直以外，熔融聚合时粘度高，无法得到高分子量产物，因此，缺乏冲击韧性。为了改善韧性，有人尝试将脂肪族二羟基化合物或芳香族双酚化合物共聚。
具体而言，专利文献8公开了一种聚碳酸酯树脂组合物，其中包含由ISB和脂肪族 烃的二羟基化合物两种结构单元构成的聚碳酸酯和芳香族聚碳酸酯树脂，前一种聚碳酸酯中源自脂肪族烃的二羟基化合物的结构单元含量为45摩尔％以上。另外，在专利文献9中公开了一种聚碳酸酯树脂组合物，其在芳香族聚碳酸酯树脂中混合了含ISB和脂肪族烃的二羟基化合物结构单元的聚碳酸酯树脂，由此铅笔硬度优异。
现有技术文献
专利文献
专利文献1：国际公开第2004/111106号小册子
专利文献2：国际公开第2007/063823号小册子
专利文献3：国际公开第2005/066239号小册子
专利文献4：国际公开第2006/041190号小册子
专利文献5：日本特开2009-062501号公报
专利文献6：日本特开2009-020963号公报
专利文献7：日本特开2011-127108号公报
专利文献8：国际公开第2011/071162号小册子
专利文献9：国际公开第2012/1117212号小册子
发明内容
发明所要解决的课题
然而，存在以下问题：含脂肪族二羟基化合物共聚物的耐热性不足，含芳香族双酚化合物共聚物的耐热性虽高，但从反应活性方面考虑，无法得到足够分子量的聚碳酸酯树脂。因此，如专利文献8所述包含45摩尔％以上脂肪族二羟基化合物的ISB共聚聚碳酸酯树脂和芳香族聚碳酸酯树脂的树脂组合物虽然透明性、色相、热稳定性、成形性及机械强度优异，但如若为进一步提高耐热性将组合物的玻璃化转变温度提高到120℃以上，则需要将芳香族聚碳酸酯树脂的含有率提高至50重量％以上。这必然降低生物质含有率，因此，从环境方面考虑不优选。另外，如专利文献9所述在芳香族聚碳酸酯树脂中混合包含ISB和脂肪族烃的二羟基化合物两种结构单元的聚碳酸酯树脂，该聚碳酸酯树脂组合物实质上存在全光透射率低于20％、透明性差问题。
本发明是鉴于这种背景而完成的，提供一种透明性优异，并且以高水平均衡地兼备生物质含有率、耐热性、机械强度的聚碳酸酯树脂组合物、其制造方法、及聚碳酸酯树脂组合物的成形体。
用于解决课题的技术方案
本发明人等为了解决上述课题进行了潜心研究，结果发现，含有特定的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的聚碳酸酯树脂组合物具有优异的透明性，并且高度均衡地兼备生物质含有率、耐热性及机械强度，由此完成了本发明。本发明的要点在于下述[1]～[16]。
[1]一种聚碳酸酯树脂组合物，其中包括含有源自下述式(1)所示化合物结构单元的聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)及下述式(2)、(3)及(4)中的一种以上的化合物(C)，其特征在于，该化合物(C)的添加量相对于含有聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的树脂组合物100重量份其含有0.1重量份以上且10重量份以下。
[化学式1]
Figure PCTCN2015082743-appb-000001
[化学式2]
Figure PCTCN2015082743-appb-000002
(式中，R1及R2表示互相独立的碳原子数0～4的烷基或具有酰胺键的碳原子数0～4的烷基，X表示硫原子，或在R1或R2具有酰胺键的情况下表示碳原子数2～8的2价连接基团。R3、R4、R5及R6表示互相独立的氢原子或碳原子数1～4的烷基。)
[化学式3]
Figure PCTCN2015082743-appb-000003
(式中，R7表示取代或者非取代的碳原子数2～10的烷基，p表示4～45的整数。)
[化学式4]
Figure PCTCN2015082743-appb-000004
(式中，R8表示含有碳原子数1～18的脂肪族或芳香环的亚烷基。R9表示直链状或者环状的碳原子数1～20的羰基或芳香族羰基。n表示2～3的整数。)
[2]根据权利要求一所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树脂组合物经差示扫描量热分析测定只有一个玻璃化转变温度。
[3]根据权利要求一或二所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树脂组合物在厚度为1mm的成形体中的全光透过率为80％以上。
[4]根据权利要求三或四所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树脂组合物经差示扫描量热分析测定的玻璃化温度为90℃以上且200℃以下。
发明效果
本发明的聚碳酸酯树脂组合物及其成形体具有优异的透明性，并且高度均衡地兼备生物质含有率、耐热性及机械强度。本发明的聚碳酸酯树脂组合物由上述组份通过添加工序及反应工序而得到。
具体实施方式
以下，对本发明的实施方式详细地进行说明，但以下记载的构成要素的说明为本发明的实施方式的一个例子(代表例)，只要本发明不超出其要点，则不限定于以下的内容。
[聚碳酸酯树脂(A)]
上述聚碳酸酯树脂(A)优选为以相对于源自全部二羟基化合物的结构单元100摩尔％超过50摩尔％的比例含有源自下述式(1)所示二羟基化合物的结构单元(简称“结构单元(a)”)的聚碳酸酯树脂。聚碳酸酯树脂(A)可以为结构单元(a)的均聚碳酸酯树脂，也可以为将结构单元(a)以外的结构单元共聚而成的聚碳酸酯树脂。从优化冲击韧性的观点考虑，优选为共聚聚碳酸酯树脂。
[化学式5]
Figure PCTCN2015082743-appb-000005
作为上述式(1)所示的二羟基化合物，可以举出：处于立体异构体关系的异山梨醇(ISB)、异二缩甘露醇及异艾杜醇。这些二羟基化合物可以单独使用1种，也可以组合使用2种以上。
上述通式(1)所示的二羟基化合物中，从获得和制造的容易性、耐气候性、光学特性、成形性、耐热性及碳中性的方面考虑，最优选为植物来的丰富且易从各种淀粉转化的山梨糖醇进行脱水缩合而得到异山梨醇(ISB)。
需要说明的是，上述通式(1)所示的二羟基化合物容易被氧慢慢地氧化。因此，在保存或使用时，为了防止氧化分解，优选不混入水分并且使用脱氧剂或在氮气气氛下进行。
另外，聚碳酸酯树脂(A)优选为含有源自通式(1)所示的二羟基化合物的结构单元(a)， 与脂肪族烃的二羟基化合物、脂环式烃的二羟基化合物、或含有醚键的二羟基化合物中选取1种以上二羟基化合物的结构单元(简称“结构单元(b)”)的共聚聚碳酸酯树脂。这些二羟基化合物由于具有柔软的分子结构，因此，通过使用这些二羟基化合物作为原料，可提高聚碳酸酯树脂的冲击韧性。这些二羟基化合物中，优选使用使韧性提高效果较大的脂肪族烃的二羟基化合物、脂环式烃的二羟基化合物，最优选使用脂环式烃的二羟基化合物。作为脂肪族烃的二羟基化合物、脂环式烃的二羟基化合物、及含有醚键的二羟基化合物的具体例如下所述。
选用脂肪族烃的二羟基化合物包括：乙二醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,5-庚二醇、1,6-己二醇、1,9-壬二醇、1,10-癸二醇1,12-十二烷二醇等直链状脂肪族二羟基化合物；1,3-丁二醇、1,2-丁二醇、新戊二醇、己二醇等具有支链的脂肪族二羟基化合物。
选用脂环式烃的二羟基化合物包括：1,2-环己烷二甲醇、1,3-环己烷二甲醇、1,4-环己烷二甲醇、三环癸烷二甲醇、五环十五烷二甲醇、2,6-十氢化萘二甲醇、1,5-十氢化萘二甲醇、2,3-十氢化萘二甲醇、2,3-降冰片烷二甲醇、2,5-降冰片烷二甲醇、1,3-金刚烷二甲醇、柠檬烯等由萜烯化合物衍生的二羟基化合物等所例示的作为脂环式烃的伯醇的二羟基化合物；1,2-环己烷二醇、1,4-环己烷二醇、1,3-金刚烷二醇、氢化双酚A、2,2,4,4-四甲基-1,3-环丁二醇等所例示的作为脂环式烃的仲醇或叔醇的二羟基化合物。
含有醚键的二羟基化合物，可以举出：氧亚烷基二醇类或含有缩醛环的二羟基化合物。
作为氧亚烷基二醇类，例如可以采用二乙二醇、三乙二醇、四乙二醇、聚乙二醇及聚丙二醇等。
作为含有缩醛环的二羟基化合物，例如可以采用下述结构式(5)所示螺二醇或下述结构式(6)所示的二恶烷二醇等。
[化学式6]
Figure PCTCN2015082743-appb-000006
[化学式7]
Figure PCTCN2015082743-appb-000007
在上述聚碳酸酯树脂(A)中，上述结构单元(a)相对于源自全部二羟基化合物的结构单 元100摩尔％的含有比例优选超过50摩尔％，更优选为55摩尔％以上且95摩尔％以下，进一步优选为60摩尔％以上且90摩尔％以下，特别优选为65摩尔％以上且85摩尔％以下。在结构单元(a)的含有比例为50摩尔％以下的情况下，除生物质含有率变低以外，耐热性变得不充分。另一方面，结构单元(a)也可以为100摩尔％，但从提高分子量的观点及耐冲击性的观点考虑，优选进行共聚。
另外，上述聚碳酸酯树脂(A)可以进一步含有上述结构单元(a)及上述结构单元(b)以外的结构单元。作为这样的结构单元(二羟基化合物)，例如可以采用具有芳香族基团的二羟基化合物等。但是，在上述聚碳酸酯树脂(A)中含有源自含有芳香族基团的二羟基化合物的结构单元的情况下，由于前述理由，有可能无法得到高分子量的聚碳酸酯树脂，缺乏冲击韧性。因此，相对于源自全部二羟基化合物的结构单元100摩尔％，源自含有芳香族基团的二羟基化合物的结构单元的含有比例优选为10摩尔％以下，更优选为5摩尔％以下。
作为含有芳香族基团的二羟基化合物，例如可以采用以下的二羟基化合物，但也可以采用它们以外的二羟基化合物。2,2-双(4-羟基苯基)丙烷、2,2-双(3-甲基-4-羟基苯基)丙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、2,2-双(4-羟基-3,5-二乙基苯基)丙烷、2,2-双(4-羟基-(3-苯基)苯基)丙烷、2,2-双(4-羟基-(3,5-二苯基)苯基)丙烷、2,2-双(4-羟基-3,5-二溴苯基)丙烷、双(4-羟基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)戊烷、1,1-双(4-羟基苯基)-1-苯基乙烷、双(4-羟基苯基)二苯基甲烷、1,1-双(4-羟基苯基)-2-乙基己烷、1,1-双(4-羟基苯基)癸烷、双(4-羟基-3-硝基苯基)甲烷、3,3-双(4-羟基苯基)戊烷、1,3-双(2-(4-羟基苯基)-2-丙基)苯、1,3-双(2-(4-羟基苯基)-2-丙基)苯、2,2-双(4-羟基苯基)六氟丙烷、1,1-双(4-羟基苯基)环己烷、双(4-羟基苯基)砜、2,4’-二羟基二苯基砜、双(4-羟基苯基)硫醚、双(4-羟基-3-甲基苯基)硫醚、双(4-羟基苯基)二硫醚、4,4’-二羟基二苯基醚、4,4’-二羟基-3,3’-二氯二苯基醚等芳香族双酚化合物；2,2-双(4-(2-羟基乙氧基)苯基)丙烷、2,2-双(4-(2-羟基丙氧基)苯基)丙烷、1,3-双(2-羟基乙氧基)苯、4,4’-双(2-羟基乙氧基)联苯、双(4-(2-羟基乙氧基)苯基)砜等具有键合于芳香族基团的醚基的二羟基化合物；9,9-双(4-(2-羟基乙氧基)苯基)芴、9,9-双(4-羟基苯基)芴、9,9-双(4-羟基-3-甲基苯基)芴、9,9-双(4-(2-羟基丙氧基)苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-甲基苯基)芴、9,9-双(4-(2-羟基丙氧基)-3-甲基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-异丙基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-异丁基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-叔丁基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-环己基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-苯基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3,5-二甲基苯基)芴、9,9-双(4-(2-羟基乙氧基)-3-叔丁基-6-甲基苯基)芴、9,9-双(4-(3-羟基-2,2-二甲基丙氧基)苯基)芴等具有芴环的二羟基化合物。
上述其它的二羟基化合物可根据聚碳酸酯树脂所要求的特性适宜选择。另外，上述其它的二羟基化合物可以仅使用1种，也可以混合使用多种。通过将上述其它的二羟基化合物与上述式(1)所示的二羟基化合物并用，可得到聚碳酸酯树脂(A)的柔软性及机械物性的改善、以及成形性的改善等效果。
