WO2017020185A1 - Polycarbonate resin composite - Google Patents

Polycarbonate resin composite Download PDF

Info

Publication number
WO2017020185A1
WO2017020185A1 PCT/CN2015/085764 CN2015085764W WO2017020185A1 WO 2017020185 A1 WO2017020185 A1 WO 2017020185A1 CN 2015085764 W CN2015085764 W CN 2015085764W WO 2017020185 A1 WO2017020185 A1 WO 2017020185A1
Authority
WO
WIPO (PCT)
Prior art keywords
polycarbonate resin
compound
bis
resin
resin composition
Prior art date
Application number
PCT/CN2015/085764
Other languages
French (fr)
Chinese (zh)
Inventor
田中智彦
吴国章
苏莉莉
赖文钦
严谨
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 PCT/CN2015/085764 priority Critical patent/WO2017020185A1/en
Priority to CN201580081573.4A priority patent/CN107849344B/en
Publication of WO2017020185A1 publication Critical patent/WO2017020185A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/04—Aromatic polycarbonates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • 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 composite which is excellent in transparency and excellent in rigidity, a method for producing the same, and a molded article obtained by molding the resin composite.
  • a conventional aromatic polycarbonate resin containing a structure derived from bisphenol A or the like is widely used as an industrial transparent material for electric, mechanical, automotive, and the like because of its excellent transparency and heat resistance. Further, plastics used as optical materials are used for lenses, optical disks, and the like.
  • the aromatic polycarbonate resin has been proposed to be blended with various glass fillers.
  • the refractive index (refractive index at a wavelength of 589 nm, hereinafter nd) of E glass which is an example of a general glass fiber material to be blended in an aromatic polycarbonate resin is about 1.55
  • aromatic poly Since the refractive index of the carbonate resin is as high as 1.580 to 1.590, when a fiber composed of ordinary E glass is dispersed in an aromatic polycarbonate resin, there is a problem that transparency is lowered due to a difference in refractive index.
  • a glass fiber composition in which a glass filler having a specific composition having a refractive index of 1.570 to 1.600 is blended in an aromatic polycarbonate resin to prevent transparency is disclosed (see Patent Document 1).
  • the glass fiber composition has a problem of hydrolysis of the resin due to alkali ions eluted from the glass, and in order to improve it, a glass fiber composition having a specific composition whose refractive index is adjusted to 1.570 to 1.600 is also disclosed ( Refer to Patent Document 2).
  • a glass fiber composition which is yellow is suppressed when the glass filler is blended in an aromatic polycarbonate resin (see Patent Document 3).
  • an aromatic-aliphatic group containing an aliphatic carbonate repeating unit derived from an aliphatic dihydroxy compound derived from isosorbide, 1,4-cyclohexanedimethanol, or tricyclodecane dimethanol is also disclosed.
  • Copolymerized polycarbon A polycarbonate resin composition having excellent transparency of a glass filler of a specific composition having a refractive index of 1.500 to 1.540 (see Patent Document 5).
  • Patent Document 1 Japanese Patent Publication No. 62-001338
  • Patent Document 2 Japanese Patent Laid-Open No. Hei 5-155638
  • Patent Document 3 Japanese Laid-Open Patent Publication No. 2007-153729
  • Patent Document 4 International Publication No. 2011/071162
  • Patent Document 5 International Gazette No. 2014/069659
  • the transparent polycarbonate resin compositions of Patent Documents 1 to 3 and 5 have problems in that a glass filler having a special composition is required, but E glass which has been conventionally used as a glass filler cannot be used, and as a result, cost becomes expensive, and polycarbonate is expensive. Since the refractive index of the ester resin composition becomes high, the average light transmittance is low.
  • the present invention has been made in view of such a background, and provides a polycarbonate resin composite which is excellent in transparency and has high rigidity, and a molded body comprising the same.
  • the inventors of the present invention have conducted intensive studies and found that an inexpensive glass filler using E glass which has been conventionally used as a raw material is excellent in transparency, and a polycarbonate resin composite having high rigidity and a high rigidity thereof are used.
  • the formed body thus formed completed the present invention. That is, the gist of the present invention lies in the following [1] to [6].
  • a resin composite comprising a resin composition comprising a polycarbonate resin (A) and an aromatic polycarbonate resin (B) containing a constituent unit derived from a compound represented by the following formula (1)
  • the glass filler (C) is contained in an amount of 10 parts by weight to 150 parts by weight per 100 parts by weight of the object (X), and the average light transmittance measured by a sheet having a thickness of 1 mm is 50% or more.
  • the polycarbonate resin composite of the present invention and a molded article thereof are excellent in transparency and excellent in rigidity.
  • the polycarbonate resin (A) contains a constituent 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 constituent unit derived from all the diols. This is referred to as a "polycarbonate resin constituting the unit (a)").
  • the polycarbonate resin (A) may be a homopolycarbonate resin constituting the unit (a), or may be a polycarbonate resin obtained by copolymerizing constituent units other than the constituent unit (a). From the viewpoint of excellent impact resistance, 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.
  • Isosorbide Isosorbide
  • the dihydroxy compound represented by the above formula (1) is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage or at the time of manufacture, it is preferable to carry out without using water and using a deoxidizer or under a nitrogen atmosphere.
  • the polycarbonate resin (A) is preferably a constituent unit (a) containing a dihydroxy compound derived from the general formula (1), and a dihydroxy compound derived from an aliphatic hydrocarbon or an alicyclic hydrocarbon.
  • a copolymerized polycarbonate resin of a constituent unit of one or more kinds of dihydroxy compounds in the group consisting of a hydroxy compound and an ether-containing dihydroxy compound hereinafter referred to as "constituting unit (b)"). Since these dihydroxy compounds have a soft molecular structure, the toughness of the obtained polycarbonate resin can be improved by using these dihydroxy compounds as a raw material.
  • dihydroxy compounds a dihydroxy compound of an aliphatic hydrocarbon or a dihydroxy compound of an alicyclic hydrocarbon having a large effect of improving toughness 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 are as follows.
  • the dihydroxy compound of the aliphatic hydrocarbon for example, the following dihydroxy compound can be used.
  • Glycol 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-anthracene a linear aliphatic dihydroxy compound such as alcohol 1,12-dodecanediol; a branched fat such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol or ethylene glycol Group dihydroxy compounds.
  • the dihydroxy compound of the alicyclic hydrocarbon for example, the following dihydroxy compound can be used. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-ten Hydrogenated naphthalene dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-gold a dihydroxy compound as a primary alcohol of an alicyclic hydrocarbon exemplified by a dihydroxy compound derived from a terpene compound, such as alkane dimethanol or limonene; 1,2-cyclohexanediol, 1,4-cyclohexane a secondary alcohol or a tertiary exemplified as an alicyclic hydrocarbon exemplified by an alcohol,
  • ether-containing dihydroxy compound examples include 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 (2) or a dioxane diol represented by the following structural formula (3) can be used.
  • the content ratio of the above-mentioned structural unit (a) to 100 mol% of the constituent unit derived from all dihydroxy compounds is preferably more than 50% by mol, more preferably 55% by mol or more and 95% by mol. % or less is more preferably 60% by mole or more and 90% by mole or less, and particularly preferably 65% by mole or more and 85% by mole or less.
  • the 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 constituent units other than the above structural unit (a) and the above structural unit (b).
  • a structural unit (other dihydroxy compound) for example, a dihydroxy compound containing an aromatic group or the like can be used.
  • the content of the constituent unit derived from the aromatic group-containing dihydroxy compound is preferably 10% by mole or less based on 100% by mole of the constituent unit derived from all the dihydroxy compounds. More preferably, it is 5 mol% or less.
  • 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, mechanical properties, and improvement in moldability of the polycarbonate resin (A) 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 or a heat stabilizer.
  • a stabilizer such as a reducing agent, an antioxidant, a deoxidizing agent, a light stabilizer, an antacid, a pH stabilizer or a heat stabilizer.
  • the dihydroxy compound represented by the above formula (1) has a property of being easily deteriorated in an acidic state. Therefore, by using an alkali stabilizer in the synthesis of the polycarbonate resin (A), deterioration of the dihydroxy compound represented by the above formula (1) can be suppressed, and the obtained polycarbonate resin composite can be further improved. quality.
  • 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, an aqueous solution of a dihydroxy compound containing an alkali stabilizer is preferred.
  • the content of the alkaline stabilizer is set such that the pH 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 the amount%. At this time, an effect of preventing deterioration of the dihydroxy compound represented by the above formula (1) can be obtained, and modification of the hydroxy compound can be prevented.
  • the content of the alkaline stabilizer is more preferably 0.001 to 0.1% by mass from the viewpoint of further improving these effects.
  • carbonic acid diester used for the raw material of the polycarbonate resin (A) a compound represented by the following formula (4) 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. Can be 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 can be used. 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 impurities such as chloride ions, and the impurities may hinder the polycondensation reaction or may cause deterioration of the color tone of the obtained polycarbonate resin. Therefore, it is preferred 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 by-produced monohydroxy compound or the like 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 Group IA. a metal compound and/or a Group IIA metal compound.
  • 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, aminoquine Porphyrin and hydrazine.
  • 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 rate can be increased. Therefore, a polycarbonate resin having a desired molecular weight can be obtained without necessarily increasing the polymerization temperature. Further, it is possible to suppress the occurrence of side reactions. As a result, the color tone of the polycarbonate resin (A) can be further prevented from being deteriorated, and coloring during molding can be further prevented.
  • sodium in the polycarbonate resin (A) is considered in consideration of the influence of the compound containing sodium, potassium or cesium on the color tone of the polycarbonate resin or the influence of iron on the polycarbonate resin.
  • the total content of potassium, barium, and iron is preferably 1 ppm by mass or less.
  • the color tone of the polycarbonate resin can be further prevented from being deteriorated, and the color tone of the polycarbonate resin can be further improved.
  • the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is more preferably 0.5 ppm by mass or less.
  • 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 in the above range in terms of the total content of sodium, potassium, rubidium and iron.
  • the polycarbonate resin (A) can be obtained by polycondensing a dihydroxy compound and a carbonic acid diester used as a raw material of a dihydroxy compound or the like 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.
  • the dissolution rate can be increased or the solubility can be sufficiently increased, and problems such as curing can be sufficiently avoided.
  • the thermal deterioration of the dihydroxy compound can be sufficiently suppressed, and as a result, the color tone of the obtained polycarbonate resin (A) can be further improved, and weather resistance can be improved.
  • the operation of mixing the dihydroxy compound and the carbonic acid diester of the raw material is preferably carried out in an atmosphere having an oxygen concentration of 10 vol% or less, more preferably 0.0001 to 10 vol%, particularly preferably 0.0001 to 5 vol%, still more preferably 0.0001 to 1 vol%. At this time, the color tone can be made better, and the reactivity can be improved.
  • the polycarbonate resin (A) it is preferred to use a carbonic acid diester in a molar ratio of from 0.90 to 1.20 with respect to all the dihydroxy compounds used for the reaction. At this time, an increase in the amount of the hydroxyl terminal of the polycarbonate resin (A) can be suppressed, and therefore, the thermal stability of the polymer can be improved. Therefore, the coloring at the time of molding can be further prevented or the speed of the transesterification reaction can be increased. In addition, a desired high molecular weight body can be obtained more reliably.
  • the amount of use of the carbonic acid diester is more preferably 0.95 to 1.10 in a molar ratio.
  • 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 form of the reaction may be a batch type or a continuous type, or a combination method of a batch type and a continuous type, and it is preferable to use a continuous type which can obtain a polycarbonate resin with less heat-receiving processes, and is excellent in productivity.
  • 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. At this time, the distillation of the unreacted monomer is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester is easily adjusted to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. In addition, a desired molecular weight and a polymer having a terminal group can be obtained more reliably.
  • 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, when the obtained resin is melt-processed, the melt viscosity may fluctuate, and it is difficult to maintain the quality of the molded article constant. 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 is usually 45 to 180 ° C, preferably 80 to 150 ° C, and particularly preferably 100 to 130 ° C, depending on the monomer to be used.
  • the reflux rate can be sufficiently increased, the effect can be sufficiently obtained, and the effect of distilling off the monohydroxy compound to be distilled off can be sufficiently enhanced.
  • the decrease in the reaction rate can be prevented, and the coloration of the obtained resin can be further prevented.
  • the refrigerant warm water, steam, heat medium oil or the like can be used, and steam or heat medium oil is preferable.
  • the color tone of the obtained polycarbonate resin (A) is made better, and it is important to select the kind and amount of the above-mentioned catalyst.
  • the polycarbonate resin (A) is produced by a process of using a polymerization catalyst and usually two or more stages.
  • 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 effect can be improved.
  • the polymerization reactor used in the production of the polycarbonate resin (A) may be at least two or more as described above, but it is preferably three or more, preferably from 3 to 5, from the viewpoint of production efficiency and the like, and particularly preferably 4.
  • the number of the polymerization reactors is two or more, a plurality of reaction stages having different conditions may be further carried out in each polymerization reactor or the temperature and pressure may be continuously changed.
  • the polymerization catalyst may be added to the raw material preparation tank or the raw material storage tank, or may be directly added to the polymerization reactor. From the viewpoint of the stability of the supply and the control of the polycondensation reaction, it is preferred to provide a catalyst supply line in the middle of the raw material line before being supplied to the polymerization reactor and supply the polymerization catalyst as an aqueous solution.
  • the temperature of the polycondensation reaction By adjusting the temperature of the polycondensation reaction, productivity can be improved and an increase in the heat-receiving process of the article can be avoided. Further, the volatilization of the monomer and the decomposition or coloration of the polycarbonate resin (A) can be further prevented.
  • 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 0.1 to 10 hours, It is preferably set in the range of 0.5 to 3 hours.
  • the first stage reaction is preferably carried out while distilling off the produced monohydroxy compound to the outside of the reaction system.
  • the second stage it is preferable to gradually reduce the pressure of the reaction system from the pressure in the first stage, and to continuously remove the generated monohydroxy compound to the outside of the reaction system, and to make the pressure (absolute pressure) of the final reaction system 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 maximum temperature of the internal temperature of the polymerization reactor in all the reaction stages. Set to 210 to 240 °C. In order to suppress the decrease in the polymerization rate in the latter half of the reaction, the deterioration due to the heat transfer process is minimized, and it is preferable to use a horizontal reactor excellent in plug flowability and interface renewability in the final stage of the polycondensation reaction.