用作聚碳酸酯树脂(A)的原料的二羟基化合物可以含有还原剂、抗氧化剂、脱氧剂、光稳定剂、抗酸剂、pH稳定剂及热稳定剂等稳定剂。特别是上述式(1)所示的二羟基化合物具有在酸性状态下容易变质的性质，因此，通过在聚碳酸酯树脂(A)的合成过程中使用碱性稳定剂，可抑制上述式(1)所示的二羟基化合物的变质，进而可进一步提高得到的聚碳酸酯树脂组合物的品质。
作为碱性稳定剂，例如可以采用以下的化合物。长周期型周期表(Nomenclature of Inorganic Chemistry IUPAC Recommendations2005)中的IA族或IIA族金属的氢氧化物、碳酸盐、磷酸盐、亚磷酸盐、次磷酸盐、硼酸盐及脂肪酸盐；四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、三甲基乙基氢氧化铵、三甲基苄基氢氧化铵、三甲基苯基氢氧化铵、三乙基甲基氢氧化铵、三乙基苄基氢氧化铵、三乙基苯基氢氧化铵、三丁基苄基氢氧化铵、三丁基苯基氢氧化铵、四苯基氢氧化铵、苄基三苯基氢氧化铵、甲基三苯基氢氧化铵及丁基三苯基氢氧化铵等碱性铵化合物；二乙胺、二丁胺、三乙胺、吗啉、N-甲基吗啉、吡咯烷、哌啶、3-氨基-1-丙醇、乙二胺、N-甲基二乙醇胺、二乙基乙醇胺、二乙醇胺、三乙醇胺、4-氨基吡啶、2-氨基吡啶、N,N-二甲基-4-氨基吡啶、4-二乙基氨基吡啶、2-羟基吡啶、2-甲氧基吡啶、4-甲氧基吡啶、2-二甲氨基咪唑、2-甲氧基咪唑、咪唑、2-巯基咪唑、2-甲基咪唑及氨基喹啉等胺系化合物以及二(叔丁基)胺及2,2,6,6-四甲基哌啶等受阻胺系化合物。
上述二羟基化合物中的上述碱性稳定剂的含量没有特别限定，由于上述式(1)所示的二羟基化合物在酸性状态下不稳定，因此，优选设定碱性稳定剂的含量以使含有碱性稳定剂的二羟基化合物的水溶液的pH为7左右。
若碱性稳定剂的量过少，则有可能无法得到防止上述式(1)所示的二羟基化合物变质的效果。另一方面，若碱性稳定剂的量过多，则有时由于碱性稳定剂的原因而招致上述二羟基化合物的改性。为了避免这种问题，优选使碱性稳定剂相对于上述式(1)所示的二羟基化合物的含量为0.0001～1质量％，更优选为0.001～0.1质量％。
作为用于上述聚碳酸酯树脂[A]的原料的碳酸二酯，通常可采用下述通式(9)所示的化合物。这些碳酸二酯可单独使用1种，也可以并用2种以上。
[化学式8]
Figure PCTCN2015082743-appb-000008
在上述通式(9)中，A1及A2分别为取代或者非取代的碳原子数1～18的脂肪族烃基或取代或者非取代的芳香族烃基，A1和A2可以相同也可以不同。作为A1及A2，优选采用取代或者非取代的芳香族烃基，更优选采用非取代的芳香族烃基。
作为上述通式(9)所示的碳酸二酯，例如可以采用碳酸二苯酯(DPC)及碳酸二甲苯酯等取代碳酸二苯酯、碳酸二甲酯、碳酸二乙酯以及碳酸二叔丁酯等。这些碳酸二酯中，优选使用碳酸二苯酯或取代碳酸二苯酯，特别优选使用碳酸二苯酯。另外，碳酸二酯有时含有氯化物离子等杂质，杂质有时阻碍缩聚反应或使得到的聚碳酸酯树脂的色调变差，因此，因此根据需要优选使用利用蒸馏等进行了精制的碳酸二酯。
聚碳酸酯树脂(A)可通过利用酯交换反应使上述的二羟基化合物和碳酸二酯缩聚来合成。更详细而言，可通过在缩聚的同时将酯交换反应中副反应产生的单羟基化合物等去除到体系外而得到。
上述酯交换反应在酯交换反应催化剂(以下，将酯交换反应催化剂称为“聚合催化剂”。)的存在下进行。聚合催化剂的种类可对酯交换反应的反应速度及得到的聚碳酸酯树脂(A)的品质造成非常大的影响。
作为聚合催化剂，只要可满足得到的聚碳酸酯树脂(A)的透明性、色调、耐热性、耐气候性及机械强度就没有限定。作为聚合催化剂，例如可使用长周期型周期表中的IA族或IIA族(以下，记为“IA族”、“IIA族”。)的金属化合物、以及碱性硼化合物、碱性磷化合物、碱性铵化合物及胺系化合物等碱性化合物，其中，优选IA族金属化合物及/或IIA族金属化合物。
作为上述IA族金属化合物，例如可以采用以下的化合物。氢氧化钠、氢氧化钾、氢氧化锂、氢氧化铯、碳酸氢钠、碳酸氢钾、碳酸氢锂、碳酸氢铯、碳酸钠、碳酸钾、碳酸锂、碳酸铯、乙酸钠、乙酸钾、乙酸锂、乙酸铯、硬脂酸钠、硬脂酸钾、硬脂酸锂、硬脂酸铯、硼氢化钠、硼氢化钾、硼氢化锂、硼氢化铯、苯基化硼钠、苯基化硼钾、苯基化硼锂、苯基化硼铯、苯甲酸钠、苯甲酸钾、苯甲酸锂、苯甲酸铯、磷酸氢二钠、磷酸氢二钾、磷酸氢二锂、磷酸氢二铯、苯基磷酸二钠、苯基磷酸二钾、苯基磷酸二锂、苯基磷酸二铯；钠、钾、锂、铯的醇盐、酚盐；双酚A的二钠盐、二钾盐、二锂盐和二铯盐等。
作为IA族金属化合物，从聚合活性和得到的聚碳酸酯树脂的色调的观点考虑，优选锂化合物。
作为上述IIA族金属化合物，例如可以采用以下的化合物。氢氧化钙、氢氧化钡、氢氧化镁、氢氧化锶、碳酸氢钙、碳酸氢钡、碳酸氢镁、碳酸氢锶、碳酸钙、碳酸钡、碳酸镁、碳酸锶、乙酸钙、乙酸钡、乙酸镁、乙酸锶、硬脂酸钙、硬脂酸钡、硬脂酸镁及硬脂酸锶等。
作为IIA族金属化合物，优选镁化合物、钙化合物或钡化合物，从聚合活性和得到的聚碳酸酯树脂的色调的观点考虑，进一步优选镁化合物及/或钙化合物，最优选钙化合物。
另外，也可以与上述IA族金属化合物及/或IIA族金属化合物一同辅助性地并用碱性硼化合物、碱性磷化合物、碱性铵化合物及胺系化合物等碱性化合物，特别优选仅使用IA族金属化合物及/或IIA族金属化合物。
作为上述碱性磷化合物，例如可以采用以下的化合物。三乙基膦、三正丙基膦、三异丙基膦、三正丁基膦、三苯基膦、三丁基膦和季鏻盐等。
作为上述碱性铵化合物，例如可以采用以下的化合物。四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、三甲基乙基氢氧化铵、三甲基苄基氢氧化铵、三甲基苯基氢氧化铵、三乙基甲基氢氧化铵、三乙基苄基氢氧化铵、三乙基苯基氢氧化铵、三丁基苄基氢氧化铵、三丁基苯基氢氧化铵、四苯基氢氧化铵、苄基三苯基氢氧化铵、甲基三苯基氢氧化铵及丁基三苯基氢氧化铵等。
作为上述胺系化合物，例如可以采用以下的化合物。4-氨基吡啶、2-氨基吡啶、N,N-二甲基-4-氨基吡啶、4-二乙基氨基吡啶、2-羟基吡啶、2-甲氧基吡啶、4-甲氧基吡啶、2-二甲氨基咪唑、2-甲氧基咪唑、咪唑、2-巯基咪唑、2-甲基咪唑、氨基喹啉及胍等。
上述聚合催化剂的使用量优选每1mol用于反应的全部二羟基化合物为0.1～300μmol，更优选为0.5～100μmol，特别优选为1～50μmol。
作为聚合催化剂，在使用含有选自由长周期型周期表中的IIA族金属及锂构成的组中的至少1种金属的化合物的情况下，特别是在使用镁化合物及/或钙化合物的情况下，聚合催化剂的使用量以含有该金属的化合物的金属原子量计，优选每1mol用于反应的全部二羟基化合物为0.1μmol以上，更优选0.3μmol以上，特别优选0.5μmol以上。另外，作为上限，优选10μmol以下，更优选5μmol以下，特别优选3μmol以下。
若聚合催化剂的使用量过少，则聚合速度变慢，因此，要想得到期望的分子量的聚碳酸酯树脂，不得不相应地提高聚合温度。因此，得到的聚碳酸酯树脂(A)的色调变差的有可能变高，或未反应的原料在聚合途中挥发而导致二羟基化合物和碳酸二酯的摩尔比率被破坏，有可能无法达到期望的分子量。另一方面，若聚合催化剂的使用量过多，则有可 能并发不优选的副反应，招致得到的聚碳酸酯树脂(A)的色调恶化或成形加工时的树脂着色。
另外，IA族金属中，若钠、钾或铯大量含于聚碳酸酯树脂中，则有可能对色调造成不良影响。另外，若铁大量含于聚碳酸酯树脂中，则也同样有可能对色调造成不良影响。而且，这些金属不仅会来自使用的催化剂、而且还会从原料或反应装置中混入。不论出处，聚碳酸酯树脂(A)中的这些金属的化合物的合计量优选以钠、钾、铯及铁的合计含量计为1质量ppm以下，进一步优选为0.5质量ppm以下。
(聚碳酸酯树脂(A)的合成)
聚碳酸酯树脂(A)可通过在聚合催化剂的存在下，通过酯交换反应使上述式(1)所示的二羟基化合物等用作原料的二羟基化合物和碳酸二酯缩聚而得到。
作为原料的二羟基化合物和碳酸二酯优选在酯交换反应前均匀地混合。混合的温度通常为80℃以上，优选为90℃以上，且通常为250℃以下，优选为200℃以下，进一步优选为150℃以下的范围，其中，优选100℃以上且120℃以下。若混合的温度过低，则有可能溶解速度慢或溶解度不足，常常会招致固化等不良情况。另一方面，若混合的温度过高，则有时招致二羟基化合物的热劣化，结果有可能使得到的聚碳酸酯树脂(A)的色调变差，或对耐气候性造成不良影响。
从抑制色调恶化及反应活性降低的观点考虑，混合原料的二羟基化合物和碳酸二酯的操作优选在氧浓度10vol％以下、进而0.0001～10vol％、尤其是0.0001～5vol％、特别是0.0001～1vol％的气氛下进行。
为了得到聚碳酸酯树脂(A)，相对于用于反应的全部二羟基化合物，优选以0.90～1.20的摩尔比率使用碳酸二酯，更优选以0.95～1.10的摩尔比率使用碳酸二酯。若该摩尔比率变小，则有可能所制造的聚碳酸酯树脂(A)的羟基末端量增加，从而聚合物的热稳定性变差，在成形时导致着色，或酯交换反应的速度降低、或无法得到期望的高分子量体。
另外，若该摩尔比率变大，则有时酯交换反应的速度降低，或难以制造期望的分子量的聚碳酸酯树脂(A)。酯交换反应速度的降低导致反应受热过程增加，因此有可能使得到的聚碳酸酯树脂(A)的色调、耐气候性变差。进而，若碳酸二酯相对于全部二羟基化合物的摩尔比率增大，则有时聚碳酸酯树脂(A)中的残存碳酸二酯量增加，招致成形时的污染或臭味的问题，不优选。
使二羟基化合物和碳酸二酯缩聚的方法在上述催化剂存在下使用多个反应器以多阶段实施。反应的形式可以为分批式或连续式、或者分批式和连续式的组合方法，优选采用能够以更少的受热过程得到聚碳酸酯树脂，且生产效率也以连续式为优。
从聚合速度的控制及得到的聚碳酸酯树脂(A)的品质的观点考虑，重要的是根据反应阶段适当地选择夹套温度和内温、反应体系内的压力。具体而言，优选在缩聚反应的反应初期在相对低温、低真空下得到预聚物，在反应后期在相对高温、高真空使分子量上升至规定的值。例如，若在缩聚反应的进度达到规定的值之前温度、压力的任一方变化过快，则招致未反应的单体馏出，有可能使二羟基化合物和碳酸二酯的摩尔比率偏离期望的比率。其结果，有可能招致聚合速度的降低或无法得到具有期望的分子量或末端基团的聚合物。
另外，缩聚反应中的聚合速度由羟基末端和碳酸酯基末端的平衡控制。因此，若末端基团的平衡因未反应单体的馏出而发生变动，则有可能难以将聚合速度控制为一定或得到的树脂的分子量的变动变大。树脂的分子量由于与熔融粘度相关，因此，在熔融加工时，有时因熔融粘度发生变动，难以维持成形品的品质。这种问题在以连续式进行缩聚反应时特别容易产生。
为了抑制馏出的未反应单体的量，有效的办法是在聚合反应器中使用回流冷凝器，特别是在未反应单体多的反应初期显示较高的效果。导入至回流冷凝器的制冷剂的温度可以根据使用的单体适宜选择，通常导入至回流冷凝器的制冷剂的温度在该回流冷凝器的入口为45～180℃、优选为80～150℃，特别优选为100～130℃。若制冷剂的温度过高，则回流量减少，其效果降低，相反若该温度过低，则有时本来应该蒸馏除去的单羟基化合物的蒸馏除去效率降低，招致反应率的降低及得到的树脂的着色。作为制冷剂，可使用温水、蒸气、热介质油等，优选蒸气、热介质油。
为了在将聚合速度维持在适当速度、抑制单体的馏出的同时，不损害得到的聚碳酸酯树脂(A)的色调，重要的是上述的聚合催化剂的种类和量的选定。
聚碳酸酯树脂(A)使用聚合催化剂并通常经过2阶段以上的工序来制造。缩聚反应可以使用1个缩聚反应器并依次改变条件以2阶段以上的工序进行，但从生产效率的观点考虑，优选使用多个反应器并改变各自的条件以多阶段进行。
从高效地进行缩聚反应的观点考虑，重要的是在反应液中所含的单体多的反应初期一边维持必要的聚合速度一边抑制单体的挥发。另外，在反应后期，重要的是通过充分蒸馏除去副反应产生的单羟基化合物使平衡向缩聚反应侧移动。因此，在反应初期优选的反应条件和在反应后期优选的反应条件通常不同。因此，通过使用串联配置的多个反应器，可容易地变更各自的条件，提高生产效率。
聚碳酸酯树脂(A)的制造中所使用的聚合反应器如上所述只要为至少2个以上即可，但从生产效率等观点考虑为3个以上，优选为3～5个，特别优选为4个。若聚合反应器为 2个以上，则在各聚合反应器中可以进一步进行多个条件不同的反应阶段或连续地改变温度、压力。
聚合催化剂可以添加于原料制备槽或原料贮槽，也可以直接添加于聚合反应器。从供给的稳定性、缩聚反应的控制的观点考虑，优选在供给至聚合反应器之前的原料管线的中途设置催化剂供给管线并以水溶液供给聚合催化剂。