  • the pressure of the polymerization reactor in the final stage is adjusted to be a method having good workability.
  • 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 reactivity of the polycarbonate resin (A) may not be able to satisfy the desired molecular weight because the end group balance slightly changes and the reactivity is extremely lowered.
  • the polycarbonate resin (A) obtained in the polymerization reactor of the final stage preferably contains 10 mol/ton or more of both the hydroxyl terminal and the carbonate terminal.
  • one terminal group is preferably 60 mol/ton or less.
  • the residual amount of the monohydroxy compound in the resin can be reduced at the outlet of the polymerization reactor.
  • the residual amount of the monohydroxy compound in the resin in the outlet of the polymerization reactor is preferably 2,000 ppm by mass or less, more preferably 1,500 ppm by mass or less, still more preferably 1,000 ppm by mass or less.
  • the residual amount of the monohydroxy compound is preferably small, but if it is reduced to less than 100 ppm by mass, it is necessary to use a pole.
  • the amount of the terminal group of one side is reduced end-to-end, and the pressure of the polymerization reactor is maintained at an operating condition such as 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 by-produced monohydroxy compound 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. At this time, the heat resistance and the biomass content of the polycarbonate resin composite described above can be improved in a balanced manner. From the same viewpoint, 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. On the other hand, the glass transition temperature of the polycarbonate resin (A) is preferably 170 ° C or higher. At this time, the melt viscosity can be reduced by the above melt polymerization, and a polymer having a sufficient molecular weight can be obtained.
  • 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 further improving the molecular weight and preventing the 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 is usually 0.30 dL/g or more, preferably 0.33 dL/g or more. At this time, the mechanical strength of the molded article can be further improved. On the other hand, the reduced viscosity is usually 1.20 dL/g or less, more preferably 1.00 dL/g or less, still more preferably 0.80 dL/g or less. At this time, the fluidity at the time of molding can be improved, and productivity or moldability can be further improved.
  • the reduced viscosity of the polycarbonate resin (A) is a solution in which the concentration of the resin is accurately adjusted to 0.6 g/dL using dichloromethane as a solvent, and the temperature is 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.
  • the molded article of the resin composite can be prevented from becoming brittle, and the mechanical properties can be further improved.
  • the fluidity at the time of molding processing can be improved, and the appearance of the molded article can be prevented from being impaired or the dimensional accuracy can be deteriorated.
  • coloring or foaming caused by an increase in the temperature of the resin due to shear heat generation can be further prevented.
  • the melt viscosity of the polycarbonate resin (A) is more preferably 600 Pa ⁇ s or more and 2500 Pa ⁇ s or less, and still more preferably 800 Pa ⁇ s or more and 2000 Pa ⁇ s or less.
  • 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, and the like; Ammonium salt of tetramethylammonium sulfonate, tetrabutylammonium dodecylbenzenesulfonate, etc.; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate 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 (5) or the following structural formula (6).
  • 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 further suppressed.
  • phosphoric acid As the specific phosphorus-based compound containing the partial structure represented by the above structural formula (5) or structural formula (6), 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, nitrile (methylenephosphonic acid), propylphosphonic anhydride, and the like.
  • 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, dibenzyl 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. In this case, the effect of catalyst deactivation and coloring inhibition of the above specific phosphorus-based compound can be sufficiently obtained. Further, in this case, in particular, in the durability test of high temperature and high humidity, the coloring of the polycarbonate resin (A) can be further prevented.
  • the content of the specific phosphorus-based compound is preferably 0.5 mol equivalent or more and 5 mol equivalent or less, more preferably 0.7 mol equivalent or more and 4 mol equivalent or less, and particularly preferably 0.8 mol, based on 1 mol of the metal atom of the polymerization catalyst. It is equal to or more than 3 mol equivalents.
  • the aromatic polycarbonate resin (B) is a polycarbonate resin having a constituent unit derived from an aromatic dihydroxy compound represented by the following formula (7) as a main constituent unit.
  • R 1 to R 8 in the above formula (7) 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 (2) 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.
  • an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aromatic group having 6 to 20 carbon atoms which may have a substituent is preferable.
  • the divalent group of Y in the formula (2) 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.
  • 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 constituent unit derived from the dihydroxy compound is derived from the following formula (2).
  • the content ratio of the constituent unit derived from the dihydroxy compound represented by the above formula (2) to 100 mol% of the total constituent 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 constituent unit derived from a dihydroxy compound having a moiety represented by the above formula (1). However, when a constituent unit derived from a dihydroxy compound having a moiety represented by the above formula (1) is contained, a polycarbonate resin having a constituent unit different from the polycarbonate resin (A) is used.
  • the constituent unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) is a constituent unit from which a hydrogen atom is removed from the hydroxyl group of the dihydroxy compound.
  • Specific examples of the equivalent dihydroxy compound include the following dihydroxy compounds.
  • a halogenated bisphenol compound such as 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane or 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane.
  • dihydroxy compound examples include bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxyphenyl)methane, and bis(4-hydroxy-3-methyl group).
  • Phenyl)methane 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyl) -3,3,5-trimethylphenyl)cyclohexane, bis(4-hydroxyphenyl)phenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1 , 1-bis(4-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane
  • bis(4-hydroxy-phenyl)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) is determined by using dichloromethane as a solvent, and the polycarbonate concentration is accurately adjusted to 0.60 g/dl, and the temperature is measured at 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. More than one species.
  • the glass filler (C) for a resin composite of the present invention is an alkaline earth metal oxide such as SiO 2 of 52 to 56%, Al 2 O 3 of 12 to 16%, MgO or CaO, which is generally called E glass.
  • the glass filler (C) of the present invention has a refractive index measured at a wavelength of 589 nm of 1.550 or more and 1.560 or less.
  • the lower limit is preferably 1.552 or more, and particularly preferably 1.554 or more.
  • the upper limit is preferably 1.559 or less, and particularly preferably 1.558 or less.
  • the glass filler (C) of the present invention has an Abbe number of 50 or more and 60 or less. Further, in order to obtain a resin composite, the Abbe number is good, and the lower limit is preferably 52 or more, and particularly preferably 54 or more. The upper limit is preferably 58 or less, and particularly preferably 56 or less.
  • the glass filler (C) of the present invention is preferably used in the form of glass fibers, glass powder, glass flakes, ground fibers or glass beads, and in particular, in order to improve rigidity, it is preferably used in the form of glass fibers.
  • the diameter of the glass fiber is not particularly limited, and glass fibers of 3 to 25 ⁇ m can be preferably used. When it is thinner than 3 ⁇ m, the contact area between the glass fiber and the resin composition (X) may increase to cause diffuse reflection, and the transparency of the resin composite or the molded article may be lowered. When it is thicker than 25 ⁇ m, the strength of the glass fiber may be weak, and as a result, the strength of the molded article may be lowered. Moreover, in order to obtain a resin composite, the tensile stress is good, and the lower limit is preferably 5 ⁇ m or more, and particularly preferably 8 ⁇ m or more. The upper limit is preferably 20 ⁇ m or less, and particularly preferably 15 ⁇ m or less.
  • the form of the glass fiber can be appropriately selected depending on the characteristics required for the molding method or the molded article, and is not particularly limited. For example, chopped strands, rovings, mats, cloth, ground fibers, and the like can be mentioned.
  • the glass filler (C) of the present invention is preferably subjected to surface treatment using a treating agent containing a coupling agent.
  • a coupling agent a silane coupling agent, a borane coupling agent, an aluminate coupling agent, a titanate coupling agent, or the like can be used.
  • a silane coupling agent is preferably used from the viewpoint of good adhesion between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) and glass.
  • an aminosilane coupling agent, an epoxysilane coupling agent, an acrylic silane salt coupling agent, or the like can be used.
  • an aminosilane coupling agent is preferably used.
  • the amount of the glass filler (C) to be added in the invention is 10 to 150 parts by weight, preferably 10 to 100 parts by weight, particularly preferably 11 to 67 parts by weight, per 100 parts by weight of the resin composition (X).
  • the amount is less than 10 parts by weight, the effect of improving the rigidity is insufficient.
  • the amount is more than 150 parts by weight, the melt fluidity of the resin composite may be lowered. The filling of the shape becomes insufficient.
  • the transesterification catalyst (D) of the present invention is not particularly limited as long as it can promote the transesterification reaction of the polycarbonate resin (A) and the aromatic polycarbonate resin (B).
  • the transesterification reaction is produced by heating at the time of kneading of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the production of the above resin composition (X), and can be passed through a transesterification catalyst (D). ) to promote.
  • the compatibility between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the resin composition (X) is improved, so that the transparency of the resin composition (X) can be improved.
  • the transesterification catalyst (D) may, for example, be a compound containing at least one selected from the group consisting of a metal compound of Group IA and a metal compound of Group IIA, a tin compound, a basic nitrogen-containing compound, and the like.
  • Examples of the metal compound of Group IA and Group IIA in the transesterification catalyst (D) include lithium, sodium, potassium, rubidium, cesium, cesium, magnesium, calcium, strontium, barium, and the like.
  • the transesterification catalyst (D) is preferably a metal having a electronegativity of 0.7 to 1.1 in the metals of Groups IA and IIA, more preferably a metal of 0.75 to 1.0, still more preferably a metal of 0.75 to 0.98.
  • Specific examples thereof include hydrazine (0.79), potassium (0.82), sodium (0.93), lithium (0.98), hydrazine (0.89), hydrazine (0.95), and calcium (1.0).
  • the values in parentheses are electronegativity.
  • the transesterification catalyst (D) may, for example, be a metal salt composed of the above metal, an organic acid such as a carboxylic acid, a carbonic acid, an alcohol or a phenol, nitric acid, phosphoric acid or boric acid. Further, examples of the metal salt include halides and hydroxides of the above metals.
  • the acid dissociation constant (pKa) of the counter ion of the metal ion in the transesterification catalyst (D) is preferably from 2 to 16.
  • the transparency of the resin composition of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) can be improved without increasing the amount of the metal-converted catalyst, and the deterioration of the hue can be further prevented.
  • the acid dissociation constant (pKa) of the counter ion of the metal ion in the transesterification catalyst (D) is more preferably from 3 to 11, particularly preferably from 5 to 10.
  • the metal compound of Group IA used as the transesterification catalyst (D) for example, the following compounds can be employed.
  • At least one selected from the group consisting of a sodium compound, a potassium compound, and an antimony compound is preferable, and a potassium compound and/or an antimony compound are more preferable from the viewpoint of transparency, color tone, and heat and humidity resistance.
  • Particularly preferred are potassium hydrogencarbonate, cesium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium acetate, cesium acetate, potassium stearate, and strontium stearate.
  • the metal compound of Group IIA used as the transesterification catalyst (D) for example, the following compounds can be employed.
  • a calcium compound is preferred from the viewpoint of transparency and color tone.
  • Particularly preferred are calcium hydroxide, calcium hydrogencarbonate, and calcium acetate.
  • the metal amount derived from the metal compound of Group IA and Group IIA which is the transesterification catalyst (D) is preferably 0.8 ppm by weight or more and 1000 ppm by weight or less. Also depending on the kind of the metal, when it exceeds 1000 ppm by weight, the color tone of the resin composition is deteriorated, and the moist heat resistance is lowered. When it is less than 0.8 ppm by weight, the transparency of the resin composition is insufficient. From the same viewpoint, the amount of the metal derived from the transesterification catalyst (D) is more preferably 0.9 ppm by weight or more and 100 ppm by weight or less, and particularly preferably 1 ppm by weight or more and 10 ppm by weight or less.
  • the transesterification catalyst (D) introduced in the polycarbonate resin composition is usually higher than the polymerization catalyst of the polycarbonate resin (A) as a raw material or the polymerization catalyst of the aromatic polycarbonate resin (B).
  • an acidic compound such as butyl p-toluenesulfonate is deactivated after the polymerization step. Therefore, it is preferred to additionally add a transesterification catalyst (D).
  • the amount of the metal compound derived from the Group IA and Group IIA which is the above-mentioned transesterification catalyst (D) depends on the kind of the metal, and is composed of the polycarbonate resin (A) and the aromatic polycarbonate resin (B).
  • the resin composition is 0.5 to 1000 ppm by weight, preferably 1 to 100 ppm by weight, and particularly preferably 1 to 10 ppm by weight, in terms of metal. When it is less than 0.5 ppm by weight, the transparency of the resin composition becomes insufficient. On the other hand, when it is more than 1000 ppm by weight, it is transparent, but the coloring is strong, and the molecular weight (melt viscosity) of the resin composition is lowered, and a resin composite excellent in impact resistance cannot be obtained.
  • the tin-based compound used as the transesterification reaction catalyst (D) is one or more compounds selected from the following formula (2) or (3).
  • R represents an alkyl group or an aryl group having 1 to 15 carbon atoms
  • X1 to X4 represent an alkyl group having 1 to 15 carbon atoms, an aryl group, an allyloxy group, a cyclohexyl group, a hydroxyl group, or a halogen-containing compound.
  • the monovalent group may be the same or different.
  • X5 represents a sulfur or an oxygen atom.
  • dibutyltin oxide methylphenyltin oxide, tetraethyltin oxide, hexaethyltin oxide, cyclohexyltin oxide, behenyltin oxide, and triethylamine.
  • dibutyltin dilaurate is mentioned.
  • stannic acid may be used, and in this case, an alkylstannic acid such as methyl stannic acid, ethyl stannic acid or butyl stannic acid may be mentioned.
  • the amount of the tin-based compound to be used as the compound (D) is 0.001 part by weight or more and 5 parts by weight based on 100 parts by weight of the resin composition containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). the following. It is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. Further, it is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less. When the amount is less than 0.001 part by weight, the effect of the transparency is insufficient. When the amount is more than 5 parts by weight, the coloring is remarkable, but the coloring is remarkable, the molecular weight is lowered, and the mechanical strength is insufficient.
  • the basic nitrogen-containing compound used as the transesterification catalyst (D) may, for example, be a basic ammonium compound or an amine compound.
  • the basic ammonium compound for example, the following compounds can be used. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylhydrogen Ammonium Oxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide, Tributylphenylammonium Hydroxide, Tetraphenyl Examples of ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium
  • 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 basic nitrogen-containing compound to be used as the compound (D) is 0.001 parts by weight or more and 5 parts by weight based on 100 parts by weight of the resin composition containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). Parts by weight or less. It is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. Further, it is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less.
  • the amount is less than 0.001 part by weight, the effect of the transparency is insufficient.
  • the amount is more than 5 parts by weight, the coloring is remarkable, but the coloring is remarkable, the molecular weight is lowered, and the mechanical strength is insufficient.
  • the solid compound in the method of adding the above-mentioned transesterification catalyst (D), 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 same ones as the catalyst deactivator described above can be used.
  • the amount of the acidic compound (E) to be added is preferably 0.5 molar equivalent or more and 5 molar equivalent or less with respect to 1 molar equivalent of the compound (D) contained in the polycarbonate resin composition. At this time, the moist heat resistance can be further improved, and the thermal stability during molding or the like can be further improved. From the same viewpoint, the amount of the acidic compound (E) to be added is more preferably 0.6 to 2 molar equivalents per 1 molar equivalent of the compound (D), and still more preferably 0.7 to 1 molar equivalent.
  • the resin composite containing the polycarbonate resin composition (X) is preferably a molded article having a thickness of 1 mm and having an average light transmittance of 50% or more in the thickness direction.
  • the average light transmittance is more preferably 65% or more, and still more preferably 70% or more from the viewpoints of suitability for use in a transparent use and good image clarity at the time of dyeing.
  • the method of measuring the average light transmittance will be described in the examples to be described later.
  • the peak of the glass transition temperature measured by the DSC method is preferably single. Further, the glass transition temperature of the polycarbonate resin composition is preferably 100 ° C or more and 200 ° C or less. At this time, since heat resistance can be further improved, deformation of the molded article can be further prevented. In addition, in this case, thermal deterioration of the polycarbonate resin (A) at the time of production of the resin composition can be further suppressed, and impact resistance can be further improved. Further, thermal deterioration of the resin composition at the time of molding can be further suppressed. From the same viewpoint, the glass transition temperature of the polycarbonate resin composition 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 resin composition (X) contains a polycarbonate resin (A) and an aromatic polycarbonate resin (B) containing a constituent unit derived from the compound represented by the above formula (1), and can be obtained by using a polycarbonate resin ( A) and the aromatic polycarbonate resin (B) are adjusted to a predetermined range.
  • the mixing ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the above resin composition (X) is preferably a difference in refractive index between a single substance of the resin composition (X) and the glass filler (C). Adjust to 0.01 or less. It is preferably 0.005 or less, and particularly preferably 0.003 or less. When the refractive index difference is more than 0.01, the average light transmittance is lowered and the transparency is poor.
  • the compounding ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the above resin composition (X) is preferably an Abbe number of the above resin composition (X) and a glass filler (C).
  • the difference between the Abbe numbers of the single substances is adjusted to be 25 or less. It is preferably 24 or less, and particularly preferably 23 or less.
  • additives can be added to the above polycarbonate resin composition.
  • additives there are antioxidants, UV absorbers, light stabilizers, mold release agents, heat stabilizers, flame retardants, flame retardant aids, inorganic fillers other than glass fillers, impact modifiers, hydrolysis inhibitors,
  • an additive which is usually used in a polycarbonate resin can be used.
  • the antioxidant a general antioxidant used in the resin can be used, but from oxidation stability, heat From the viewpoint of stability, a phosphite-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant are preferable.
  • the amount of the antioxidant added is preferably 5 parts by weight or less based on 100 parts by weight of the resin composition (X). At this time, it is possible to more reliably prevent contamination of the mold at the time of molding, and to obtain a molded article having a more excellent surface appearance. From the same viewpoint, the amount of the antioxidant added is more preferably 3 parts by weight or less, still more preferably 2 parts by weight or less based on 100 parts by weight of the resin composition (X).
  • the amount of the antioxidant added is preferably 0.001 part by weight or more based on 100 parts by weight of the resin composition (X). At this time, the improvement effect with respect to the formation stability can be fully obtained. From the same viewpoint, the amount of the antioxidant added is more preferably 0.002 parts by weight or more, and still more preferably 0.005 parts by weight or more based on 100 parts by weight of the resin composition (X).
  • phosphite-based antioxidant examples include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and trisphosphonium phosphite.
  • trioctyl phosphite tris(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, Monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol II Phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di Tert-butylphenyl) pentaerythritol diphosphite
  • tridecyl phenyl phosphite tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and double (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite.
  • These compounds may be used alone or in combination of two or more.
  • sulfur-based antioxidant examples include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and dimyristyl- 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra ( 3-laurylthiopropionate), bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl] sulfide, octadecyl disulfide Ether, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis(2-naphthol), and the like.
  • pentaerythritol tetrakis(3-laurylthiopropionate) is
  • phenolic antioxidant examples include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and trisole.
  • an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable, and specifically, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyl is preferable.
  • Phenyl)propionate pentaerythritol-tetra ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate ⁇ , 1,6-hexanediol-bis[3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl) Phenylene or the like is further preferably pentaerythritol-tetra ⁇ 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. These compounds may be used alone or in combination of two or more.
  • Examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound, a triazine-based compound, a benzoate-based compound, a hindered amine-based compound, a phenyl salicylate-based compound, and a cyano group.
  • An acrylate type compound, a malonate type compound, an oxalic acid aniline type compound, etc. may be used alone or in combination of two or more.
  • benzotriazole-based compound examples include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole and 2-(2'-hydroxyl group). -3'-tert-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3'-methyl-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-dodecylphenyl)benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-tert-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, Methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert
  • 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-based compound examples include ethyl 2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate. .
  • 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. At this time, the weather resistance of the molded article can be further improved. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 900 or less. Further, the molecular weight of the light stabilizer is preferably 300 or more. At this time, heat resistance can be improved, and contamination of the mold at the time of molding can be prevented more reliably. As a result, a molded article having a more excellent surface appearance can be obtained. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 400 or more. Further, the light stabilizer is preferably a compound having a piperidine structure.
  • 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 resin composition (X).
  • the coloring of the polycarbonate resin composition can be further prevented.
  • a darkness having a deep and clear feeling can be obtained.
  • the light resistance of the polycarbonate resin composition can be further improved, and the polycarbonate resin composition can exhibit excellent light resistance even when applied to, for example, automotive interior and exterior decoration applications.
  • the content of the light stabilizer 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 based on 100 parts by weight of the resin composition (X).
  • the aromatic polycarbonate resin (B) tends to be easily decomposed by the hindered amine light stabilizer. Therefore, in the case where the ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is increased, the amount of the aromatic polycarbonate resin (B) is preferably small, and it is preferable to set the light stabilizer in a small amount. 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 When the amount of the fatty acid ester of the polyol is adjusted within this range, the effect of addition can be sufficiently obtained, and during the mold release during the molding process, cracking of the molded article due to mold release failure can be more reliably prevented. Further, in this case, it is possible to further suppress the white turbidity of the resin composite or the increase in the adhering matter adhering to the mold during the forming process.
  • 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, 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 stearic acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, and stearic acid single sorbitol.
  • Alcohol ester behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, pentaerythritol tetradecanoate, propylene glycol monostearate, isopropyl palmitate, Sorbitol monostearate and the like.
  • 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 can also be, for example, an aromatic polyester, an aliphatic polyester, a polyamide, a polystyrene, a polyolefin, an acrylic, an amorphous polyolefin, or the like without deteriorating the effects of the present invention.
  • One or two or more kinds of biodegradable resins such as ABS and AS, such as a synthetic resin, a polylactic acid, and a polystyrene succinate, are kneaded and used as a polymer alloy.
  • silica, alumina, titania, calcium sulfate powder, gypsum, gypsum whisker other than the above-mentioned glass filler (C) may be added in a range in which designability can be maintained.
  • Calcium silicate such as barium sulfate, talc, mica or wollastonite
  • carbon black graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber , inorganic fillers such as stainless steel fiber, potassium titanate fiber, their whiskers, powdered organic fillers such as wood powder, bamboo powder, coconut starch, softwood powder, pulp powder; crosslinked polyester, polystyrene, styrene ⁇ Saccular/spherical organic filler such as acrylic copolymer or urea resin; carbon Fibrous organic fillers such as fibers, synthetic fibers, and natural fibers.
  • the polycarbonate resin composite can be produced by using a mixer such as a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a kneading roll or an extruder to simultaneously apply the above components in a certain ratio.
  • a mixer such as a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a kneading roll or an extruder to simultaneously apply the above components in a certain ratio.
  • the mixing may be carried out in any order to perform the production.
  • a substance which can be mixed under reduced pressure is more preferable.
  • a glass filler (C) after previously preparing the resin composition (X) containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B).
  • a glass filler (C) it is preferred to produce the resin composition (X) in an extruder, and then introduce the glass filler (C) into an extruder by a side feeder.
  • the polycarbonate resin composite 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. Therefore, it is suitable for interior parts for vehicles.
  • the polycarbonate resin composite is excellent in hue, transparency, mechanical strength, and the like, and is excellent in stability in hue and optical properties under moist heat. Therefore, it can be applied to injection of electric and electronic parts, parts for automobiles, and applications for glass replacement. Forming field; film, sheet material; extrusion molding in the field of bottles and containers; lens applications such as camera lenses, viewfinder lenses, CCD or CMOS lenses, etc.
  • the polycarbonate resin composite is excellent in transparency, mechanical strength, and the like, it is colored by using a coloring agent or the like, and is excellent in image clarity. Therefore, it can be applied to interior and exterior decorative parts for automobiles, electrical and electronic parts, frames, and the like.
  • automotive exterior parts such as fenders, bumpers, instrument panels, door panels, side trims, pillars, radiator grilles, side protectors, side trims, rear protectors, rear trims, various spoilers , hood, roof panel, trunk lid, detachable top, window reflector, mirror housing, outer door handle, etc.
  • interior trim parts of automobiles there are, for example, instrument panels, center console panels, instrument components, various switches, car navigation components, car audio and video components, and automatic mobile computer components.
  • an electric and electronic component or a housing for example, an external component such as a desktop computer or a notebook computer, an external component of a printer, a copying machine, a scanner, and a facsimile machine (a multifunction peripheral including the same), and an external decorative component and display device (for a OA device) Exterior decorative parts such as CRT, liquid crystal, plasma, projector, and organic EL, external decorative parts such as a mouse, keyboard keys, switch mechanism components such as various switches, and game machines (home game machines, business game machines) And exterior parts such as pinball machines and slot machines. Further, a portable information terminal (so-called PDA), a mobile phone, a portable book (a dictionary, etc.), and a portable battery can be cited.
  • PDA portable information terminal
  • a mobile phone a portable book (a dictionary, etc.)
  • a portable battery can be cited.
  • a device for reading and recording media (CD, MD, DVD, next-generation high-density disk, hard disk, etc.), reading device (IC card, artificial intelligence media, memory stick, etc.), optical camera, digital camera, parabolic antenna , electric tools, VTR, iron, hair dryer, rice cooker, microwave oven, hot plate, audio equipment, lighting equipment, refrigerator, air conditioner, air purifier, negative ion generator and clock, etc.
  • Electrical OA equipment household electrical products.
  • the surface of the molded body may be deteriorated to lower the transparency.
  • the laminated transparent resin layer may be a curable resin layer such as a hard coat layer or a clear coat layer, or a transparent thermoplastic resin film may be laminated by in-mold molding.
  • 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 Tg of the polycarbonate resin composition was raised from 25 ° C to 200 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere using a differential scanning calorimeter "DSC7" manufactured by Perkinelmer Co., Ltd., and held at 200 ° C for 3 minutes.
  • the temperature was lowered to 25 ° C at a cooling rate of 20 ° C / min, and after maintaining at 25 ° C for 3 minutes, and then raised to 200 ° C at a heating rate of 5 ° C / min, the obtained DSC curve was obtained according to the method of JIS-K7121.
  • the value of Tmg was performed. Specifically, the case where the peak of the DSC curve is single is evaluated. When the singularity is " ⁇ " and the peak of the DSC curve is plural, the singularity is "x".
  • the pellet of the polycarbonate resin composite was dried at 90 ° C for 4 hours or more using a hot air dryer. Then, the dried pellets were supplied to a molding machine (Haitian Plastics Group, HTF861TJ), and molded at a resin temperature of 240 ° C, a mold temperature of 60 ° C, and a molding cycle of 50 seconds, thereby obtaining a formed plate (width 100 mm ⁇ length 100 mm). ⁇ thickness 1mm). According to Chinese Industrial Standards (2000). For the polycarbonate/glass fiber composite, it was hot pressed at 240 ° C (BL-6170-A-25J, Baolun Precision Testing Instrument Co., Ltd.) into a sheet of 30 mm * 20 mm * 1 mm.
  • the light transmittance of the wavelength in the range of 300 nm to 800 nm was measured using a UV/vis spectrophotometer (SHIMADZU, UV2550), and the average light transmittance of the sample was calculated therefrom.
  • the average light transmittance is set to 50% or more.
  • a drop of bromo naphthalene was dropped on a 2WAJ, Shanghai Optical Instrument Factory, and a polycarbonate resin composition (X) of 10 mm * 10 mm * 1 mm was placed to make it fully contacted, and it was read in sunlight. Number of shells.
  • a 17 mm*7.5 mm*0.4 mm polycarbonate/glass fiber composite sample was measured for modulus of elasticity using DMA (Q800, TA).
  • the test conditions were as follows: amplitude 5 ⁇ m, frequency 10 Hz, temperature 30 ° C, film stretching mode.
  • 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.]
  • 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, 90 minutes, and a second vertical stirred reactor: 195 ° C, 10 kPa, 45 minutes, and third standing Stirred reactor: 210 ° C, 3 kPa, 45 minutes, 4th horizontal stirred reactor: 225 ° C, 0.5 kPa, 90 minutes.
  • the inside of the fourth horizontally stirred reactor was operated while finely adjusting the reduced viscosity of the obtained polycarbonate resin to 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 then the resin was supplied to the exhaust type twin-screw extruder in a molten state [TEX30 ⁇ , L manufactured by Nippon Steel Co., Ltd. /D: 42.0, L (mm): length of the screw, D (mm): diameter of the screw].