若缩聚反应的温度过低，则招致生产率的降低或施加于制品的受热过程增大，若该温度过高，则不仅招致单体的挥发，而且有可能助长聚碳酸酯树脂(A)的分解或着色。具体而言，作为第1段反应中的反应条件，可以采用以下的条件。即，聚合反应器的内温的最高温度通常在150～250℃、优选在160～240℃、进一步优选在170～230℃的范围设定。另外，聚合反应器的压力(以下，压力表示绝对压力)通常在1～110kPa、优选在5～70kPa，进一步优选在7～30kPa的范围设定。另外，反应时间通常在0.1～10小时、优选在0.5～3小时的范围设定。第1段反应一边将产生的单羟基化合物蒸馏去除至反应体系外一边实施。
第2段以后，将反应体系的压力从第1段的压力慢慢地降低，一边持续将产生的单羟基化合物去除到反应体系外一边使最终反应体系的压力(绝对压力)为1kPa以下。另外，聚合反应器的内温的最高温度通常在200～260℃、优选在210～250℃的范围设定。另外，反应时间通常在0.1～10小时、优选在0.3～6小时、特别优选在0.5～3小时的范围设定。
若过度提高聚合温度、延长聚合时间，则存在得到的聚碳酸酯树脂(A)的色调变差的倾向。特别是为了抑制聚碳酸酯树脂(A)的着色或热劣化、得到色调良好的聚碳酸酯树脂(A)，优选将全部反应阶段中的聚合反应器的内温的最高温度设为210～240℃。为了抑制反应后半段的聚合速度的降低，将受热过程所致的劣化控制在最小限度，优选在缩聚反应的最终阶段使用在栓塞流性和界面更新性优异的卧式反应器。
在连续聚合中，为了将最终得到的聚碳酸酯树脂(A)的分子量控制为一定水准，有必要根据需要调节聚合速度。此时，调整最终阶段的聚合反应器的压力为操作性良好的方法。
另外，如上所述由于聚合速度因羟基末端和碳酸酯基末端的比率发生变化，因此，可以有意地减少一方的末端基团，抑制聚合速度，相应地将最终阶段的聚合反应器的压力保持为高真空，由此可减少以单羟基化合物为代表的树脂中的残存低分子成分。但是，此时，若一方的末端过少，则仅由于末端基团平衡稍微变动，反应性会极端降低，得到的聚碳酸酯树脂(A)的分子量有可能无法满足期望的分子量。为了避免这种问题，最终阶段的聚合反应器中得到的聚碳酸酯树脂(A)优选羟基末端和碳酸酯基末端均含有10mol/ton以上。另一方面，若两方的末端基团过多，则聚合速度变快，分子量变动过高，因此，一方 的末端基团优选为60mol/ton以下。
通过如上将末端基的量和最终阶段的聚合反应器的压力调整为优选的范围，可在聚合反应器的出口减少树脂中的单羟基化合物的残存量。聚合反应器的出口中的树脂中的单羟基化合物的残存量优选为2000质量ppm以下，更优选为1500质量ppm以下，进一步优选为1000质量ppm以下。通过如上减少聚合反应器的出口中的单羟基化合物的含量，可在之后工序中容易地进行单羟基化合物等的脱挥。
单羟基化合物的残存量优选较少，但若减少至低于100质量ppm，则需要采用极端地减少一方的末端基团的量，且将聚合反应器的压力保持为高真空这样的运行条件。此时，如上所述，难以将得到的聚碳酸酯树脂(A)的分子量保持为一定水准，因此，通常为100质量ppm以上，优选为150质量ppm以上。
从资源有效利用的观点考虑，副反应产生的单羟基化合物优选在根据需要进行精制后作为其它化合物的原料进行再利用。例如在单羟基化合物为苯酚的情况下，可用作碳酸二苯酯或双酚A等的原料。
聚碳酸酯树脂(A)的玻璃化转变温度优选90℃以上。玻璃化转变温度低于90℃时，树脂组合物，有可能难以取得耐热性和生物质含有率的平衡。从进一步提高耐热性和生物质含有率的平衡的观点考虑，聚碳酸酯树脂(A)的玻璃化温度更优选100℃以上，进一步优选110℃以上，特别优选120℃以上。另一方面，聚碳酸酯树脂(A)的玻璃化转变温度优选170℃以下。在玻璃化温度超过170℃的情况下，聚合过程的熔融粘度变高，难以得到足够分子量的聚合物。另外，通过提高聚合温度来降低熔融粘度、提高分子量方法因构成结构单元(a)的耐热性不足，有可能容易着色。从提高分子量和防止着色的均衡性观点考虑，聚碳酸酯树脂(A)的玻璃化转变温度更优选165℃以下，进一步优选160℃以下，特别优选150℃以下。
聚碳酸酯树脂(A)的分子量可以以还原粘度表示，还原粘度越高，表示分子量越大。若聚碳酸酯树脂(A)的还原粘度过低，则成形品的机械强度有可能变低。因此，还原粘度通常为0.30dL/g以上，优选为0.33dL/g以上。另一方面，若还原粘度过大，则存在成形时流动性降低、生产率或加工性能降低的倾向。因此，还原粘度通常为1.20dL/g以下，优选为1.00dL/g以下，进一步优选为0.80dL/g以下。另外，聚碳酸酯树脂(A)的还原粘度使用以二氯甲烷作为溶剂将树脂组合物的浓度精密地调整为0.6g/dL的溶液，利用乌伯娄德粘度管在温度20.0℃±0.1℃的条件下测得的值。对于还原粘度的测定方法的详细情况在实施例中进行说明。
聚碳酸酯树脂(A)的熔融粘度优选400Pa·s以上且3000Pa·s以下，进一步优选600Pa· s以上且2500Pa·s以下，特别优选800Pa·s以上且2000Pa·s以下。若聚碳酸酯树脂(A)的熔融粘度低于上述范围，则有可能树脂组合物的成形品变脆，无法成为具有充分的机械物性的材料。另一方面，若熔融粘度高于上述范围，则有可能在成形加工时流动不足而损害成形品的外观，或尺寸精度变差。另外，存在因剪切发热使树脂温度上升而产生着色或发泡的担心。另外，在本说明书中，所谓熔融粘度是指使用毛细管流变仪[东洋精机(株)制]测得的温度240℃、剪切速度91.2sec-1下的熔融粘度。对于熔融粘度的测定方法的详细情况在后述的实施例中进行说明。
聚碳酸酯树脂(A)优选含有催化剂失活剂。作为催化剂失活剂，只要为酸性物质且具有聚合催化剂的失活功能就没有特别限定，例如可以举出：磷酸、磷酸三甲酯、磷酸三乙酯、亚磷酸、辛基磺酸四丁基锍盐、苯磺酸四甲基锍盐、苯磺酸四丁基锍盐、十二烷基苯磺酸四丁基锍盐、对甲苯磺酸四丁基锍盐这样的锍盐；癸基磺酸四甲基铵盐、十二烷基苯磺酸四丁基铵盐这样的铵盐；及苯磺酸甲酯、苯磺酸丁酯、对甲苯磺酸甲酯、对甲苯磺酸丁酯、十六烷基磺酸乙酯这样的烷基酯等。
上述催化剂失活剂优选包含含有下述结构式(10)或下述结构式(11)所示的部分结构中的任一者的磷系化合物(以下，称为“特定磷系化合物”。)。上述特定磷系化合物在缩聚反应结束后，即例如在混炼工序或颗粒化工序等时添加，由此使后述的聚合催化剂失活，可抑制其以后缩聚反应不必要地进行。其结果，可抑制在成形工序等中加热聚碳酸酯树脂(A)时的缩聚的进行，进而可抑制上述单羟基化合物的脱离。另外，通过使聚合催化剂失活，可抑制高温下的聚碳酸酯树脂(A)的着色。
[化学式9]
Figure PCTCN2015082743-appb-000009
[化学式10]
Figure PCTCN2015082743-appb-000010
作为含有上述结构式(10)或结构式(11)所示的部分结构的特定磷系化合物，可以采用磷酸、亚磷酸、膦酸、次磷酸、聚磷酸、膦酸酯、酸性磷酸酯等。特定磷系化合物中，催化剂失活和着色抑制的效果进一步优异的是亚磷酸、膦酸、膦酸酯，特别优选亚磷酸。
作为膦酸，例如可以采用以下的化合物。膦酸(亚磷酸)、甲基膦酸、乙基膦酸、乙烯基膦酸、癸基膦酸、苯基膦酸、苄基膦酸、氨基甲基膦酸、亚甲基二膦酸、1-羟基乙烷-1,1-二膦酸、4-甲氧基苯基膦酸、氮川三(亚甲基膦酸)、丙基膦酸酐等。
作为膦酸酯，例如可以采用以下的化合物。膦酸二甲酯、膦酸二乙酯、膦酸双(2-乙基己)酯、膦酸二月桂酯、膦酸二油烯酯、膦酸二苯酯、膦酸二苄酯、甲基膦酸二甲酯、甲基膦酸二苯酯、乙基膦酸二乙酯、苄基膦酸二乙酯、苯基膦酸二甲酯、苯基膦酸二乙酯、苯基膦酸二丙酯、(甲氧基甲基)膦酸二乙酯、乙烯基膦酸二乙酯、羟基甲基膦酸二乙酯、(2-羟基乙基)膦酸二甲酯、对甲基苄基膦酸二乙酯、二乙基膦酰基乙酸、二乙基膦酰基乙酸乙酯、二乙基膦酰基乙酸叔丁酯、(4-氯苄基)膦酸二乙酯、氰基膦酸二乙酯、氰基甲基膦酸二乙酯、3,5-二叔丁基-4-羟基苄基膦酸二乙酯、二乙基膦酰基乙醛二乙基缩醛、(甲基硫代甲基)膦酸二乙酯等。
作为酸性磷酸酯，例如可以采用以下的化合物。磷酸二甲酯、磷酸二乙酯、磷酸二乙烯酯、磷酸二丙酯、磷酸二丁酯、磷酸双(丁氧基乙基)酯、磷酸双(2-乙基己基)酯、磷酸二异三癸基酯、磷酸二油烯酯、磷酸二硬脂酯、磷酸二苯酯、磷酸二苄酯等磷酸二酯、或二酯和单酯的混合物、氯磷酸二乙酯、磷酸硬脂酯锌盐等。
上述特定磷系化合物可单独使用1种，也可以以任意的组合及比率混合使用2种以上。
上述聚碳酸酯树脂(A)中的特定磷系化合物的含量以磷原子计优选为0.1质量ppm以上且5质量ppm以下。若上述特定磷系化合物的含量过少，则催化剂失活及着色抑制的效果有可能变得不充分。另一方面，若上述特定磷系化合物的含量过多，则聚碳酸酯树脂(A)反而有可能着色。另外，此时，特别是在高温、高湿度的耐久试验中，聚碳酸酯树脂(A)容易着色。
另外，上述特定磷系化合物通过根据聚合催化剂的量调节含量，可更可靠地得到催 化剂失活及着色抑制的效果。上述特定磷系化合物的含量相对于聚合催化剂的金属原子1mol，优选以磷原子的量计为0.5倍mol以上且5倍mol以下，更优选为0.7倍mol以上且4倍mol以下，特别优选为0.8倍mol以上且3倍mol以下。
[芳香族聚碳酸酯树脂(B)]
上述芳香族聚碳酸酯树脂(B)为将源自下述通式(12)所示的芳香族二羟基化合物的结构单元作为主结构单元的聚碳酸酯树脂。
[化学式11]
Figure PCTCN2015082743-appb-000011
上述通式(12)中的R1～R8分别独立地表示氢原子或取代基。Y表示单键或2价基团。作为通式(12)中的R1～R8的取代基，表示可以具有取代基的碳原子数1～10的烷基、可以具有取代基的碳原子数1～10的烷氧基、卤素基团、碳原子数1～10的卤代烷基、或可以具有取代基的碳原子数6～20的芳香族基团。其中，优选可以具有取代基的碳原子数1～10的烷基或可以具有取代基的碳原子数6～20的芳香族基团。作为通式(12)中的Y的2价基团，可以举出：可以具有取代基的碳原子数1～6的链状结构的亚烷基、可以具有取代基的碳原子数1～6的链状结构的烷叉基、可以具有取代基的碳原子数3～6的环状结构的亚烷基、可以具有取代基的碳原子数3～6的环状结构的烷叉基、-O-、-S-、-CO-或-SO2-。在此，作为取代基，只要不阻碍本发明的效果就没有特别限定，通常分子量为200以下。另外，作为碳原子数1～6的链状结构的亚烷基所具有的取代基，优选芳基，特别优选苯基。芳香族聚碳酸酯树脂(B)可以为均聚物，也可以为共聚物，在为共聚物的情况下，优选为源自二羟基化合物的总结构单元中源自所述通式(2)所示的二羟基化合物的结构单元最多的聚碳酸酯树脂。在芳香族聚碳酸树脂(B)中，源自上述通式(2)所示的二羟基化合物的结构单元相对于源自全部二羟基化合物的总结构单元100摩尔％的含有比率更优选为50摩尔％以上，进一步优选为70摩尔％以上，特别优选为90摩尔％以上。
另外，芳香族聚碳酸酯树脂(B)可以为支链结构，也可以为直链结构，还可以为支链结构和直链结构的混合物。进而，芳香族聚碳酸酯树脂(B)也可以含有源自具有上述通式(1)所示的部位的二羟基化合物的结构单元。但是，在含有源自具有上述通式(1)所示的部位的二羟基化合物的结构单元的情况下，可使用与聚碳酸酯树脂(A)不同的结构单元的聚碳酸酯树脂。
源自构成芳香族聚碳酸酯树脂(B)的二羟基化合物的结构单元为从二羟基化合物的羟 基中去除了氢原子的结构单元。作为相当的二羟基化合物的具体例，可以举出下述的二羟基化合物。
4,4’-联苯酚、2,4’-联苯酚、3,3’-二甲基-4,4’-二羟基-1,1’-联苯、3,3’-二甲基-2,4’-二羟基-1,1’-联苯、3,3’-二(叔丁基)-4,4’-二羟基-1,1’-联苯、3,3’,5,5’-四甲基-4,4’-二羟基-1,1’-联苯、3,3’,5,5’-四-(叔丁基)-4,4’-二羟基-1,1’-联苯、2,2’,3,3’,5,5’-六甲基-4,4’-二羟基-1,1’-联苯等联苯化合物。