  • the polycarbonate resin that passed through the extruder was passed through a candle-type filter (manufactured by SUS316) having a mesh size of 10 ⁇ m in the same molten state, and the foreign matter was filtered.
  • 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.
  • Water injection devolatilization was performed by adding 2000 mass ppm of water to the resin in the vicinity of the second exhaust port. 0.1 parts by mass, 0.05 parts by mass, and 0.3 parts, respectively, are added to 100 parts by mass of the polycarbonate resin in the vicinity of the third exhaust port. Parts by mass of Irganox 1010, AS 2112, E-275.
  • an ISB/CHDM copolymer polycarbonate resin was obtained.
  • 0.65 mass ppm of phosphorous acid (0.24 mass ppm in terms of phosphorus atom) was added to the above polycarbonate resin.
  • phosphorous acid was added as follows.
  • the masterbatch of the ethanol solution in which the phosphorous acid was mixed was applied to the pellet of the polycarbonate resin obtained in Production Example 1, and was placed from the vicinity of the first exhaust port of the extruder (on the resin supply port side of the extruder).
  • the master batch was supplied in an amount of 1 part by mass based on 100 parts by mass of the polycarbonate resin in the extruder.
  • PC-A1 The polycarbonate resin (A) obtained in Production Example 1 is referred to as "PC-A1".
  • phosphorous acid 0.65 mass ppm of phosphorous acid (0.24 mass ppm in terms of phosphorus atom) was added to the above polycarbonate resin.
  • phosphorous acid was added as follows. The masterbatch of the ethanol solution in which the phosphorous acid was mixed was applied to the pellet of the polycarbonate resin obtained in Production Example 1, and was placed from the vicinity of the first exhaust port of the extruder (on the resin supply port side of the extruder). The master batch was supplied in an amount of 1 part by mass based on 100 parts by mass of the polycarbonate resin in the extruder.
  • PC-B NOVAREX 7022J manufactured by Mitsubishi Engineering Plastics Co., Ltd. (100 mol% aromatic polycarbonate resin of bisphenol A constituent unit, reduced viscosity of polycarbonate resin 0.51 dL/g)
  • the polycarbonate resin composite of the examples includes the polycarbonate resin (A) and the aromatic polycarbonate resin (B) containing the constituent units derived from the compound represented by the above formula (1).
  • the molded article having a thickness of 1 mm of the polycarbonate resin composite had an average light transmittance of 50% or more. It was found that such a polycarbonate resin composite is excellent in transparency and excellent in rigidity.

Abstract

A polycarbonate resin composite having excellent transparency and rigidity comprises 10-150 parts by weight of a glass filler (C) per 100 parts by weight of a resin composition (X). The resin composition (X) comprises an aromatic polycarbonate resin (B) and a polycarbonate resin (A) comprising a constituent unit derived from a compound of the following formula (1). The average light transmittance of the composite is 50% above, measured with a 1-mm thick sheet.

Description

聚碳酸酯树脂复合物Polycarbonate resin composite 技术领域Technical field
本发明涉及一种透明性优异、刚性优异的聚碳酸酯树脂复合物、其制造方法、及将该树脂复合物成形而成的成形体。The present invention relates to a polycarbonate resin composite which is excellent in transparency and excellent in rigidity, a method for producing the same, and a molded article obtained by molding the resin composite.
背景技术Background technique
含有源自双酚A等的结构的现有的芳香族聚碳酸酯树脂由于其优异的透明性、耐热性，作为工业用的透明材料广泛用于电气、机械、汽车领域等。另外，也作为光学材料用的塑料用于透镜或光盘等。A conventional aromatic polycarbonate resin containing a structure derived from bisphenol A or the like is widely used as an industrial transparent material for electric, mechanical, automotive, and the like because of its excellent transparency and heat resistance. Further, plastics used as optical materials are used for lenses, optical disks, and the like.
芳香族聚碳酸酯树脂为了进一步抑制热膨胀和提高强度，提出有配合各种玻璃填料。但是，作为配合于芳香族聚碳酸酯树脂的一般的玻璃纤维材料的一个例子的E玻璃的折射率(波长589nm下的折射率、以下设为nd)为1.55左右，与此相对，芳香族聚碳酸酯树脂的折射率高达1.580～1.590，因此，若在芳香族聚碳酸酯树脂中分散由通常的E玻璃构成的纤维，则存在因折射率之差异会导致透明性降低的问题。In order to further suppress thermal expansion and increase strength, the aromatic polycarbonate resin has been proposed to be blended with various glass fillers. However, the refractive index (refractive index at a wavelength of 589 nm, hereinafter nd) of E glass which is an example of a general glass fiber material to be blended in an aromatic polycarbonate resin is about 1.55, whereas aromatic poly Since the refractive index of the carbonate resin is as high as 1.580 to 1.590, when a fiber composed of ordinary E glass is dispersed in an aromatic polycarbonate resin, there is a problem that transparency is lowered due to a difference in refractive index.
为了解决该问题，公开有一种通过将折射率调整为1.570～1.600的特定的组成的玻璃填料配合于芳香族聚碳酸酯树脂，从而不会降低透明性的玻璃纤维组合物(参照专利文献1)。另外，所述玻璃纤维组合物存在因自玻璃溶出的碱离子引起树脂的水解的问题，为了对其进行改良，也公开有一种折射率调整为1.570～1.600的特定的组成的玻璃纤维组合物(参照专利文献2)。另外，还公开有一种不仅透明性优异，而且在芳香族聚碳酸酯树脂中配合玻璃填料时，抑制变为黄色的玻璃纤维组合物(参照专利文献3)。In order to solve this problem, a glass fiber composition in which a glass filler having a specific composition having a refractive index of 1.570 to 1.600 is blended in an aromatic polycarbonate resin to prevent transparency is disclosed (see Patent Document 1). . Further, the glass fiber composition has a problem of hydrolysis of the resin due to alkali ions eluted from the glass, and in order to improve it, a glass fiber composition having a specific composition whose refractive index is adjusted to 1.570 to 1.600 is also disclosed ( Refer to Patent Document 2). In addition, it is also disclosed that a glass fiber composition which is yellow is suppressed when the glass filler is blended in an aromatic polycarbonate resin (see Patent Document 3).
另一方面，芳香族聚碳酸酯树脂在长时间暴露于紫外线或可见光的场所使用时，色相或透明性、机械强度变差，因此，在室外或照明装置的附近的使用存在限制。因此，公开有一种包含含有源自异山梨醇所代表的二羟基化合物的构成单元和源自脂肪族烃的二羟基化合物的构成单元45摩尔％以上的聚碳酸酯树脂和芳香族聚碳酸酯树脂的聚碳酸酯树脂组合物(参照专利文献4)。On the other hand, when the aromatic polycarbonate resin is used in a place where it is exposed to ultraviolet light or visible light for a long period of time, the hue, transparency, and mechanical strength are deteriorated. Therefore, there is a limitation in use in the outdoor or in the vicinity of the lighting device. Therefore, a polycarbonate resin and an aromatic polycarbonate resin containing 45 mol% or more of a constituent unit containing a dihydroxy compound represented by isosorbide and a dihydroxy compound derived from an aliphatic hydrocarbon are disclosed. Polycarbonate resin composition (refer to Patent Document 4).
另外，还公开有一种包含含有源自异山梨醇、1,4-环己烷二甲醇、三环癸烷二甲醇这样的脂肪族二羟基化合物的脂肪族碳酸酯重复单元的芳香族-脂肪族共聚聚碳 酸酯树脂和折射率调整为1.500～1.540的特定组成的玻璃填料的透明性优异的聚碳酸酯树脂组合物(参照专利文献5)。Further, an aromatic-aliphatic group containing an aliphatic carbonate repeating unit derived from an aliphatic dihydroxy compound derived from isosorbide, 1,4-cyclohexanedimethanol, or tricyclodecane dimethanol is also disclosed. Copolymerized polycarbon A polycarbonate resin composition having excellent transparency of a glass filler of a specific composition having a refractive index of 1.500 to 1.540 (see Patent Document 5).
现有技术文献Prior art literature
专利文献Patent literature
专利文献1：日本特公昭62-001338号公报Patent Document 1: Japanese Patent Publication No. 62-001338
专利文献2：日本特开平5-155638号公报Patent Document 2: Japanese Patent Laid-Open No. Hei 5-155638
专利文献3：日本特开2007-153729号公报Patent Document 3: Japanese Laid-Open Patent Publication No. 2007-153729
专利文献4：国际公开第2011/071162号小册子Patent Document 4: International Publication No. 2011/071162
专利文献5：国际公报第2014/069659号小册子Patent Document 5: International Gazette No. 2014/069659
发明内容Summary of the invention
发明要解决的课题Problem to be solved by the invention
然而，专利文献1～3及5的透明聚碳酸酯树脂组合物存在如下问题：需要特殊组成的玻璃填料，但是不能使用一直以来用作玻璃填料的E玻璃，结果成本变得昂贵，且聚碳酸酯树脂组合物的折射率变高，因此，平均光线透过率变低。However, the transparent polycarbonate resin compositions of Patent Documents 1 to 3 and 5 have problems in that a glass filler having a special composition is required, but E glass which has been conventionally used as a glass filler cannot be used, and as a result, cost becomes expensive, and polycarbonate is expensive. Since the refractive index of the ester resin composition becomes high, the average light transmittance is low.
本发明是鉴于这种背景而完成的，提供一种透明性优异，并且兼备高刚性的聚碳酸酯树脂复合物、及由其构成的成形体。The present invention has been made in view of such a background, and provides a polycarbonate resin composite which is excellent in transparency and has high rigidity, and a molded body comprising the same.
用于解决课题的技术方案Technical solution for solving the problem
本发明人等为了解决上述课题进行了潜心研究，结果发现，使用以一直以来使用的E玻璃作为原料的廉价的玻璃填料且透明性优异，并且兼备高刚性的聚碳酸酯树脂复合物及由其构成的成形体，以至完成了本发明。即，本发明的要点在于下述的[1]～[6]。In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies and found that an inexpensive glass filler using E glass which has been conventionally used as a raw material is excellent in transparency, and a polycarbonate resin composite having high rigidity and a high rigidity thereof are used. The formed body thus formed completed the present invention. That is, the gist of the present invention lies in the following [1] to [6].
[1]一种树脂复合物，其相对于包含含有源自下述式(1)所示的化合物的构成单元的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的树脂组合物(X)100重量份含有10重量份～150重量份的玻璃填料(C)，其特征在于，以厚度1mm的片材测得的平均光线透过率为50％以上。[1] A resin composite comprising a resin composition comprising a polycarbonate resin (A) and an aromatic polycarbonate resin (B) containing a constituent unit derived from a compound represented by the following formula (1) The glass filler (C) is contained in an amount of 10 parts by weight to 150 parts by weight per 100 parts by weight of the object (X), and the average light transmittance measured by a sheet having a thickness of 1 mm is 50% or more.
[化学式1] [Chemical Formula 1]
Figure PCTCN2015085764-appb-000001
Figure PCTCN2015085764-appb-000001
[2]根据[1]所述的树脂复合物，其特征在于，相对于所述聚碳酸酯树脂(A)中的源自全部二醇的构成单元100摩尔％，以超过50摩尔％的比例含有源自下述式(1)所示的二羟基化合物的构成单元。[2] The resin composite according to [1], which is a ratio of more than 50% by mole based on 100% by mole of the constituent units derived from all the diols in the polycarbonate resin (A) A constituent unit derived from a dihydroxy compound represented by the following formula (1) is contained.
[化学式2][Chemical Formula 2]
Figure PCTCN2015085764-appb-000002
Figure PCTCN2015085764-appb-000002
[3]根据[1]或[2]所述的树脂复合物，其特征在于，所述树脂组合物(X)含有聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)和酯交换反应催化剂(D)及/或酸性化合物(E)。[3] The resin composite according to [1] or [2], wherein the resin composition (X) contains a polycarbonate resin (A), an aromatic polycarbonate resin (B), and an ester. The reaction catalyst (D) and/or the acidic compound (E) are exchanged.
[4]根据[1]～[3]中任一项所述的树脂复合物，其特征在于，所述树脂组合物(X)以波长589nm测得的折射率和以波长589nm测得的玻璃填料(C)单一物质的折射率之差为0.01以下。[4] The resin composite according to any one of [1] to [3] wherein the resin composition (X) has a refractive index measured at a wavelength of 589 nm and a glass measured at a wavelength of 589 nm. The difference in refractive index of the single substance of the filler (C) is 0.01 or less.
[5]根据[1]～[4]中任一项所述的树脂复合物，其特征在于，所述玻璃填料(C)以波长589nm测得的折射率为1.550以上且1.560以下。[5] The resin composite according to any one of [1] to [4] wherein the glass filler (C) has a refractive index measured at a wavelength of 589 nm of 1.550 or more and 1.560 or less.
[6]根据[1]～[5]中任一项所述的树脂复合物，其特征在于，所述树脂组合物(X)的阿贝数和玻璃填料(C)单一物质的阿贝数之差为25以下。[6] The resin composite according to any one of [1] to [5] wherein the Abbe number of the resin composition (X) and the Abbe number of the single substance of the glass filler (C). The difference is 25 or less.
发明效果Effect of the invention
本发明的聚碳酸酯树脂复合物及其成形体的透明性优异，并且刚性优异。The polycarbonate resin composite of the present invention and a molded article thereof are excellent in transparency and excellent in rigidity.
具体实施方式detailed description
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例(代表例)，只要不超出其要点，本发明则并不限定于以下的内容。Hereinafter, the embodiment of the present invention will be described in detail, but the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to the following unless it goes beyond the point.
[聚碳酸酯树脂(A)] [Polycarbonate Resin (A)]
上述聚碳酸酯树脂(A)优选为相对于源自全部二醇的构成单元100摩尔％以超过50摩尔％的比例含有源自下述式(1)所示的二羟基化合物的构成单元(在此将其称为“构成单元(a)”)的聚碳酸酯树脂。聚碳酸酯树脂(A)可以为构成单元(a)的均聚碳酸酯树脂，也可以为将构成单元(a)以外的构成单元共聚而成的聚碳酸酯树脂。从耐冲击性优异的观点考虑，优选为共聚聚碳酸酯树脂。It is preferable that the polycarbonate resin (A) contains a constituent 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 constituent unit derived from all the diols. This is referred to as a "polycarbonate resin constituting the unit (a)"). The polycarbonate resin (A) may be a homopolycarbonate resin constituting the unit (a), or may be a polycarbonate resin obtained by copolymerizing constituent units other than the constituent unit (a). From the viewpoint of excellent impact resistance, a copolymerized polycarbonate resin is preferred.