双(4-羟基-3,5-二甲基苯基)甲烷、双(4-羟基苯基)甲烷、双(4-羟基-3-甲基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、1,1-双(4-羟基苯基)丙烷、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟基苯基)丁烷、2,2-双(4-羟基苯基)戊烷、2,2-双(4-羟基苯基)-3-甲基丁烷、2,2-双(4-羟基苯基)己烷、2,2-双(4-羟基苯基)-4-甲基戊烷、1,1-双(4-羟基苯基)环戊烷、1,1-双(4-羟基苯基)环己烷、双(3-苯基-4-羟基苯基)甲烷、1,1-双(3-苯基-4-羟基苯基)乙烷、1,1-双(3-苯基-4-羟基苯基)丙烷、2,2-双(3-苯基-4-羟基苯基)丙烷、1,1-双(4-羟基-3-甲基苯基)乙烷、2,2-双(4-羟基-3-乙基苯基)丙烷、2,2-双(4-羟基-3-异丙基苯基)丙烷、2,2-双(4-羟基-3-仲丁基苯基)丙烷、1,1-双(4-羟基-3,5-二甲基苯基)乙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、1,1-双(4-羟基-3,6-二甲基苯基)乙烷、双(4-羟基-2,3,5-三甲基苯基)甲烷、1,1-双(4-羟基-2,3,5-三甲基苯基)乙烷、2,2-双(4-羟基-2,3,5-三甲基苯基)丙烷、双(4-羟基-2,3,5-三甲基苯基)苯基甲烷、1,1-双(4-羟基-2,3,5-三甲基苯基)苯基乙烷、1,1-双(4-羟基-3,3,5-三甲基苯基)环己烷、双(4-羟基苯基)苯基甲烷、1,1-双(4-羟基苯基)-1-苯基乙烷、1,1-双(4-羟基苯基)-1-苯基丙烷、双(4-羟基苯基)二苯基甲烷、双(4-羟基苯基)二苄基甲烷、4,4’-[1,4-亚苯基双(1-甲基亚乙基)]双[苯酚]、4,4’-[1,4-亚苯基双亚甲基]双[苯酚]、4,4’-[1,4-亚苯基双(1-甲基亚乙基)]双[2,6-二甲基苯酚]、4,4’-[1,4-亚苯基双亚甲基]双[2,6-二甲基苯酚]、4,4’-[1,4-亚苯基双亚甲基]双[2,3,6-三甲基苯酚]、4,4’-[1,4-亚苯基双(1-甲基亚乙基)]双[2,3,6-三甲基苯酚]、4,4’-[1,3-亚苯基双(1-甲基亚乙基)]双[2,3,6-三甲基苯酚]、4,4'-二羟基二苯基醚、4,4'-二羟基二苯基砜、4,4'-二羟基二苯基硫醚、3,3’,5,5’-四甲基-4,4’-二羟基二苯基醚、3,3’,5,5’-四甲基-4,4’-二羟基二苯基砜、3,3’,5,5’-四甲基-4,4’-二羟基二苯硫醚酚酞、4,4'-[1,4-亚苯基双(1-甲基亚乙烯基)]双酚、4,4'-[1,4-亚苯基双(1-甲基亚乙烯基)]双[2-甲基苯酚]、(2-羟基苯基)(4-羟基苯基)甲烷、(2-羟基-5-甲基苯基)(4-羟基-3-甲基苯基)甲烷、1,1-(2-羟基苯基)(4-羟基苯基)乙烷、2,2-(2-羟基苯基)(4-羟基苯基)丙烷、1,1-(2-羟基苯基)(4-羟基苯基)丙烷等双酚化合物。
2,2-双(3,5-二溴-4-羟基苯基)丙烷、2,2-双(3,5-二氯-4-羟基苯基)丙烷等卤代双酚化合物。
作为其中优选的二羟基化合物，可以举出：双(4-羟基-3,5-二甲基苯基)甲烷、双(4-羟基苯基)甲烷、双(4-羟基-3-甲基苯基)甲烷、1,1-双(4-羟基苯基)乙烷、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、1,1-双(4-羟基苯基)环己烷、1,1-双(4-羟基-3,3,5-三甲基苯基)环己烷、双(4-羟基苯基)苯基甲烷、1,1-双(4-羟基苯基)-1-苯基乙烷、1,1-双(4-羟基苯基)-1-苯基丙烷、双(4-羟基苯基)二苯基甲烷、2-羟基苯基(4-羟基苯基)甲烷、2,2-(2-羟基苯基)(4-羟基苯基)丙烷。
其中，特别优选双(4-羟基苯基)甲烷、双(4-羟基-3-甲基苯基)甲烷、双(4-羟基-3,5-甲基苯基)甲烷、2,2-双(4-羟基苯基)丙烷、2,2-双(4-羟基-3-甲基苯基)丙烷、2,2-双(4-羟基-3,5-二甲基苯基)丙烷、1,1-双(4-羟基苯基)环己烷、1,1-双(4-羟基-3,3,5-三甲基苯基)环己烷。
芳香族聚碳酸酯树脂(B)的制造方法可使用光气法、酯交换法、吡啶法等以往已知的任一方法。以下，作为一例，对利用酯交换法的芳香族聚碳酸酯树脂(B)的制造方法进行说明。
酯交换法为添加二羟基化合物、碳酸二酯、碱性催化剂、以及中和该碱性催化剂的酸性物质进行熔融酯交换缩聚的制造方法。作为二羟基化合物，可以举出上述例示的联苯化合物、双酚化合物。
作为碳酸二酯的代表例，可以举出：碳酸二苯酯、碳酸二甲苯酯、碳酸双(氯苯)酯、碳酸间甲苯酯、碳酸二萘基酯、碳酸双(联苯)酯、碳酸二乙酯、碳酸二甲酯、碳酸二丁酯、碳酸二环己酯等。其中，特别优选使用碳酸二苯酯。
从力学特性和成形加工性的平衡考虑，芳香族聚碳酸酯树脂(B)的粘均分子量通常为8,000以上且30,000以下，优选为10,000以上且25,000以下的范围。另外，芳香族聚碳酸酯树脂(B)的还原粘度使用二氯甲烷作为溶剂，将聚碳酸酯浓度精密地调整为0.60g/dl，在温度20.0℃±0.1℃下进行测定，通常为0.23dl/g以上且0.72dl/g以下，优选在0.27dl/g以上0.61dl/g以下的范围内。
另外，在本发明中，芳香族聚碳酸酯树脂(B)可仅单独使用1种，或混合使用2种以上。
[化合物(C)]
上述化合物(C)为选自下述式(2)、(3)及(4)中的一种以上的化合物。
通式(2)所示的化合物为下述式(2)所示的化合物。
[化学式12]
Figure PCTCN2015082743-appb-000012
(式中，R1及R2表示互相独立的碳原子数0～4的烷基或具有酰胺键的碳原子数0～4的烷基，X表示硫原子，或在R1或R2具有酰胺键的情况下表示碳原子数2～8的2价连接基团。R3、R4、R5及R6表示互相独立的氢原子或碳原子数1～4的烷基。)
具体而言，可以举出：4,4'-硫代双(2-叔丁基-5-甲基苯基)＝k300(Sumilizer WX-R)、4,4’-硫代双(2,6-二叔丁基苯基)、4,4’-[硫代双(亚甲基)]双[2,6-双(1,1-二甲基乙基)苯酚]、硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]＝k1098(IRGANOX1035)等。其中，优选4,4'-硫代双(2-叔丁基-5-甲基苯基)及硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
通式(3)所示的化合物为下述式(3)所示的化合物。
[化学式13]
Figure PCTCN2015082743-appb-000013
(式中，R7表示取代或者非取代的碳原子数2～10的烷基，p表示4～45的整数。)＝相当于分子量200～2000
具体而言，可以举出：聚乙二醇、聚丙二醇等，但并不受这些化合物任何限定。作为通式(3)所示的化合物，优选分子量200～2000的聚乙二醇，特别优选分子数600～1500的聚乙二醇。这些可单独使用1种，也可以并用2种以上。
通式(4)所示的化合物为下述式(4)所示的化合物。
[化学式13]
Figure PCTCN2015082743-appb-000014
(式中，R8表示含有碳原子数1～18的脂肪族或芳香环的亚烷基。R9表示直链状或者环状的碳原子数1～20的羰基或芳香族羰基。n表示2～3的整数。)
上述化合物(C)的添加量相对于含有聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的树脂组合物100重量份为0.1重量份以上且10重量份以下。优选为0.5重量份以上，进一步优选为1重量份以上。另外，优选为8重量份以下，进一步优选为5重量份以下。添加量 低于0.1重量份时，透明化的效果不充分，若多于10重量份，则有时虽然透明化，但着色显著，分子量的降低也较大，机械强度不充分。
对上述化合物(C)的添加方法而言，固体的化合物可在固体的状态下供给，可溶解于水或溶剂的化合物可形成水溶液或溶液进行供给。另外，可以添加于聚碳酸酯树脂原料，在水溶液或溶液的情况下，可以从挤出机的原料投入口投入，也可以使用泵等从料筒添加液体。
[聚碳酸酯树脂组合物]
上述聚碳酸酯树脂组合物优选将其成形而成的厚度2mm的成形体的厚度方向的全光透过率为80％以上。上述全光透过率更优选85％以上，进一步优选88％以上，特别优选90％以上。另外，总光线透射率的测定方法在后述的实施例中进行说明。雾度也可通过与全光透过率同样的方法进行测定。
另外，在聚碳酸酯树脂组合物中，优选以DSC法测定呈单一的玻璃化转化温度。此外，聚碳酸酯树脂组合物的玻璃化转变温度优选100℃以上且200℃以下。在玻璃化转变温度低于100℃的情况下，有可能在耐湿热性试验或耐气候性试验时发生变形。另一方面，若玻璃化转变温度超过200℃，则聚碳酸酯树脂(A)成分容易热分解，若在成形时长期滞留，则有可能产生银条纹或发泡等外观不良。在制造树脂组合物时，聚碳酸酯树脂(A)有可能受到热劣化而导致耐冲击性降低。聚碳酸酯树脂的玻璃化转变温度更优选110℃以上且190℃以下，进一步优选120℃以上且180℃以下。
显示上述规定的全光透过率及玻璃化转变温度的聚碳酸酯树脂组合物包含含有源自上述式(1)所示的化合物的结构单元的聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)和上述特定的化合物(C)，可通过将该化合物(C)的含量调整为上述规定的范围来实现。
上述聚碳酸酯树脂组合物中的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的配合比可根据期望的物性任意地选择。从提高生物质含有率的观点考虑，聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的重量比(A/B)优选为95/5～50/50，更优选为90/10～60/40。若偏离上述范围，则有可能难以较好地均衡耐热性、耐冲击性及生物质含有率。
[其它的添加剂]
上述聚碳酸酯树脂组合物中可添加各种添加剂。作为上述添加剂，有染颜料、抗氧化剂、UV吸收剂、光稳定剂、脱模剂、热稳定剂、阻燃剂、阻燃助剂、无机填充剂、冲击改良剂、水解抑制剂、发泡剂、成核剂等，可使用聚碳酸酯树脂中通常使用的添加剂。
“染颜料”
作为染颜料，可以举出：无机颜料、有机颜料、及有机染料等有机染颜料。
作为无机颜料，具体而言，例如可以举出：炭黑；氧化钛、锌华、氧化铁红、氧化铬、铁黑、钛黄、锌-铁系棕、铜-铬系黑、铜-铁系黑等氧化物系颜料等。
作为有机颜料及有机染料等有机染颜料，具体而言，例如可以举出：酞菁系染颜料；偶氮系、硫靛系、紫环酮系、苝系、喹吖酮系、二恶嗪系、异吲哚满酮系、喹酞酮系等缩合多环染颜料；蒽醌系、紫环酮系、苝系、次甲基系、喹啉系、杂环系、甲基系染颜料等。
这些染颜料可单独使用1种，也可以混合使用2种以上。
作为上述无机颜料、有机颜料及有机颜染料等有机染颜料中，优选无机颜料，通过无机颜料作为着色剂，即使将成形品在室外等使用也可长时间保持清晰映现性等。
染颜料的量相对于聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的合计100重量份为0.05重量份以上且5重量份以下。更优选为0.05重量份以上且3重量份以下，进一步优选为0.1重量份以上且2重量份以下。着色剂的量低于0.05重量份时，不易得到具有清晰映现性的染色成形品。若多于5重量份，则成形品的表面粗糙度变大，不易得到具有清晰映现性的染色成形品。
“抗氧剂”
作为抗氧化剂，可使用树脂中所使用的一般的抗氧剂，但从氧化稳定性、热稳定性的观点考虑，优选亚磷酸酯系抗氧化剂、硫系抗氧化剂及酚系抗氧化剂。在此，抗氧化剂的添加量相对于聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的合计100重量份，通常优选0.001重量份以上，更优选0.002重量份以上，进一步优选0.005重量份以上。另外，抗氧化剂的添加量相对于上述合计100重量份，通常优选5重量份以下，更优选3重量份以下，进一步优选2重量份以下。若上述抗氧化剂的添加量多于5重量份，则有时在成形时污染模具，无法得到优异的表面外观的成形品。若低于0.001重量份，则存在无法得到相对于成形稳定性的充分的改良效果的倾向。
(亚磷酸酯系抗氧剂)
作为亚磷酸酯系抗氧剂，可以举出：亚磷酸三苯酯、亚磷酸三(壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三癸酯、亚磷酸三辛酯、亚磷酸三(十八烷基)酯、亚磷酸二癸基单苯基酯、亚磷酸二辛基单苯基酯、亚磷酸二异丙基单苯基酯、亚磷酸单丁基二苯基酯、亚磷酸单癸基二苯基酯、亚磷酸单辛基二苯基酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、2,2-亚甲基双(4,6-二叔丁基苯基)辛基亚磷酸酯、双(壬基苯基)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯等。
其中，优选使用亚磷酸三壬基苯基酯、亚磷酸三(2,4-二叔丁基苯基)酯、双(2,4-二叔 丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯。这些化合物可使用1种或并用2种以上。
(硫系抗氧剂)
作为硫系抗氧剂，例如可以举出：二月桂基-3,3’-硫代二丙酸酯、双十三烷基-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯、月桂基硬脂基-3,3’-硫代二丙酸酯、季戊四醇四(3-月桂基硫代丙酸酯)、双[2-甲基-4-(3-月桂基硫代丙酰基氧基)-5-叔丁基苯基]硫醚、十八烷基二硫醚、巯基苯并咪唑、2-巯基-6-甲基苯并咪唑、1,1’-硫代双(2-萘酚)等。上述中，优选季戊四醇四(3-月桂基硫代丙酸酯)。这些化合物可使用1种或并用2种以上。
(酚系抗氧剂)
作为酚系抗氧化剂，例如可以举出：季戊四醇四(3-巯基丙酸酯)、季戊四醇四(3-月桂基硫代丙酸酯)、甘油-3-硬脂基硫代丙酸酯、三乙二醇-双[3-(3-叔丁基-5-甲基-4-羟苯基)丙酸酯]、1,6-己二醇-双[3-(3,5-二叔丁基-4-羟苯基)丙酸酯]、季戊四醇-四[3-(3,5-二叔丁基-4-羟苯基)丙酸酯]、十八烷基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、N,N-六亚甲基双(3,5-二叔丁基-4-羟基-氢化肉桂酰胺)、3,5-二叔丁基-4-羟基-苄基膦酸酯-二乙基酯、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、4,4’-亚联苯基二次膦酸四(2,4-二叔丁基苯基)酯、3,9-双{1,1-二甲基-2-[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酰基氧基]乙基}-2,4,8,10-四氧杂螺(5,5)十一烷、2,6-二叔丁基对甲酚、2,6-二叔丁基-4-乙基苯酚等化合物。
这些化合物中，优选被碳原子数5以上的烷基取代1个以上的芳香族单羟基化合物，具体而言，优选十八烷基-3-(3,5-二叔丁基-4-羟苯基)丙酸酯、季戊四醇-四{3-(3,5-二叔丁基-4-羟苯基)丙酸酯}、1,6-己二醇-双[3-(3,5-二叔丁基-4-羟苯基)丙酸酯]、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯等，进一步优选季戊四醇-四{3-(3,5-二叔丁基-4-羟苯基)丙酸酯。这些化合物可使用1种或并用2种以上。
“UV吸收剂”
作为紫外线吸收剂，可以举出：苯并三唑系化合物、二苯甲酮系化合物、三嗪系化合物、苯甲酸酯系化合物、受阻胺系化合物、水杨酸苯酯系化合物、氰基丙烯酸酯系化合物、丙二酸酯系化合物、草酰苯胺系化合物等。这些可单独使用1种或并用2种以上。
作为苯并三唑系化合物的更具体的例子，可以举出：2-(2’-羟基-3’-甲基-5’-己基苯基)苯并三唑、2-(2’-羟基-3’-叔丁基-5’-己基苯基)苯并三唑、2-(2’-羟基-3’,5’-二叔丁基苯基)苯并三唑、2-(2’-羟基-3’-甲基-5’-叔辛基苯基)苯并三唑、2-(2’-羟基-5’-叔十二烷基苯基)苯并 三唑、2-(2’-羟基-3’-甲基-5’-叔十二烷基苯基)苯并三唑、2-(2’-羟基-5’-叔丁基苯基)苯并三唑、甲基-3-(3-(2H-苯并三唑-2-基)-5-叔丁基-4-羟苯基)丙酸酯等。
作为三嗪系化合物，可以举出：2-[4-[(2-羟基-3-十二烷氧基丙基)氧基]-2-羟苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,4-双(2,4-二甲基苯基)-6-(2-羟基-4-异辛氧基苯基)-均三嗪、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[(己基)氧基]-苯酚(BASF·Japan公司制、Tinuvin1577FF)等。
作为羟基二苯甲酮系化合物，可以举出：2,2’-二羟基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮、2-羟基-4-辛氧基二苯甲酮等。
作为氰基丙烯酸酯系化合物，可以举出：乙基-2-氰基-3,3-二苯基丙烯酸酯、2’-乙基己基-2-氰基-3,3-二苯基丙烯酸酯等。
作为丙二酸酯系化合物，可以举出：2-(1-芳基次烷基)丙二酸酯类。其中，优选丙二酸[(4-甲氧基苯基)-亚甲基]-二甲基酯(Clariant公司制、HostavinPR-25)、2-(对甲氧基亚苄基)丙二酸二甲酯。
作为草酰苯胺系化合物，可以举出：2-乙基-2’-乙氧基-草酰苯胺(Clariant公司制、Sanduvor VSU)等。
其中，优选2-(2’-羟基-3’-叔丁基-5’-己基苯基)苯并三唑、2-(2’-羟基-5’-叔丁基苯基)苯并三唑、2-[4-[(2-羟基-3-十二烷氧基丙基)氧基]-2-羟基苯基]-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、2,2’、4,4’-四羟基二苯甲酮。
“光稳定剂”
作为光稳定剂，可以举出：受阻胺系光稳定剂，其分子量优选1000以下，更优选900以下。若分子量超过1000，则有可能在制成成形品时无法充分得到耐气候性。另外，分子量优选300以上，更优选400以上。分子量低于300时，有时缺乏耐热性，在成形时污染模具，无法得到优异的表面外观的成形品。进而，优选具有哌啶结构的化合物。在此规定的哌啶结构只要成为饱和六元环的胺结构即可，还包含哌啶结构的一部分被取代基取代的结构。作为取代基，可以举出碳原子数4以下的烷基，特别优选甲基。特别优选具有多个哌啶结构的化合物，优选这些多个哌啶结构由酯结构连结的化合物。
作为这样的光稳定剂，可以举出：4-哌啶醇-2,2,6,6-四甲基-4-苯甲酸酯、双(2,2,6,6-四甲基-哌啶基)癸二酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、四(2,2,6,6-四甲基哌啶-4-羧酸)1,2,3,4-丁烷四基、2,2,6,6-四甲基-哌啶醇与十三烷基醇和1,2,3,4-丁烷四羧酸的缩合物、1,2,2,6,6-五甲基-4-哌啶基、及十三烷醇和十三烷基-1,2,3,4-丁烷四羧酸酯、双(1,2,3,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯、癸二酸 双(2,2,26,6-四甲基-1-(辛氧基)-4-哌啶基)酯、1,1-二甲基乙基过氧化氢和辛烷的反应生成物、1-[2-[3-(3,5-二叔丁基-4-羟基苯基)丙酰氧基]乙基]-4-[3-(3,5-二叔丁基-4-4-羟苯基)丙酰氧基]乙基]-2,2,6,6-四甲基哌啶、四(1,2,2,6,6-五甲基-4-哌啶基)1,2,3,4-丁烷四羧酸酯、聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}六亚甲基{(2,2,6,6-四甲基-4-哌啶基)亚氨基}]、N,N'-双(2,2,6,6-四甲基-4-哌啶基)-1,6-己二胺聚合物和2,4,6-三氯-1,3,5-三嗪、1,2,3,4-丁烷四羧酸和2,2,6,6-四甲基-4-哌啶醇和β,β,β,β-四甲基-3,9-(2,4,8,10-四氧螺环[5,5]十一烷-二乙醇的缩合物、N,N’-双(3-氨基丙基)乙二胺-2,4-双[N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基]-6-氯-1,3,5-三嗪缩合物、琥珀酸二甲酯-1-(2-羟基乙基)-4-羟基-2,2,6,6-四甲基哌啶缩聚物等。
光稳定剂的含量相对于聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的合计100重量份优选为0.001重量份以上且5重量份以下。更优选为0.005重量份以上且3重量份以下，进一步优选为0.01重量份以上且1重量份以下。若受阻胺系光稳定剂的添加量多于5重量份，则存在着色的倾向，即使添加着色剂也不易得到具有深度和清澈感的漆黑。若添加量低于0.001重量份，则有可能在将聚碳酸酯树脂组合物用于例如汽车内外装饰品用途时无法充分地得到耐气候性。另外，芳香族聚碳酸酯树脂(B)存在容易因受阻胺系光稳定剂而分解的倾向。因此，对聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的比率而言，在芳香族聚碳酸酯树脂(B)变多的情况下，优选谨慎地设定光稳定剂的添加量。
“脱模剂”
对聚碳酸酯树脂组合物而言，作为用于赋予成形时的脱模性的脱模剂，可相对于上述聚碳酸酯树脂100重量份含有0.0001重量份以上且2重量份以下的多元醇的脂肪酸酯。
在多元醇的脂肪酸酯的含量低于0.0001重量份的情况下，有可能无法充分得到添加效果，在成形加工中的脱模时，因脱模不良而导致成形品开裂。另一方面，在超过2重量份的情况下，有可能树脂组合物发生白浊或在成形加工时附着于模具的附着物变多。更优选多元醇的脂肪酸酯的含量为0.01重量份以上且1.5重量份以下，进一步优选为0.1重量份以上且1重量份以下。
作为多元醇的脂肪酸酯，优选碳原子数1～碳原子数20的多元醇和碳原子数10～碳原子数30的饱和脂肪酸的偏酯或全酯。作为这种多元醇和饱和脂肪酸的偏酯或全酯，可以举出：硬脂酸单甘油酯、硬脂酸二甘油酯、硬脂酸甘油三脂、硬脂酸单山梨醇酯、山嵛酸单甘油酯、季戊四醇单硬脂酸酯、季戊四醇二硬脂酸酯、季戊四醇四硬脂酸酯、季戊四醇四壬酸酯、丙二醇单硬脂酸酯、棕榈酸异丙酯、山梨糖醇酐单硬脂酸酯等。其中，优选使用硬脂酸单甘油酯、硬脂酸甘油三酯、季戊四醇四硬脂酸酯。
另外，从耐热性及耐湿性的观点考虑，作为多元醇的脂肪酸酯，更优选全酯。
作为脂肪酸，优选高级脂肪酸，更优选碳原子数10～碳原子数30的饱和脂肪酸。作为这种脂肪酸，可以举出：肉豆蔻酸、月桂酸、棕榈酸、硬脂酸、山嵛酸等。
另外，在多元醇的脂肪酸酯中，多元醇优选为乙二醇。此时，在添加于树脂时，可在不损伤树脂的透明性的情况下提高脱模性。
另外，上述多元醇的脂肪酸酯优选为二元醇的脂肪酸二酯。此时，在添加于树脂时，可抑制湿热环境下的树脂组合物的分子量的降低。
在本实施方式中，配合于聚碳酸酯树脂组合物中的脱模剂的添加时期、添加方法没有特别限定。作为添加时期，例如可以举出：在利用酯交换法制造聚碳酸酯树脂的情况下的聚合反应结束时；进而无论聚合方法如何，在聚碳酸酯树脂组合物和其它配合剂的混炼途中等的聚碳酸酯树脂组合物发生熔融的状态；使用挤出机等与颗粒或粉末等固体状态的聚碳酸酯树脂组合物共混、混炼时等。作为添加方法，可以举出：在聚碳酸酯树脂组合物中直接混合或混炼脱模剂的方法；以使用少量的聚碳酸酯树脂组合物或其它树脂等和脱模剂而制作的高浓度母料的形式进行添加的方法。
“其它的树脂”
另外，上述聚碳酸酯树脂组合物也可在不损害本发明的效果的范围内与例如芳香族聚酯、脂肪族聚酯、聚酰胺、聚苯乙烯、聚烯烃、丙烯酸、非晶聚烯烃、ABS、AS等合成树脂、聚乳酸、聚丁烯琥珀酸酯等生物降解性树脂等中的1种或2种以上混炼，用作聚合物合金。
“无机填充剂、有机填充剂”
在上述聚碳酸酯树脂组合物中，也可在能够维持设计性的范围内添加玻璃纤维、玻璃磨碎纤维、玻璃鳞片、玻璃珠、二氧化硅、氧化铝、二氧化钛、硫酸钙粉体、石膏、石膏晶须、硫酸钡、滑石、云母、硅灰石等硅酸钙；炭黑、石墨、铁粉、铜粉、二硫化钼、碳化硅、碳化硅纤维、氮化硅、氮化硅纤维、黄铜纤维、不锈钢纤维、钛酸钾纤维、它们的晶须等无机填充剂；以及木粉、竹粉、椰子淀粉、软木粉、浆粉等粉末状有机充填剂；交联聚酯、聚苯乙烯、苯乙烯-丙烯酸共聚物、尿素树脂等囊状-球状有机填充剂；碳纤维、合成纤维、天然纤维等纤维状有机填充剂。
[聚碳酸酯树脂组合物的制造方法]
上述聚碳酸酯树脂组合物可通过以下操作制造：进行添加工序，在上述特定的聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)中，添加以金属量换算计为0.5重量ppm以上且1000重量ppm以下的上述特定的化合物(C)；然后，进行使聚碳酸酯树脂(A)和芳香族聚 碳酸酯树脂(B)进行熔融反应的反应工序。在反应工序中，通过存在化合物(C)，促进聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的酯交换反应，得到相溶性高的树脂组合物。另外，作为聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)、化合物(C)，可使用与上述同样的聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)、化合物(C)。
聚碳酸酯树脂组合物可如下制造：将上述成分以特定的比例同时或者以任意顺序，通过转鼓混合机、V型混合机、诺塔混合机、班伯里混炼机、混炼辊或挤出机等混合机混合，从而进行制造。其中，在熔融混合时，更优选可在减压的状态下混合的物质。
[成形体]
聚碳酸酯树脂组合物可通过注射成形法、挤出成形法、压缩成形法等通常已知的方法来成形。通过成形得到的成形体其色调、透明性、耐热性、耐气候性、光学特性、及机械强度优异，且残存低分子成分及异物少，因此，适于车辆用内装饰零件。
[实施例]
以下，通过实施例进一步详细地说明本发明，但只要不超出其要点，本发明并不限于以下的实施例。
[评价方法]
以下，聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)及树脂组合物的物性或特性的评价通过以下方法进行。
(1)还原粘度的测定
使聚碳酸酯树脂(A)或芳香族聚碳酸酯树脂(B)的样品溶解于二氯甲烷，制备0.6g/dL浓度的聚碳酸酯树脂溶液。使用森友理化工业公司制乌伯娄德型粘度管在温度20.0℃±0.1℃的条件下测定溶剂的通过时间t0和溶液的通过时间t，基于下式(i)算出相对粘度ηrel。接着，由相对粘度ηrel基于下式(ii)求得比粘度ηsp。