[化学式4][Chemical Formula 4]
Figure PCTCN2015085764-appb-000003
Figure PCTCN2015085764-appb-000003
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单独使用1种，也可以组合使用2种以上。Examples of the dihydroxy compound represented by the above formula (1) include isosorbide (ISB), isomannide, and isoidide in a stereoisomer relationship. These dihydroxy compounds may be used alone or in combination of two or more.
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、耐热性及碳中和的方面考虑，最优选为通过对由作为植物来源的资源而丰富存在并且可容易地获得的各种淀粉制造的山梨糖醇进行脱水缩合而得到的异山梨糖醇(ISB)。Among the dihydroxy compounds represented by the above formula (1), from the viewpoints of availability, ease of production, weather resistance, optical properties, moldability, heat resistance, and carbon neutralization, it is most preferable to Isosorbide (ISB) obtained by dehydration condensation of various starch-produced sorbitol which is abundant in plant resources and which can be easily obtained.
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，在保存中或制造时，为了防止由氧引起的分解，优选不混入水分并且使用脱氧剂或在氮气气氛下进行。In addition, the dihydroxy compound represented by the above formula (1) is easily oxidized by oxygen. Therefore, in order to prevent decomposition by oxygen during storage or at the time of manufacture, it is preferable to carry out without using water and using a deoxidizer or under a nitrogen atmosphere.
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构成单元(a)、源自选自由脂肪族烃的二羟基化合物、脂环式烃的二羟基化合物、及含有醚的二羟基化合物构成的组中的1种以上二羟基化合物的构成单元(在此将其称为“构成单元(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，可提高得到的聚碳酸酯树脂的韧性。这些二羟基化合物中，优选使用使韧性提高的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、及含有醚的二羟基化合物的具体例如下所述。Further, the polycarbonate resin (A) is preferably a constituent unit (a) containing a dihydroxy compound derived from the general formula (1), and a dihydroxy compound derived from an aliphatic hydrocarbon or an alicyclic hydrocarbon. A copolymerized polycarbonate resin of a constituent unit of one or more kinds of dihydroxy compounds in the group consisting of a hydroxy compound and an ether-containing dihydroxy compound (hereinafter referred to as "constituting unit (b)"). Since these dihydroxy compounds have a soft molecular structure, the toughness of the obtained polycarbonate resin can be improved by using these dihydroxy compounds as a raw material. Among these dihydroxy compounds, a dihydroxy compound of an aliphatic hydrocarbon or a dihydroxy compound of an alicyclic hydrocarbon having a large effect of improving toughness 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 are as follows.
作为脂肪族烃的二羟基化合物，例如可以采用以下的二羟基化合物。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、乙二醇等具有支链的脂肪族二羟基化合物。As the dihydroxy compound of the aliphatic hydrocarbon, for example, the following dihydroxy compound can be used. Glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-anthracene a linear aliphatic dihydroxy compound such as alcohol 1,12-dodecanediol; a branched fat such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol or ethylene glycol Group dihydroxy compounds.
作为脂环式烃的二羟基化合物，例如可以采用以下的二羟基化合物。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。As the dihydroxy compound of the alicyclic hydrocarbon, for example, the following dihydroxy compound can be used. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-ten Hydrogenated naphthalene dimethanol, 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-gold a dihydroxy compound as a primary alcohol of an alicyclic hydrocarbon exemplified by a dihydroxy compound derived from a terpene compound, such as alkane dimethanol or limonene; 1,2-cyclohexanediol, 1,4-cyclohexane a secondary alcohol or a tertiary exemplified as an alicyclic hydrocarbon exemplified by an alcohol, 1,3-adamantanediol, hydrogenated bisphenol A, 2,2,4,4-tetramethyl-1,3-cyclobutanediol or the like a dihydroxy compound of an alcohol.
作为含有醚的二羟基化合物，可以举出：氧亚烷基二醇类或含有缩醛环的二羟基化合物。Examples of the ether-containing dihydroxy compound include an oxyalkylene glycol or a dihydroxy compound containing an acetal ring.
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。As the oxyalkylene glycol, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol or the like can be used.
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(2)所示的螺二醇或下述结构式(3)所示的二噁烷二醇等。As the dihydroxy compound containing an acetal ring, for example, a spiro diol represented by the following structural formula (2) or a dioxane diol represented by the following structural formula (3) can be used.
[化学式5][Chemical Formula 5]
Figure PCTCN2015085764-appb-000004
Figure PCTCN2015085764-appb-000004
[化学式6][Chemical Formula 6]
Figure PCTCN2015085764-appb-000005
Figure PCTCN2015085764-appb-000005
在上述聚碳酸酯树脂(A)中，上述构成单元(a)相对于源自全部二羟基化合物的构成单元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。在构成单元(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，构成单元(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。In the polycarbonate resin (A), the content ratio of the above-mentioned structural unit (a) to 100 mol% of the constituent unit derived from all dihydroxy compounds is preferably more than 50% by mol, more preferably 55% by mol or more and 95% by mol. % or less is more preferably 60% by mole or more and 90% by mole or less, and particularly preferably 65% by mole or more and 85% by mole or less. When the content ratio of the constituent unit (a) is 50% by mole or less, the biomass content rate is changed. In addition to low, heat resistance is insufficient. On the other hand, 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.
另外，上述聚碳酸酯树脂(A)可以进一步含有上述构成单元(a)及上述构成单元(b)以外的构成单元。作为这样的构成单元(其它二羟基化合物)，例如可以采用含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构成单元的情况下，由于上述理由，有可能无法得到高分子量的聚碳酸酯树脂，耐冲击性的提高效果降低。因此，从进一步提高耐冲击性的观点考虑，相对于源自全部二羟基化合物的构成单元100摩尔％，源自含有芳香族基团的二羟基化合物的构成单元的含有比例优选为10摩尔％以下，更优选为5摩尔％以下。Further, the polycarbonate resin (A) may further contain constituent units other than the above structural unit (a) and the above structural unit (b). As such a structural unit (other dihydroxy compound), for example, a dihydroxy compound containing an aromatic group or the like can be used. However, when the polycarbonate resin (A) contains a constituent unit derived from a dihydroxy compound containing an aromatic group, a polycarbonate resin having a high molecular weight may not be obtained, and impact resistance may not be obtained. The improvement effect is reduced. Therefore, from the viewpoint of further improving the impact resistance, the content of the constituent unit derived from the aromatic group-containing dihydroxy compound is preferably 10% by mole or less based on 100% by mole of the constituent unit derived from all the dihydroxy compounds. More preferably, it is 5 mol% or less.
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)硅烷、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。As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be used, but dihydroxy compounds other than these may be used. 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethyl Phenyl)propane, 2,2-bis(4-hydroxy-3,5-diethylphenyl)propane, 2,2-bis(4-hydroxy-(3-phenyl)phenyl)propane, 2, 2-bis(4-hydroxy-(3,5-diphenyl)phenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(4-hydroxyphenyl) Methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 1, 1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-2-ethylhexane 1,1-bis(4-hydroxyphenyl)silane, bis(4-hydroxy-3-nitrophenyl)methane, 3,3-bis(4-hydroxyphenyl)pentane, 1,3-double (2-(4-Hydroxyphenyl)-2-propyl)benzene, 1,3-bis(2-(4-hydroxyphenyl)-2-propyl)benzene, 2,2-bis(4-hydroxyl) Phenyl)hexafluoropropane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)sulfone, 2,4'-dihydroxydiphenylsulfone, bis(4-hydroxyl) Phenyl) sulfide, bis(4-hydroxy-3-methylphenyl) sulfide, bis(4-hydroxyphenyl)disulfide, 4,4'-dihydroxydiphenyl ether, 4,4' -dihydroxy- An aromatic bisphenol compound such as 3,3'-dichlorodiphenyl ether; 2,2-bis(4-(2-hydroxyethoxy)phenyl)propane, 2,2-bis(4-(2- Hydroxypropoxy)phenyl)propane, 1,3-bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy)biphenyl, bis(4-(2-hydroxyl) a dihydroxy compound having an ether group bonded to an aromatic group such as ethoxy)phenyl)sulfone; 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene, 9,9- Bis(4-hydroxyphenyl)anthracene, 9,9-bis(4-hydroxy-3-methylphenyl)anthracene, 9,9-bis(4-(2-hydroxypropoxy)phenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-methylphenyl)anthracene, 9,9-bis(4-(2-hydroxypropoxy)-3-methylphenyl) Indole, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-isobutyl Phenyl, fluorene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)- 3-cyclohexylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-benzene Phenyl, quinone, 9,9-bis(4-(2-hydroxyethoxy)-3,5-dimethylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy) , 3-tert-butyl-6-methylphenyl)anthracene, 9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)phenyl)anthracene, etc. Dihydroxy compound.
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、机械物性的改善、及成形性的改善等效果。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, mechanical properties, and improvement in moldability of the polycarbonate resin (A) can be obtained.
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稳定剂或热稳定剂等稳定剂。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复合物的品质。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 or a heat stabilizer. In particular, the dihydroxy compound represented by the above formula (1) has a property of being easily deteriorated in an acidic state. Therefore, by using an alkali stabilizer in the synthesis of the polycarbonate resin (A), deterioration of the dihydroxy compound represented by the above formula (1) can be suppressed, and the obtained polycarbonate resin composite can be further improved. quality.
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。As 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 Basic ammonium compounds such as ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide; diethylamine, dibutylamine, triethylamine, morpholine , N-methylmorpholine, pyrrolidine, piperidine, 3-amino-1-propanol, ethylenediamine, N-methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N,N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine Amine compounds such as 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline, and di(tert-butyl)amine and A hindered amine compound such as 2,2,6,6-tetramethylpiperidine.
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，优选含有碱性稳定剂的二羟基化合物的水溶液的pH为7左右的方式设定碱性稳定剂的含量。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, an aqueous solution of a dihydroxy compound containing an alkali stabilizer is preferred. The content of the alkaline stabilizer is set such that the pH is about 7.
碱性稳定剂相对于上述式(1)所示的二羟基化合物的含量优选为0.0001～1质 量％。此时，可得到防止上述式(1)所示的二羟基化合物的变质的效果，并且可防止羟基化合物的改性。从进一步提高这些效果的观点考虑，碱性稳定剂的含量更优选为0.001～0.1质量％。The content of the alkaline stabilizer relative to the dihydroxy compound represented by the above formula (1) is preferably 0.0001 to 1 the amount%. At this time, an effect of preventing deterioration of the dihydroxy compound represented by the above formula (1) can be obtained, and modification of the hydroxy compound can be prevented. The content of the alkaline stabilizer is more preferably 0.001 to 0.1% by mass from the viewpoint of further improving these effects.
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(4)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。As the carbonic acid diester used for the raw material of the polycarbonate resin (A), a compound represented by the following formula (4) can be usually used. These carbonic acid diesters may be used alone or in combination of two or more.
[化学式7][Chemical Formula 7]
Figure PCTCN2015085764-appb-000006
Figure PCTCN2015085764-appb-000006
在上述通式(4)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。In the above formula (4), 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. Can be different. As 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.
作为上述通式(4)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，优选根据需要使用利用蒸馏等进行了精制的碳酸二酯。As the carbonic acid diester represented by the above formula (4), for example, diphenyl carbonate such as diphenyl carbonate (DPC) or ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate can be used. Ester and the like. Among these carbonic acid diesters, diphenyl carbonate or substituted diphenyl carbonate is preferably used, and diphenyl carbonate is particularly preferably used. Further, the carbonic acid diester may contain impurities such as chloride ions, and the impurities may hinder the polycondensation reaction or may cause deterioration of the color tone of the obtained polycarbonate resin. Therefore, it is preferred to use a carbonic acid diester which is purified by distillation or the like as needed.
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生的单羟基化合物等除去到体系外而得到。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 by-produced monohydroxy compound or the like in the transesterification reaction to the outside of the system while polycondensation.
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。The above transesterification reaction is carried out in the presence of a transesterification catalyst (hereinafter, 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).
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。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). As the polymerization catalyst, for example, a metal compound of Group IA or Group IIA (hereinafter referred to as "Group IA" or "Group IIA") in the long-period periodic table, and a basic boron compound, a basic phosphorus compound, and the like can be used. 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.
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。As the above Group IA metal compound, for example, the following compounds can be used. Sodium hydroxide, potassium hydroxide, Lithium hydroxide, barium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, barium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, barium carbonate, sodium acetate, potassium acetate, lithium acetate, barium acetate, stearic acid Sodium, potassium stearate, lithium stearate, barium stearate, sodium borohydride, potassium borohydride, lithium borohydride, barium borohydride, sodium phenylborohydride, potassium phenylate, boron phenylate Lithium, boron phenyl hydride, sodium benzoate, potassium benzoate, lithium benzoate, bismuth benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dihydrogen phosphate, disodium phenyl phosphate, benzene Dipotassium phosphate, diphenyl phenyl phosphate, diphenyl phenyl phosphate; alkoxides, phenates of sodium, potassium, lithium, cesium; disodium salt, dipotassium salt, dilithium salt and diterpene salt of bisphenol A Wait.
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。As the Group IA metal compound, a lithium compound is preferred from the viewpoint of polymerization activity and color tone of the obtained polycarbonate resin.
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。As the above Group IIA metal compound, for example, the following compounds can be used. Calcium hydroxide, barium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, barium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, barium carbonate, calcium acetate, barium acetate, Magnesium acetate, barium acetate, calcium stearate, barium stearate, magnesium stearate and barium stearate.
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。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.
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。Further, 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 Group IA. a metal compound and/or a Group IIA metal compound.
作为上述碱性化合物，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。As the basic compound, for example, the following compounds can be used. Triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, and quaternary phosphonium salts, and the like.
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。As the above basic ammonium compound, for example, the following compounds can be used. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylhydrogen Ammonium Oxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide, Tributylphenylammonium Hydroxide, Tetraphenyl Examples of ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.