ηrel＝t/t0···(i)
ηsp＝ηrel-1···(ii)
将得到的比粘度ηsp除以溶液的浓度c(g/dL)，由此求得还原粘度(ηsp/c)。该还原粘度的值越高，意味着分子量越大。
(2)玻璃化转变温度(Tg)的测定
使用差示扫描热量计(DSC：Modulate DSC 2910,TA America)在氮气氛下以升温速度10℃/min测定玻璃化转变温度。将具有单一转变温度的情况设为○、有2个及2个以上转变温度的情况设为×，分别记载全部玻璃化转变温度。
(3)全光透过率的测定
依据GB2410-80标准，使用后述的厚度1mmt的热压片材并使用雾度计(上海申光株式会社制、WGW)以标准C光源测定全光透过率。通过目视，明显不透明的情况记载为不透明。
(4)断裂伸长率
依据ASTM D638标准测定断裂伸长率。
(5)生物质含有率的算出
放射性碳14(C14)在大气中通过宇宙射线以一定速度生成且以一定速度消失(半衰期：5370年)，因此在自然界存在一定量。吸收大气中的二氧化碳的植物含有一定量的该C14，因砍伐等不产生碳酸同化作用时，以一定速度消失，因此利用该性质建立放射性碳年代测定法。化石燃料由于未长时间受到宇宙射线的影响，因此，C14全部消失。另一方面，由于生物来源的化学品在停止C14供给后仅经过短时间，因此，可以说C14的含量为大致一定的值。
还使用上述方法具体说明生物质含量的算出方法。
首先，ISB-PC的ISB碳酸酯结构单元由6个生物来源的ISB的碳和1个化石燃料的DPC来源的碳构成，因此，ISB-PC的生物质含有率为生物来源的碳原子数：6/总碳原子数：7＝85.7％。在此，由于聚合物链足够长，因此，末端的影响可以忽视。另外，如后述的制造例1所述在共聚聚碳酸酯树脂的情况下，由于CHDM为源自化石燃料的原料，因此，CHDM-PC的生物质含量为生物来源的碳原子数：0/总碳原子数：9＝0％。在制造例1的ISB/CHDM＝70/30mol％的情况下，由于仅ISB-PC成分为生物来源，因此，其生物质含有率为85.7％×70mol％＝60％。
接着，如实施例所述，聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)共混时的生物质含有率由于芳香族聚碳酸酯树脂(B)为通过源自化石燃料的原料制造的聚合物，因此，其生物质含有率为0％。实施例由于以重量比共混，因此，计算各自的聚碳酸酯树脂的摩尔质量(单位：g/mol)，分别用重量除以摩尔质量，由此转换成摩尔分率。然后，通过上述聚碳酸酯树脂(A)的生物质含量和其摩尔分率的积计算共混的生物质含量。另外，关于生物质的算出，仅由树脂成分算出，对于化合物(C)、热稳定剂、脱模剂等成分未作考虑。
[使用原料]
以下的实施例及比较例中使用的化合物的缩写、及制造商如下所述。
＜二羟基化合物＞
·ISB：异山梨糖醇酐[Roquette Freres公司制]：生物来源原料
·CHDM：1,4-环己烷二甲醇[SK Chemical公司制]：源自化石燃料的原料
＜碳酸二酯＞
·DPC：碳酸二苯酯[三菱化学(株)制]：源自化石燃料的原料
＜热稳定剂(抗氧剂)＞
·Irganox 1010：季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯][BASF公司制]
·AS2112：三(2,4-二叔丁基苯基)亚磷酸酯[(株)ADEKA制](分子量646.9)
＜脱模剂＞
·E-275：乙二醇二硬脂酸酯[日油(株)制]
[聚碳酸酯树脂(A)的制造例1]＝D7340R
使用由立式搅拌反应器3台和卧式搅拌反应器1台以及双轴挤出机构成的连续聚合设备进行聚碳酸酯树脂的聚合。具体而言，首先使ISB、CHDM、及DPC分别在罐中熔融，将ISB以35.2kg/hr、CHDM以14.9kg/hr、DPC以74.5kg/hr(以摩尔比计为ISB/CHDM/DPC＝0.700/0.300/1.010)的流量连续地供给于第1立式搅拌反应器。同时，将作为催化剂的乙酸钙一水合物的水溶液供给于第1立式搅拌反应器，使其相对于全部二羟基化合物1mol为1.5μmol。各反应器的反应温度、内压、滞留时间分别设为第1立式搅拌反应器：190℃、25kPa、90分钟，第2立式搅拌反应器：195℃、10kPa、45分钟，第3立式搅拌反应器：210℃、3kPa、45分钟，第4卧式搅拌反应器：225℃、0.5kPa、90分钟。一边微调节第4卧式搅拌反应器的内压一边运行，以使得到的聚碳酸酯树脂的还原粘度为0.41dL/g～0.43dL/g。
以60kg/hr的量从第4卧式搅拌反应器抽出聚碳酸酯树脂，接下来将树脂在熔融状态下直接供给于排气型双轴挤出机[(株)日本制钢所制TEX30α、L/D：42]。将通过了挤出机的聚碳酸酯树脂继续在熔融状态下直接通过网眼10μm的蜡烛型过滤器(SUS316制)，过滤异物。然后，使聚碳酸酯树脂从模具中条状地排出，水冷使其固化后，使用旋转式刀具进行颗粒化，得到ISB/CHDM的摩尔比为70/30mol％的共聚聚碳酸酯树脂的颗粒。
上述挤出机具有3个真空排气口，在此将树脂中的残存低分子成分脱挥除去。在第2排气口的前面相对于树脂添加2000质量ppm的水，进行注水脱挥。在第3排气口的前面相对于聚碳酸酯树脂100质量份分别添加0.1质量份、0.05质量份、0.3质量份的Irganox1010、AS2112、E-275。通过以上操作，得到ISB/CHDM共聚物聚碳酸酯树脂。将制造例1中得到的聚碳酸酯树脂(A)称为“PC-A1”。
[聚碳酸酯树脂(A)的制造例2]＝D5360R
对于各原料向反应器的供给量，将ISB设为25.4kg/hr、CHDM设为25.0kg/hr、DPC设为74.8kg/hr(以摩尔比计为ISB/CHDM/DPC＝0.500/0.500/1.006)、将乙酸钙一水合物的 水溶液相对于全部二羟基化合物1mol设为1.5μmol，将得到的聚碳酸酯树脂的还原粘度由0.60dL/g变为0.63dL/g，除此以外，与上述的制造例1同样地制作树脂，得到ISB/CHDM的摩尔比为50/50mol％的聚碳酸酯树脂。将制造例2中得到的聚碳酸酯树脂(A)称为“PC-A2”。
[聚碳酸酯树脂(A)的制造例3]＝ISB/CHDM＝27/73mol％
在具备搅拌叶片及控制为100℃的回流冷凝器的聚合反应装置中，按照摩尔比率为ISB/CHDM/DPC/乙酸钙一水合物＝0.27/0.73/1.00/6.5×10-7，装入ISB、CHDM、蒸馏精制使氯化物离子浓度为10ppb以下的DPC及乙酸钙一水合物，并充分地进行氮置换。接下来，利用加热介质进行加热，在内温为100℃的时刻开始搅拌，一边进行控制使内温为100℃一边使内容物熔解并使其均匀。然后，开始升温，经40分钟使内温为210℃，在内温达到210℃的时刻进行控制以保持该温度，同时开始减压，达到210℃后经90分钟使其为13.3kPa(绝对压力、以下相同)，在保持该压力的同时进一步保持30分钟。
与聚合反应一起副反应产生的苯酚蒸气导入使用作为回流冷凝器的入口温度控制为100℃的蒸气作为制冷剂的回流冷凝器，使苯酚蒸气中含有若干量的单体成分回到聚合反应器中，未冷凝的苯酚蒸气接着导入使用45℃的温水作为制冷剂的冷凝器中回收。
使如上低聚物化的内容物暂时复压至大气压后，移至具备搅拌叶片及与上述同样地进行了控制的回流冷却器的另一聚合反应装置中，开始升温及减压，经60分钟使内温为210℃、压力为200Pa。然后，经20分钟使内温为220℃、压力为133Pa以下，在达到规定搅拌动力的时刻复压，从聚合反应装置出口经熔融状态的聚碳酸酯树脂利用造粒机进行颗粒化，得到颗粒。还原粘度为0.63dl/g。
如上操作得到ISB/CHDM的摩尔比为27/73mol％的聚碳酸酯树脂。将制造例3中得到的聚碳酸酯树脂(A)称为“PC-A3”。
[芳香族聚碳酸酯树脂(B)]
·PC-B1：三菱工程塑料公司制Iupilon S3000：双酚A结构单元100摩尔％的芳香族聚碳酸酯树脂、界面聚合法产品、还原粘度0.46dl/g)：源自化石燃料的原料
·PC-B2：三菱工程塑料公司制Iupilon S2000：双酚A结构单元100摩尔％的芳香族聚碳酸酯树脂、界面聚合法产品、还原粘度0.50dl/g)：源自化石燃料的原料
·PC-B3：三菱工程塑料公司制NOVAREX 7022：双酚A结构单元100摩尔％的芳香族聚碳酸酯树脂、酯交换法产品、还原粘度0.47dl/g)：源自化石燃料的原料
[化合物(C)]
·C-1：4,4'-硫代双(2-叔丁基-5-甲基苯基)、淄博德百益工贸株式会社制k300
·C-2：4,4’-[硫代双(亚甲基)]双[2,6-双(1,1-二甲基乙基)苯酚]、硫代二亚乙基双[3-(3,5-二叔丁基-4-羟苯基)丙酸酯]、淄博德百益工贸有限公司制k1098
·C-3：聚乙二醇(分子量：2000、国药集团化学试剂有限公司制PEG 2000)
·C-4：双酚A型环氧树脂(岳阳巴陵石油化工有限公司制CYD-011)
Figure PCTCN2015082743-appb-000015
将相应于化合物C-2～4的实施例记载于实施例10～15。
[实施例1]
将制造例2中得到的PC-A2的75重量份、作为芳香族聚碳酸酯树脂(B)的PC-B1的25重量份和作为化合物(C)的C-1的5重量份一并投入于小型混炼机(Hakke公司制Rheocord300P)，进行混炼。以转数80rpm、设定温度250℃进行15分钟混炼，得到颗粒状的树脂。将得到的颗粒利用真空干燥器在80℃下干燥12小时后，使用热压装置(上海西玛伟力橡塑机械株式会社制)在设定温度250℃、压力10MPa下加压10分钟，之后通过冷却压制使其固化，得到50mm×50mm×1mmt的试验片。将结果示于表1。
[实施例2]
将实施例1中的PC-A2变更为50重量份、PC-B1变更为50重量份、C-1变更为2.5重量份，进而将混炼时间变更为8分钟，除此以外，与实施例1同样地进行。将结果示于表1。
[实施例3]
将实施例2中的C-1变更为5重量份，除此以外，与实施例2同样地进行。将结果示于表1。
[实施例4]
将实施例3中的PC-B1变更为PC-B2，除此以外，与实施例3同样地进行。将结果示于表1。
[比较例1]
将实施例1中的C-1设为0重量份，除此以外，与实施例1同样地进行。将结果示于表1。
[比较例2]
将实施例2中的C-1设为0重量份，除此以外，与实施例2同样地进行。将结果示于表1。
[比较例3]
将比较例2中的PC-A2变更为25重量份、PC-B1变更为75重量份，除此以外，与比较例1同样地进行。将结果示于表1。
[比较例4]
将比较例1中的PC-A3变更为70重量份、PC-B3变更为30重量份，除此以外，与比较例1同样地进行。将结果示于表1。
[实施例5]
将实施例1中的PC-A2变更为90重量份、PC-B1变更为10重量份、C-1变更为0.5重量份，进而将混炼时间变更为8分钟，除此以外，与实施例1同样地进行。将结果示于表2。
[实施例6]
将实施例5中的C-1变更为2.5重量份，除此以外，与实施例5同样地进行。将结果示于表2。
[实施例7]
将实施例2中的PC-A2变更为75重量份、PC-B3变更为25重量份、进而将C-1变更为5重量份，除此以外，与实施例2同样地进行。将结果示于表2。
[实施例8]
将实施例2中的PC-A2变更为PC-A1、PC-B1变更为PC-B2、C-1变更为10重量份，除此以外，与实施例2同样地进行。将结果示于表2。
[实施例9]
将实施例2中的PC-A2变更为PC-A1、将PC-B1变更为PC-B3，分别将PC-A1设为75重量份、PC-B3设为25重量份，进而将C-1变更为10重量份，除此以外，与实施例2同样地进行。将结果示于表2。
[实施例10]
将实施例3中的C-1变更为C-1，除此以外，与实施例3同样地进行。将结果示于表2。
[实施例11]
将实施例3中的C-1 5重量份变更为C-2 10重量份，除此以外，与实施例3同样地进行。将结果示于表2。
[实施例12]
将实施例11中的PC-A2变更为PC-A1，除此以外，与实施例11同样地进行。将结果示于表2。
[实施例13]
将实施例2中的C-1 2.5重量份变更为C-3 1.25重量份，除此以外，与实施例2同样地进行。将结果示于表3。
[实施例14]
将实施例13中的C-3 1.25重量份变更为2.5重量份，除此以外，与实施例13同样地进行。将结果示于表3。
[实施例15]
将实施例2中的C-1 2.5重量份变更为C-4 7重量份，除此以外，与实施例2同样地进行。将结果示于表3。
表1
Figure PCTCN2015082743-appb-000016
表2
Figure PCTCN2015082743-appb-000017
表3
Figure PCTCN2015082743-appb-000018
而且，这样的聚碳酸酯树脂组合物的透明性优异，并且以高水平均衡较好地兼备生物质含有率、耐热性及机械强度。

Claims (4)

  1. 一种聚碳酸酯树脂组合物，其中包含含有源自下述式(1)所示的化合物的结构单元的聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)及选自下述式(2)、(3)及(4)中的一种以上的化合物(C)，其特征在于，该化合物(C)的添加量相对于含有聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)的树脂组合物100重量份其含有0.1重量份以上且10重量份以下，
    Figure PCTCN2015082743-appb-100001
    式中，R1及R2表示互相独立的碳原子数0～4的烷基或具有酰胺键的碳原子数0～4的烷基，X表示硫原子，或在R1或R2具有酰胺键的情况下表示碳原子数2～8的2价连接基团，R3、R4、R5及R6表示互相独立的氢原子或碳原子数1～4的烷基，
    Figure PCTCN2015082743-appb-100002
    式中，R7表示取代或者非取代的碳原子数2～10的烷基，p表示4～45的整数，
    Figure PCTCN2015082743-appb-100003
    式中，R8表示含有碳原子数1～18的脂肪族或芳香环的亚烷基，R9表示直链状或者环状的碳原子数1～20的羰基或芳香族羰基，n表示2～3的整数。
  2. 根据权利要求1所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树脂组合物经差示扫描量热分析测定只有一个玻璃化转变温度。
  3. 根据权利要求1或2所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树 脂组合物在厚度为1mm成形体中全光透过率为80％以上。
  4. 根据权利要求3或4所述的聚碳酸酯树脂组合物，其特征在于，所述聚碳酸酯树脂组合物经差示扫描量热分析测定的玻璃化转变温度为90℃以上且200℃以下。
PCT/CN2015/082743 2015-06-30 2015-06-30 聚碳酸酯树脂组合物、其制造方法、成形体 WO2017000149A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201580081281.0A CN107709458B (zh) 2015-06-30 2015-06-30 聚碳酸酯树脂组合物、其制造方法、成形体
PCT/CN2015/082743 WO2017000149A1 (zh) 2015-06-30 2015-06-30 聚碳酸酯树脂组合物、其制造方法、成形体