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。As the above amine-based compound, for example, 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, aminoquine Porphyrin and hydrazine.
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。The amount of the polymerization catalyst used is preferably from 0.1 to 300 μmol, more preferably from 0.5 to 100 μmol, particularly preferably from 1 to 50 μmol per 1 mol of all dihydroxy compounds used for the reaction.
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。In the case of using a compound containing at least one metal selected from the group consisting of a Group IIA metal and lithium in the long-period periodic table as the polymerization catalyst, particularly in the case of using a magnesium compound and/or a calcium compound The amount of the polymerization catalyst to be used is preferably 0.1 μmol or more, more preferably 0.3 μmol or more, and particularly preferably 0.5 μmol 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 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.
通过将聚合催化剂的使用量调整在上述范围，可提高聚合速度，因此，可在不一定需要提高聚合温度的情况下得到期望分子量的聚碳酸酯树脂。进而，可抑制伴有副反应。其结果，可更进一步防止聚碳酸酯树脂(A)的色调变差，可更进一步防止成形加工时的着色。By adjusting the amount of the polymerization catalyst to be used in the above range, the polymerization rate can be increased. Therefore, a polycarbonate resin having a desired molecular weight can be obtained without necessarily increasing the polymerization temperature. Further, it is possible to suppress the occurrence of side reactions. As a result, the color tone of the polycarbonate resin (A) can be further prevented from being deteriorated, and coloring during molding can be further prevented.
IA族金属中，若考虑含有钠、钾、或铯的化合物对聚碳酸酯树脂的色调带来的影响或铁对聚碳酸酯树脂带来的影响，则聚碳酸酯树脂(A)中的钠、钾、铯、及铁的合计含量优选为1质量ppm以下。此时，可更进一步防止聚碳酸酯树脂的色调变差，可使聚碳酸酯树脂的色调更进一步变得良好。从同样的观点考虑，聚碳酸酯树脂(A)中的钠、钾、铯、及铁的合计含量更优选为0.5质量ppm以下。另外，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在上述范围。Among the Group IA metals, sodium in the polycarbonate resin (A) is considered in consideration of the influence of the compound containing sodium, potassium or cesium on the color tone of the polycarbonate resin or the influence of iron on the polycarbonate resin. The total content of potassium, barium, and iron is preferably 1 ppm by mass or less. At this time, the color tone of the polycarbonate resin can be further prevented from being deteriorated, and the color tone of the polycarbonate resin can be further improved. From the same viewpoint, the total content of sodium, potassium, cesium, and iron in the polycarbonate resin (A) is more preferably 0.5 ppm by mass or less. In addition, 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 in the above range in terms of the total content of sodium, potassium, rubidium and iron.
(聚碳酸酯树脂(A)的合成)(Synthesis of Polycarbonate Resin (A))
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)所示的用作二羟基化合物等的原料的二羟基化合物和碳酸二酯缩聚而得到。The polycarbonate resin (A) can be obtained by polycondensing a dihydroxy compound and a carbonic acid diester used as a raw material of a dihydroxy compound or the like represented by the above formula (1) by a transesterification reaction in the presence of a polymerization catalyst.
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。此时，可提高溶解速度或充分提高溶解度，可充分地避免固化等不良情况。进而，在该情况下，可充分地抑制二羟基化合物的热劣化，结果可使得到的聚碳酸酯树脂(A)的色调更进一步变得良好，并且也可提高耐气候性。 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. In this case, the dissolution rate can be increased or the solubility can be sufficiently increased, and problems such as curing can be sufficiently avoided. Further, in this case, the thermal deterioration of the dihydroxy compound can be sufficiently suppressed, and as a result, the color tone of the obtained polycarbonate resin (A) can be further improved, and weather resistance can be improved.
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、更优选是0.0001～10vol％、特别优选是0.0001～5vol％、更特别优选是0.0001～1vol％的气氛下进行。此时，可以使色调更良好，并且可提高反应性。The operation of mixing the dihydroxy compound and the carbonic acid diester of the raw material is preferably carried out in an atmosphere having an oxygen concentration of 10 vol% or less, more preferably 0.0001 to 10 vol%, particularly preferably 0.0001 to 5 vol%, still more preferably 0.0001 to 1 vol%. At this time, the color tone can be made better, and the reactivity can be improved.
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。此时，可抑制聚碳酸酯树脂(A)的羟基末端量的增加，因此，可提高聚合物的热稳定性。因此，可更进一步防止成形时的着色或提高酯交换反应的速度。另外，可进一步可靠地得到期望的高分子量体。进而，通过将碳酸二酯的使用量调整在上述范围内，可抑制酯交换反应的速度降低，可更可靠地制造期望分子量的聚碳酸酯树脂(A)。另外，在该情况下，可抑制反应时的受热过程的增大，因此，可使聚碳酸酯树脂(A)的色调和耐气候性更进一步良好。进而，在该情况下，可减少聚碳酸酯树脂(A)中的残存碳酸二酯量，可避免或缓和成形时的污染或臭味的产生。从与以上同样的观点考虑，相对于全部二羟基化合物的碳酸二酯使用量更优选以摩尔比率为0.95～1.10。In order to obtain the polycarbonate resin (A), it is preferred to use a carbonic acid diester in a molar ratio of from 0.90 to 1.20 with respect to all the dihydroxy compounds used for the reaction. At this time, an increase in the amount of the hydroxyl terminal of the polycarbonate resin (A) can be suppressed, and therefore, the thermal stability of the polymer can be improved. Therefore, the coloring at the time of molding can be further prevented or the speed of the transesterification reaction can be increased. In addition, a desired high molecular weight body can be obtained more reliably. Further, by adjusting the amount of use of the carbonic acid diester to the above range, the decrease in the rate of the transesterification reaction can be suppressed, and the polycarbonate resin (A) having a desired molecular weight can be more reliably produced. Further, in this case, since the increase in the heat receiving process at the time of the reaction can be suppressed, the color tone and weather resistance of the polycarbonate resin (A) can be further improved. Further, in this case, the amount of residual carbonic acid diester in the polycarbonate resin (A) can be reduced, and the occurrence of contamination or odor during molding can be avoided or alleviated. From the same viewpoint as above, the amount of the carbonic acid diester used relative to the entire dihydroxy compound is more preferably 0.95 to 1.10 in a molar ratio.
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，且生产率也优异的连续式。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 form of the reaction may be a batch type or a continuous type, or a combination method of a batch type and a continuous type, and it is preferable to use a continuous type which can obtain a polycarbonate resin with less heat-receiving processes, and is excellent in productivity.
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。此时，抑制未反应单体的馏出，容易将二羟基化合物和碳酸二酯的摩尔比率调整至期望的比率。其结果，可抑制聚合速度的降低。另外，可更可靠地得到期望的分子量和具有末端基团的聚合物。From the viewpoint of the control of the polymerization rate and the quality of the obtained polycarbonate resin (A), it is important to appropriately select 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. At this time, the distillation of the unreacted monomer is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester is easily adjusted to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. In addition, a desired molecular weight and a polymer having a terminal group can be obtained more reliably.
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，在将得到的树脂熔融加工时，有时熔融粘度发生变动，难以将成形品的品质保持为一定。这种问题在以连续式进行缩聚反应时特别容易产生。In addition, 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, when the obtained resin is melt-processed, the melt viscosity may fluctuate, and it is difficult to maintain the quality of the molded article constant. This problem is particularly likely to occur when the polycondensation reaction is carried out in a continuous manner.
为了抑制馏出的未反应单体的量，有效的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℃。通过将制冷剂温度调整在这些范围，可充分地提高回流量，可充分地得到其效果，并且可充分地提高应蒸馏除去的单羟基化合物的蒸馏除去效果。其结果，可防止反应率的降低，可更进一步防止得到的树脂的着色。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。In order to suppress the amount of the unreacted monomer to be distilled, it is effective to use a reflux condenser in the polymerization reactor, particularly in the initial stage of the reaction in which many unreacted monomers are present. The temperature of the refrigerant introduced into the reflux condenser The degree of the refrigerant to be used in the reflux condenser is usually 45 to 180 ° C, preferably 80 to 150 ° C, and particularly preferably 100 to 130 ° C, depending on the monomer to be used. By adjusting the temperature of the refrigerant to these ranges, the reflux rate can be sufficiently increased, the effect can be sufficiently obtained, and the effect of distilling off the monohydroxy compound to be distilled off can be sufficiently enhanced. As a result, the decrease in the reaction rate can be prevented, and the coloration of the obtained resin can be further prevented. As the refrigerant, warm water, steam, heat medium oil or the like can be used, and steam or heat medium oil is preferable.
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，使得到的聚碳酸酯树脂(A)的色调更良好，重要的是对上述的催化剂的种类和量的选定。In order to maintain the polymerization rate at an appropriate speed and suppress the distillation of the monomer, the color tone of the obtained polycarbonate resin (A) is made better, and it is important to select the kind and amount of the above-mentioned catalyst.
聚碳酸酯树脂(A)是通过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。The polycarbonate resin (A) is produced by a process of using a polymerization catalyst and usually two or more stages. 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.
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散。另外，在反应后期，为了使平衡向缩聚反应侧移动，重要的是充分蒸馏除去副生的羟基化合物。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，提高生产效果。From the viewpoint of efficiently performing the polycondensation reaction, it is important to suppress the volatilization of the monomer while maintaining the necessary polymerization rate in the initial stage of the reaction of the monomer contained in the reaction liquid. Further, in the late stage of the reaction, in order to move the equilibrium to the polycondensation reaction side, it is important to sufficiently distill off the by-produced hydroxy compound. Therefore, 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 effect can be improved.
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。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. When the number of the polymerization reactors is two or more, a plurality of reaction stages having different conditions may be further carried out in each polymerization reactor or the temperature and pressure may be continuously changed.
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。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.
通过调整缩聚反应的温度，可提高生产率和避免对制品的受热过程的增大。进而，可更进一步防止单体的挥散、及聚碳酸酯树脂(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段反应优选一边将产生的单羟基化合物蒸馏除去至反应体系外一边实施。By adjusting the temperature of the polycondensation reaction, productivity can be improved and an increase in the heat-receiving process of the article can be avoided. Further, the volatilization of the monomer and the decomposition or coloration of the polycarbonate resin (A) can be further prevented. Specifically, as 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. Further, 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. In addition, the reaction time is usually 0.1 to 10 hours, It is preferably set in the range of 0.5 to 3 hours. The first stage reaction is preferably carried out while distilling off the produced monohydroxy compound to the outside of the reaction system.
第2段以后，优选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除去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。After the second stage, it is preferable to gradually reduce the pressure of the reaction system from the pressure in the first stage, and to continuously remove the generated monohydroxy compound to the outside of the reaction system, and to make the pressure (absolute pressure) of the final reaction system 1 kPa or less. Further, 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. Further, 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.
从更进一步抑制聚碳酸酯树脂(A)的着色或热劣化、得到色调更进一步良好的聚碳酸酯树脂(A)的观点考虑，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。From the viewpoint of further suppressing coloration or thermal deterioration of the polycarbonate resin (A) and obtaining a polycarbonate resin (A) having a further excellent color tone, it is preferred to set the maximum temperature of the internal temperature of the polymerization reactor in all the reaction stages. Set to 210 to 240 °C. In order to suppress the decrease in the polymerization rate in the latter half of the reaction, the deterioration due to the heat transfer process is minimized, and it is preferable to use a horizontal reactor excellent in plug flowability and interface renewability in the final stage of the polycondensation reaction.
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，优选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。In the continuous polymerization, in order to control the molecular weight of the finally obtained polycarbonate resin (A) to a certain level, it is preferred to adjust the polymerization rate as needed. At this time, the pressure of the polymerization reactor in the final stage is adjusted to be a method having good workability.
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，分子量变得过高，因此，一方的末端基团优选为60mol/ton以下。Further, since 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. However, in this case, if the number of ends is too small, the reactivity of the polycarbonate resin (A) may not be able to satisfy the desired molecular weight because the end group balance slightly changes and the reactivity is extremely lowered. In order to avoid such a problem, 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. On the other hand, when both terminal groups are too much, the polymerization rate becomes high and the molecular weight becomes too high. Therefore, one terminal group is preferably 60 mol/ton or less.
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。By adjusting the amount of the terminal group and the pressure of the polymerization reactor in the final stage to a preferred range as above, 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. By reducing the content of the monohydroxy compound in the outlet of the polymerization reactor as described above, devolatilization of the monohydroxy compound or the like can be easily performed in the subsequent step.
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。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 use a pole. The amount of the terminal group of one side is reduced end-to-end, and the pressure of the polymerization reactor is maintained at an operating condition such as 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.
从资源有效利用的观点考虑，副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。From the viewpoint of efficient use of resources, the by-produced monohydroxy compound is preferably reused as a raw material of another compound after being purified as necessary. For example, when the monohydroxy compound is phenol, it can be used as a raw material of diphenyl carbonate or bisphenol A.
聚碳酸酯树脂(A)的玻璃化温度优选90℃以上。此时，可均衡地提高上述聚碳酸酯树脂复合物的耐热性和生物质含有率。从同样的观点考虑，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)的玻璃化温度优选170℃以上。此时，可通过上述的熔融聚合减小熔融粘度，可得到充分分子量的聚合物。另外，在想要通过提高聚合温度、降低熔融粘度来提高分子量的情况下，由于构成成分(a)的耐热性不充分，因此，有可能容易着色。从使分子量的提高和着色的防止进一步均衡的观点考虑，聚碳酸酯树脂(A)的玻璃化温度更优选165℃以下，进一步优选160℃以下，特别优选150℃以下。The glass transition temperature of the polycarbonate resin (A) is preferably 90 ° C or higher. At this time, the heat resistance and the biomass content of the polycarbonate resin composite described above can be improved in a balanced manner. From the same viewpoint, 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. On the other hand, the glass transition temperature of the polycarbonate resin (A) is preferably 170 ° C or higher. At this time, the melt viscosity can be reduced by the above melt polymerization, and a polymer having a sufficient molecular weight can be obtained. In addition, when it is desired to increase the molecular weight by increasing the polymerization temperature and lowering the melt viscosity, the heat resistance of the component (a) is insufficient, and thus coloring is likely to occur. 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 further improving the molecular weight and preventing the coloring.