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/082743 WO2017000149A1 (zh) 2015-06-30 2015-06-30 聚碳酸酯树脂组合物、其制造方法、成形体

Publications (2)

Publication Number Publication Date
WO2017000149A1 WO2017000149A1 (zh) 2017-01-05
WO2017000149A9 true WO2017000149A9 (zh) 2017-02-02

Family

ID=57607427

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/082743 WO2017000149A1 (zh) 2015-06-30 2015-06-30 聚碳酸酯树脂组合物、其制造方法、成形体

Country Status (2)

Country Link
CN (1) CN107709458B (zh)
WO (1) WO2017000149A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114790328B (zh) * 2022-05-10 2024-03-22 华东理工大学 一种脂环族聚碳酸酯组合物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6696510B2 (en) * 2001-12-10 2004-02-24 Ticona Llc Stabilized resin compositions
JP2008291053A (ja) * 2007-05-22 2008-12-04 Teijin Ltd 末端変性ポリカーボネート樹脂組成物
JP5481784B2 (ja) * 2007-12-12 2014-04-23 三菱化学株式会社 ポリカーボネート樹脂組成物及びその製造方法
CN105348503A (zh) * 2009-11-17 2016-02-24 三菱化学株式会社 聚碳酸酯树脂及由该聚碳酸酯树脂形成的透明膜
KR101814832B1 (ko) * 2009-12-10 2018-01-30 미쯔비시 케미컬 주식회사 폴리카보네이트 수지 조성물 그리고 이것을 성형하여 얻어지는 성형체, 필름, 플레이트 및 사출 성형품
CN101805506B (zh) * 2010-04-13 2012-02-22 深圳市金缙业科技有限公司 灯管料用聚碳酸酯树脂组合物及其制备方法
US8633265B2 (en) * 2011-01-19 2014-01-21 Sabic Innovative Plastics Ip B.V. UV stabilization of isosorbide polycarbonates
US9193864B2 (en) * 2012-06-22 2015-11-24 Sabic Global Technologies B.V. Polycarbonate compositions with improved impact resistance
CN104471451A (zh) * 2012-08-01 2015-03-25 三菱化学株式会社 聚碳酸酯树脂组合物及透明膜
CN103602056A (zh) * 2013-12-04 2014-02-26 深圳市兴盛迪新材料有限公司 一种适合户外使用的防霉抗菌型聚碳酸脂组合物

Also Published As

Publication number Publication date
CN107709458B (zh) 2020-06-19
WO2017000149A1 (zh) 2017-01-05
CN107709458A (zh) 2018-02-16

Similar Documents

Publication Publication Date Title
JP6714877B2 (ja) ポリカーボネート樹脂組成物、およびその成形体
KR20120117756A (ko) 폴리카보네이트 수지 조성물 그리고 이것을 성형하여 얻어지는 성형체, 필름, 플레이트 및 사출 성형품
JP6010919B2 (ja) ポリカーボネート樹脂組成物
US10526446B2 (en) Polycarbonate resin composition, method for producing same, and molded object
WO2011071166A1 (ja) ポリカーボネート樹脂組成物及び成形品
JP6743371B2 (ja) 熱可塑性樹脂組成物、及びこれを用いた成形品
KR102200887B1 (ko) 충격강도가 개선된 친환경 폴리에스테르 카보네이트 수지 조성물 및 그 제조방법
JP6671114B2 (ja) ポリカーボネート樹脂組成物、その製造方法、成形体、及びその製造方法
CN107849344B (zh) 聚碳酸酯树脂复合物
WO2017000149A1 (zh) 聚碳酸酯树脂组合物、其制造方法、成形体
WO2017000155A1 (zh) 聚碳酸酯树脂组合物、其制造方法、成形体
WO2017000154A1 (zh) 聚碳酸酯树脂组合物、其制造方法、成形体
JP7095358B2 (ja) ポリカーボネート樹脂組成物及びその成形体
JP2020073697A (ja) 熱可塑性樹脂組成物、及びこれを用いた成形品
JP6969119B2 (ja) 成形体の製造方法
JP2018150480A (ja) ポリカーボネート樹脂組成物及び成形体
JP2017179188A (ja) ポリカーボネート樹脂組成物及び成形体
JP2024144958A (ja) 医療用成形体
JP2017179189A (ja) ポリカーボネート樹脂組成物及び成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15896680

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15896680

Country of ref document: EP

Kind code of ref document: A1