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。还原粘度通常为0.30dL/g以上，优选为0.33dL/g以上。此时，可进一步提高成形品的机械强度。另一方面，还原粘度通常为1.20dL/g以下，更优选为1.00dL/g以下，进一步优选为0.80dL/g以下。此时，可提高成形时的流动性，可进一步提高生产率或成形性。另外，聚碳酸酯树脂(A)的还原粘度是使用以二氯甲烷作为溶剂而将树脂的浓度精确地调整为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。还原粘度的测定方法的详细情况在实施例中进行说明。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 is usually 0.30 dL/g or more, preferably 0.33 dL/g or more. At this time, the mechanical strength of the molded article can be further improved. On the other hand, the reduced viscosity is usually 1.20 dL/g or less, more preferably 1.00 dL/g or less, still more preferably 0.80 dL/g or less. At this time, the fluidity at the time of molding can be improved, and productivity or moldability can be further improved. Further, the reduced viscosity of the polycarbonate resin (A) is a solution in which the concentration of the resin is accurately adjusted to 0.6 g/dL using dichloromethane as a solvent, and the temperature is 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.
聚碳酸酯树脂(A)的溶融粘度优选400Pa·s以上且3000Pa·s以下。此时，可防止树脂复合物的成形品变脆，进一步提高机械物性。进而，在该情况下，可提高成形加工时的流动性，防止成形品的外观受损或尺寸精度变差。进而，在该情况下，可更进一步防止由因剪切发热使树脂温度上升而引起的着色或发泡。从同样的观点考虑，聚碳酸酯树脂(A)的溶融粘度更优选600Pa·s以上且2500Pa·s以下，进一步更优选800Pa·s以上且2000Pa·s以下。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。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。 The melt viscosity of the polycarbonate resin (A) is preferably 400 Pa·s or more and 3,000 Pa·s or less. At this time, the molded article of the resin composite can be prevented from becoming brittle, and the mechanical properties can be further improved. Further, in this case, the fluidity at the time of molding processing can be improved, and the appearance of the molded article can be prevented from being impaired or the dimensional accuracy can be deteriorated. Further, in this case, coloring or foaming caused by an increase in the temperature of the resin due to shear heat generation can be further prevented. From the same viewpoint, the melt viscosity of the polycarbonate resin (A) is more preferably 600 Pa·s or more and 2500 Pa·s or less, and still more preferably 800 Pa·s or more and 2000 Pa·s or less. In the present specification, 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.
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等的锍盐；癸基磺酸四甲基铵盐、十二烷基苯磺酸四丁基铵盐等的铵盐；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、十六烷基磺酸乙酯等的烷基酯等。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, and the like; Ammonium salt of tetramethylammonium sulfonate, tetrabutylammonium dodecylbenzenesulfonate, etc.; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate An alkyl ester such as an ester or ethyl hexadecylsulfonate.
上述催化剂失活剂优选包含含有下述结构式(5)或下述结构式(6)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，即例如在混合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，可更进一步抑制高温下的聚碳酸酯树脂(A)的着色。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 (5) or the following structural formula (6). After the polycondensation reaction is completed, that is, for example, in the mixing step or the granulation step, the polymerization catalyst described later is deactivated, and the subsequent polycondensation reaction can be suppressed from proceeding unnecessarily. As a result, it is possible to suppress the progress of the polycondensation when the polycarbonate resin (A) is heated in the molding step or the like, and it is possible to suppress the detachment of the above-mentioned monohydroxy compound. Further, by deactivating the polymerization catalyst, coloring of the polycarbonate resin (A) at a high temperature can be further suppressed.
[化学式8][Chemical Formula 8]
Figure PCTCN2015085764-appb-000007
Figure PCTCN2015085764-appb-000007
[化学式9][Chemical Formula 9]
Figure PCTCN2015085764-appb-000008
Figure PCTCN2015085764-appb-000008
作为含有上述结构式(5)或结构式(6)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。As the specific phosphorus-based compound containing the partial structure represented by the above structural formula (5) or structural formula (6), phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonate, acid phosphate or the like can be used. Among the specific phosphorus-based compounds, 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.
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、次氮基(亚甲基膦酸)、丙基膦酸酐等。 As the 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, nitrile (methylenephosphonic acid), propylphosphonic anhydride, and the like.
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、苄基膦酸二乙从、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。As the phosphonate, for example, 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, dibenzyl 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, tert-butyl diethylphosphonoacetate, diethyl (4-chlorobenzyl)phosphonate, cyano Diethyl phosphonate, diethyl cyanomethylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethylphosphonoacetaldehyde diethyl acetal, Diethyl methyl thiomethyl) phosphonate and the like.
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。As 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.
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。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.
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。此时，可充分地得到上述特定磷系化合物的催化剂失活及着色抑制的效果。另外，在该情况下，特别是在高温·高湿度的耐久试验中，可更进一步防止聚碳酸酯树脂(A)的着色。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. In this case, the effect of catalyst deactivation and coloring inhibition of the above specific phosphorus-based compound can be sufficiently obtained. Further, in this case, in particular, in the durability test of high temperature and high humidity, the coloring of the polycarbonate resin (A) can be further prevented.
另外，通过根据聚合催化剂的量调节上述特定磷系化合物的含量，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0.5mol当量以上且5mol当量以下，更优选为0.7mol当量以上且4mol当量以下，特别优选为0.8mol当量以上且3mol当量以下。In addition, by adjusting the content of the specific phosphorus-based compound according to the amount of the polymerization catalyst, the effect of catalyst deactivation and coloring inhibition can be obtained more reliably. The content of the specific phosphorus-based compound is preferably 0.5 mol equivalent or more and 5 mol equivalent or less, more preferably 0.7 mol equivalent or more and 4 mol equivalent or less, and particularly preferably 0.8 mol, based on 1 mol of the metal atom of the polymerization catalyst. It is equal to or more than 3 mol equivalents.
[芳香族聚碳酸酯树脂(B)][Aromatic Polycarbonate Resin (B)]
上述芳香族聚碳酸酯树脂(B)为将源自下述通式(7)所示的芳香族二羟基化合物的构成单元作为主构成单元的聚碳酸酯树脂。The aromatic polycarbonate resin (B) is a polycarbonate resin having a constituent unit derived from an aromatic dihydroxy compound represented by the following formula (7) as a main constituent unit.
[化学式10] [Chemical Formula 10]
Figure PCTCN2015085764-appb-000009
Figure PCTCN2015085764-appb-000009
上述通式(7)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(2)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，优选为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(2)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。R 1 to R 8 in the above formula (7) 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 (2) 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. Among them, an alkyl group having 1 to 10 carbon atoms which may have a substituent or an aromatic group having 6 to 20 carbon atoms which may have a substituent is preferable. The divalent group of Y in the formula (2) 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 -. Here, 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. Further, 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.
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构成单元中源自下述通式(2)所示的二羟基化合物的构成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构成单元相对于源自全部二羟基化合物的总构成单元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。The aromatic polycarbonate resin (B) may be a homopolymer or a copolymer. In the case of a copolymer, it is preferred that the total constituent unit derived from the dihydroxy compound is derived from the following formula (2). The polycarbonate resin having the largest constituent unit of the dihydroxy compound shown. In the aromatic polycarbonate resin (B), the content ratio of the constituent unit derived from the dihydroxy compound represented by the above formula (2) to 100 mol% of the total constituent 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.
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构成单元。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构成单元的情况下，使用与聚碳酸酯树脂(A)不同的构成单元的聚碳酸酯树脂。Further, 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 constituent unit derived from a dihydroxy compound having a moiety represented by the above formula (1). However, when a constituent unit derived from a dihydroxy compound having a moiety represented by the above formula (1) is contained, a polycarbonate resin having a constituent unit different from the polycarbonate resin (A) is used.
源自构成芳香族聚碳酸酯树脂(B)的二羟基化合物的构成单元为从二羟基化合物的羟基中除去了氢原子的构成单元。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。The constituent unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) is a constituent unit from which a hydrogen atom is removed from the hydroxyl group of the dihydroxy compound. Specific examples of the equivalent dihydroxy compound include the following dihydroxy compounds.
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。4,4'-biphenol, 2,4'-biphenol, 3,3'-dimethyl-4,4'-dihydroxy-1,1'-biphenyl, 3,3' -Dimethyl-2,4'-dihydroxy-1,1'-biphenyl, 3,3'-di(tert-butyl)-4,4'-dihydroxy-1,1'-biphenyl, 3 ,3',5,5'-tetramethyl-4,4'-dihydroxy-1,1'-biphenyl, 3,3',5,5'-tetra-(tert-butyl)-4,4 '-Dihydroxy-1,1'-biphenyl, 2,2',3,3',5,5'-hexamethyl-4,4'-dihydroxy-1,1'-biphenyl and other biphenyls Compound.
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。Bis(4-hydroxy-3,5-dimethylphenyl)methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, 1,1-double (4 -hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methyl Phenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)-3- Methyl butane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxybenzene Cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(3-phenyl-4-hydroxyphenyl)methane, 1,1-bis(3-phenyl-4- Hydroxyphenyl)ethane, 1,1-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 1,1-double (4-hydroxy-3-methylphenyl)ethane, 2,2-bis(4-hydroxy-3-ethylphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylbenzene Propane, 2,2-bis(4-hydroxy-3-sec-butylphenyl)propane, 1,1-bis(4-hydroxy-3,5-dimethylphenyl)ethane, 2,2 - bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxy-3,6-dimethylphenyl)ethane, bis(4-hydroxy-2, 3,5-trimethylphenyl) 1,1-bis(4-hydroxy-2,3,5-trimethylphenyl)ethane, 2,2-bis(4-hydroxy-2,3,5-trimethylphenyl)propane, Bis(4-hydroxy-2,3,5-trimethylphenyl)phenylmethane, 1,1-bis(4-hydroxy-2,3,5-trimethylphenyl)phenylethane, 1 , 1-bis(4-hydroxy-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)dibenzyl Methane, 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[phenol], 4,4'-[1,4-phenylenebismethylene] double [Phenol], 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[2,6-dimethylphenol], 4,4'-[1,4- Phenylenebismethylene]bis[2,6-dimethylphenol], 4,4'-[1,4-phenylenebismethylene]bis[2,3,6-trimethylphenol ], 4,4'-[1,4-phenylenebis(1-methylethylidene)]bis[2,3,6-trimethylphenol], 4,4'-[1,3- Phenylenebis(1-methylethylidene)]bis[2,3,6-trimethylphenol], 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl Sulfone, 4,4'-dihydroxydiphenyl sulfide, 3,3',5,5'-four Base-4,4'-dihydroxydiphenyl ether, 3,3',5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfone, 3,3',5,5'- Tetramethyl-4,4'-dihydroxydiphenyl sulfide phenolphthalein, 4,4'-[1,4-phenylenebis(1-methylvinylidene)]bisphenol, 4,4'-[ 1,4-phenylenebis(1-methylvinylidene)]bis[2-methylphenol], (2-hydroxyphenyl)(4-hydroxyphenyl)methane, (2-hydroxy-5- Methylphenyl)(4-hydroxy-3-methylphenyl)methane, 1,1-(2-hydroxyphenyl)(4-hydroxyphenyl)ethane, 2,2-(2-hydroxyphenyl) )(4- A bisphenol compound such as hydroxyphenyl)propane or 1,1-(2-hydroxyphenyl)(4-hydroxyphenyl)propane.
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。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.
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。Preferred examples of the dihydroxy compound 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, 2-hydroxyphenyl(4-hydroxyphenyl)methane, 2,2-( 2-hydroxyphenyl)(4-hydroxyphenyl)propane.
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。Among them, bis(4-hydroxy-phenyl)methane, bis(4-hydroxy-3-methylphenyl)methane, bis(4-hydroxy-3,5-methylphenyl)methane, 2,2 are particularly preferred. - 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-hydroxy-3,3,5-trimethylphenyl)cyclohexane.
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。As a method for producing the aromatic polycarbonate resin (B), any conventionally known method such as a phosgene method, a transesterification method, or a pyridine method can be used. Hereinafter, a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described as an example.
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。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.
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。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.
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，将聚碳酸酯浓度精确地调整为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以上且0.61dl/g以下的范围内。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) is determined by using dichloromethane as a solvent, and the polycarbonate concentration is accurately adjusted to 0.60 g/dl, and the temperature is measured at 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.
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。Further, in the present invention, the aromatic polycarbonate resin (B) may be used alone or in combination of two. More than one species.
[玻璃填料(C)][Glass filler (C)]
本发明的树脂复合物用玻璃填料(C)为由通常被称为E玻璃的、SiO2为52～56％、Al2O3为12～16％、MgO和CaO等碱土类金属氧化物的合计20～25％、Na2O或K2O的碱金属氧化物的合计0～0.8％的组成构成的玻璃填料。The glass filler (C) for a resin composite of the present invention is an alkaline earth metal oxide such as SiO 2 of 52 to 56%, Al 2 O 3 of 12 to 16%, MgO or CaO, which is generally called E glass. A glass filler having a composition of 0 to 25% of a total of 0 to 25% of an alkali metal oxide of Na 2 O or K 2 O in total.
本发明的玻璃填料(C)以波长589nm测得的折射率为1.550以上且1.560以下。另外，为了制成树脂复合物时的透明性良好，作为下限值，优选1.552以上，特别优选1.554以上。作为上限值，优选1.559以下，特别优选1.558以下。The glass filler (C) of the present invention has a refractive index measured at a wavelength of 589 nm of 1.550 or more and 1.560 or less. Moreover, in order to have good transparency in the case of producing a resin composite, the lower limit is preferably 1.552 or more, and particularly preferably 1.554 or more. The upper limit is preferably 1.559 or less, and particularly preferably 1.558 or less.
本发明的玻璃填料(C)的阿贝数为50以上且60以下。另外，为了制成树脂复合物时的阿贝数良好，作为下限值，优选52以上，特别优选54以上。作为上限值，优选58以下，特别优选56以下。The glass filler (C) of the present invention has an Abbe number of 50 or more and 60 or less. Further, in order to obtain a resin composite, the Abbe number is good, and the lower limit is preferably 52 or more, and particularly preferably 54 or more. The upper limit is preferably 58 or less, and particularly preferably 56 or less.
本发明的玻璃填料(C)优选以玻璃纤维、玻璃粉末、玻璃薄片、磨碎纤维或玻璃珠的形态使用，特别是为了提高刚性，优选以玻璃纤维的形式使用。The glass filler (C) of the present invention is preferably used in the form of glass fibers, glass powder, glass flakes, ground fibers or glass beads, and in particular, in order to improve rigidity, it is preferably used in the form of glass fibers.
玻璃纤维的直径没有特别限定，可优选使用3～25μm的玻璃纤维。在比3μm细的情况下，有时玻璃纤维和树脂组合物(X)的接触面积增大而成为漫反射的原因，树脂复合物或成形品的透明性降低。在比25μm粗的情况下，有时玻璃纤维的强度变弱，结果成形品的强度降低。另外，为了制成树脂复合物时的拉伸应力良好，作为下限值，优选5μm以上，特别优选8μm以上。作为上限值，优选20μm以下，特别优选15μm以下。The diameter of the glass fiber is not particularly limited, and glass fibers of 3 to 25 μm can be preferably used. When it is thinner than 3 μm, the contact area between the glass fiber and the resin composition (X) may increase to cause diffuse reflection, and the transparency of the resin composite or the molded article may be lowered. When it is thicker than 25 μm, the strength of the glass fiber may be weak, and as a result, the strength of the molded article may be lowered. Moreover, in order to obtain a resin composite, the tensile stress is good, and the lower limit is preferably 5 μm or more, and particularly preferably 8 μm or more. The upper limit is preferably 20 μm or less, and particularly preferably 15 μm or less.
玻璃纤维的形态可根据成形方法或成形品所要求的特性适宜选择，没有特别限定。例如可以举出：短切原丝、粗纱、垫子、布、磨碎纤维等。The form of the glass fiber can be appropriately selected depending on the characteristics required for the molding method or the molded article, and is not particularly limited. For example, chopped strands, rovings, mats, cloth, ground fibers, and the like can be mentioned.
本发明的玻璃填料(C)优选利用含有偶联剂的处理剂进行表面处理。作为偶联剂，可使用硅烷系偶联剂、硼烷系偶联剂、铝酸盐系偶联剂或钛酸盐系偶联剂等。特别是从聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)和玻璃的粘接性良好的方面考虑，优选使用硅烷偶联剂。作为硅烷偶联剂，可使用氨基硅烷系偶联剂、环氧硅烷系偶联剂、丙烯酸硅烷盐系偶联剂等。这些硅烷偶联剂中，优选使用氨基硅烷系偶联剂。The glass filler (C) of the present invention is preferably subjected to surface treatment using a treating agent containing a coupling agent. As the coupling agent, a silane coupling agent, a borane coupling agent, an aluminate coupling agent, a titanate coupling agent, or the like can be used. In particular, a silane coupling agent is preferably used from the viewpoint of good adhesion between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) and glass. As the silane coupling agent, an aminosilane coupling agent, an epoxysilane coupling agent, an acrylic silane salt coupling agent, or the like can be used. Among these silane coupling agents, an aminosilane coupling agent is preferably used.
本发明的玻璃填料(C)的添加量相对于树脂组合物(X)100重量份为10～150重量份，优选为10～100重量份，特别优选为11～67重量份。低于10重量份时，刚性的改良效果不充分，若多于150重量份，则也有时树脂复合物的熔融流动性降低，成 形品的填充变得不充分。The amount of the glass filler (C) to be added in the invention is 10 to 150 parts by weight, preferably 10 to 100 parts by weight, particularly preferably 11 to 67 parts by weight, per 100 parts by weight of the resin composition (X). When the amount is less than 10 parts by weight, the effect of improving the rigidity is insufficient. When the amount is more than 150 parts by weight, the melt fluidity of the resin composite may be lowered. The filling of the shape becomes insufficient.
[化合物(D)]：酯交换反应催化剂[Compound (D)]: Transesterification catalyst
本发明的酯交换反应催化剂(D)只要可促进聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的酯交换反应就没有特别限制。酯交换反应在制作上述树脂组合物(X)时，例如通过聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的混炼时的加热而产生，可通过酯交换反应催化剂(D)来促进。其结果，树脂组合物(X)中的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的相容性提高，因此，可提高树脂组合物(X)的透明性。酯交换反应催化剂(D)可以举出含有选自IA族的金属化合物及IIA族的金属化合物中的至少一种的化合物、锡化合物、碱性含氮化合物等。The transesterification catalyst (D) of the present invention is not particularly limited as long as it can promote the transesterification reaction of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). The transesterification reaction is produced by heating at the time of kneading of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the production of the above resin composition (X), and can be passed through a transesterification catalyst (D). ) to promote. As a result, the compatibility between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the resin composition (X) is improved, so that the transparency of the resin composition (X) can be improved. The transesterification catalyst (D) may, for example, be a compound containing at least one selected from the group consisting of a metal compound of Group IA and a metal compound of Group IIA, a tin compound, a basic nitrogen-containing compound, and the like.
＜IA族及IIA族的金属化合物＞<Metal compounds of Groups IIA and IIA>
作为酯交换反应催化剂(D)中的IA族及IIA族的金属化合物的例子，可以举出：锂、钠、钾、铷、铯、铍、镁、钙、锶、钡等。Examples of the metal compound of Group IA and Group IIA in the transesterification catalyst (D) include lithium, sodium, potassium, rubidium, cesium, cesium, magnesium, calcium, strontium, barium, and the like.
上述酯交换反应催化剂(D)优选IA族及IIA族的金属中电负性为0.7～1.1的金属，更优选0.75～1.0的金属，进一步更优选0.75～0.98的金属。具体而言，可以举出：铯(0.79)、钾(0.82)、钠(0.93)、锂(0.98)、钡(0.89)、锶(0.95)、钙(1.0)。括弧内的数值为电负性。通过采用电负性在上述范围的金属，可进一步提高聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的树脂组合物的透明性，进而，可进一步提高耐冲击性。The transesterification catalyst (D) is preferably a metal having a electronegativity of 0.7 to 1.1 in the metals of Groups IA and IIA, more preferably a metal of 0.75 to 1.0, still more preferably a metal of 0.75 to 0.98. Specific examples thereof include hydrazine (0.79), potassium (0.82), sodium (0.93), lithium (0.98), hydrazine (0.89), hydrazine (0.95), and calcium (1.0). The values in parentheses are electronegativity. By using a metal having an electronegativity in the above range, the transparency of the resin composition of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) can be further improved, and further, the impact resistance can be further improved.
作为酯交换反应催化剂(D)，可以举出由上述金属和羧酸、碳酸、醇、苯酚等有机酸、硝酸、磷酸、硼酸等构成的金属盐。另外，作为金属盐，还可以举出上述金属的卤化物、氢氧化物等。The transesterification catalyst (D) may, for example, be a metal salt composed of the above metal, an organic acid such as a carboxylic acid, a carbonic acid, an alcohol or a phenol, nitric acid, phosphoric acid or boric acid. Further, examples of the metal salt include halides and hydroxides of the above metals.
酯交换反应催化剂(D)中的金属离子的抗衡离子的酸解离常数(pKa)优选为2～16。此时，可在不增多金属换算的催化剂量的情况下提高聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的树脂组合物的透明性，可更进一步防止色相变差。从同样的观点考虑，酯交换反应催化剂(D)中的金属离子的抗衡离子的酸解离常数(pKa)更优选3～11，特别优选5～10。The acid dissociation constant (pKa) of the counter ion of the metal ion in the transesterification catalyst (D) is preferably from 2 to 16. In this case, the transparency of the resin composition of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) can be improved without increasing the amount of the metal-converted catalyst, and the deterioration of the hue can be further prevented. From the same viewpoint, the acid dissociation constant (pKa) of the counter ion of the metal ion in the transesterification catalyst (D) is more preferably from 3 to 11, particularly preferably from 5 to 10.
作为用作酯交换反应催化剂(D)的IA族的金属化合物，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。其中，从透明性、色调及耐湿热性的观点考虑，优选选自由钠化合物、钾化合物、及铯化合物构成的组中的至少一种，更优选钾化合物及/或铯化合物。特别优选为碳酸氢钾、碳酸氢铯、碳酸钾、碳酸铯、乙酸钾、乙酸铯、硬脂酸钾、硬脂酸铯。As the metal compound of Group IA used as the transesterification catalyst (D), for example, the following compounds can be employed. Sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, lithium hydrogencarbonate, barium hydrogencarbonate, sodium carbonate, potassium carbonate, lithium carbonate, barium carbonate, sodium acetate, potassium acetate, Lithium acetate, barium acetate, Sodium stearate, potassium stearate, lithium stearate, barium stearate, sodium borohydride, potassium borohydride, lithium borohydride, barium borohydride, sodium phenylborohydride, potassium phenylate, phenyl Lithium boride, borohydride phenylate, sodium benzoate, potassium benzoate, lithium benzoate, bismuth benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dihydrogen phosphate, disodium phenyl phosphate , dipotassium phenyl phosphate, dilithium phenyl phosphate, diphenyl phenyl phosphate; alkoxides, phenates of sodium, potassium, lithium, cesium; disodium salt, dipotassium salt, dilithium salt and two of bisphenol A铯 salt and so on. In particular, at least one selected from the group consisting of a sodium compound, a potassium compound, and an antimony compound is preferable, and a potassium compound and/or an antimony compound are more preferable from the viewpoint of transparency, color tone, and heat and humidity resistance. Particularly preferred are potassium hydrogencarbonate, cesium hydrogencarbonate, potassium carbonate, cesium carbonate, potassium acetate, cesium acetate, potassium stearate, and strontium stearate.
作为用作酯交换反应催化剂(D)的IIA族的金属化合物，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。其中，从透明性及色调的观点考虑，优选钙化合物。特别优选为氢氧化钙、碳酸氢钙、乙酸钙。As the metal compound of Group IIA used as the transesterification catalyst (D), for example, the following compounds can be employed. Calcium hydroxide, barium hydroxide, magnesium hydroxide, barium hydroxide, calcium hydrogencarbonate, barium hydrogencarbonate, magnesium hydrogencarbonate, barium hydrogencarbonate, calcium carbonate, barium carbonate, magnesium carbonate, barium carbonate, calcium acetate, barium acetate, Magnesium acetate, barium acetate, calcium stearate, barium stearate, magnesium stearate and barium stearate. Among them, a calcium compound is preferred from the viewpoint of transparency and color tone. Particularly preferred are calcium hydroxide, calcium hydrogencarbonate, and calcium acetate.
在树脂组合物(X)中，源自作为酯交换反应催化剂(D)的IA族及IIA族的金属化合物的金属量优选为0.8重量ppm以上且1000重量ppm以下。也取决于金属种类，若超过1000重量ppm，则树脂组合物的色调变差，另外，耐湿热性降低。若低于0.8重量ppm，则树脂组合物的透明性不充分。从同样的观点考虑，源自酯交换反应催化剂(D)的金属量更优选为0.9重量ppm以上且100重量ppm以下，特别优选为1重量ppm以上且10重量ppm以下。另外，与作为原料的聚碳酸酯树脂(A)的聚合催化剂或芳香族聚碳酸酯树脂(B)的聚合催化剂相比，聚碳酸酯树脂组合物中所导入的酯交换反应催化剂(D)通常多在例如聚合工序后利用对甲苯磺酸丁酯这样的酸性化合物使其失活，因此，优选另行添加酯交换反应催化剂(D)。In the resin composition (X), the metal amount derived from the metal compound of Group IA and Group IIA which is the transesterification catalyst (D) is preferably 0.8 ppm by weight or more and 1000 ppm by weight or less. Also depending on the kind of the metal, when it exceeds 1000 ppm by weight, the color tone of the resin composition is deteriorated, and the moist heat resistance is lowered. When it is less than 0.8 ppm by weight, the transparency of the resin composition is insufficient. From the same viewpoint, the amount of the metal derived from the transesterification catalyst (D) is more preferably 0.9 ppm by weight or more and 100 ppm by weight or less, and particularly preferably 1 ppm by weight or more and 10 ppm by weight or less. In addition, the transesterification catalyst (D) introduced in the polycarbonate resin composition is usually higher than the polymerization catalyst of the polycarbonate resin (A) as a raw material or the polymerization catalyst of the aromatic polycarbonate resin (B). In many cases, for example, an acidic compound such as butyl p-toluenesulfonate is deactivated after the polymerization step. Therefore, it is preferred to additionally add a transesterification catalyst (D).
源自作为上述酯交换反应催化剂(D)的IA族及IIA族的金属化合物的添加量也取决于金属种类，相对于由聚碳酸酯树脂(A)及芳香族聚碳酸酯树脂(B)构成的树脂组合物，以金属换算计为0.5重量ppm～1000重量ppm，优选为1重量ppm～100重量ppm，特别优选为1重量ppm～10重量ppm。低于0.5重量ppm时，树脂组合物的透明性变得不充分。另一方面，若多于1000重量ppm，则虽然变为透明，但着色强烈，另外，树脂组合物的分子量(熔融粘度)降低，无法得到耐冲击性优异的树脂复合物。The amount of the metal compound derived from the Group IA and Group IIA which is the above-mentioned transesterification catalyst (D) depends on the kind of the metal, and is composed of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). The resin composition is 0.5 to 1000 ppm by weight, preferably 1 to 100 ppm by weight, and particularly preferably 1 to 10 ppm by weight, in terms of metal. When it is less than 0.5 ppm by weight, the transparency of the resin composition becomes insufficient. On the other hand, when it is more than 1000 ppm by weight, it is transparent, but the coloring is strong, and the molecular weight (melt viscosity) of the resin composition is lowered, and a resin composite excellent in impact resistance cannot be obtained.
＜锡化合物＞ <tin compound>
作为用作酯交换反应催化剂(D)的锡系化合物为选自下述式(2)或(3)中的一种以上的化合物。The tin-based compound used as the transesterification reaction catalyst (D) is one or more compounds selected from the following formula (2) or (3).
[化学式12][Chemical Formula 12]
Figure PCTCN2015085764-appb-000010
Figure PCTCN2015085764-appb-000010
[化学式13][Chemical Formula 13]
Figure PCTCN2015085764-appb-000011
Figure PCTCN2015085764-appb-000011
(式中，R表示碳原子数1～15的烷基或芳基，X1～X4表示碳原子数1～15的烷基、芳基、烯丙氧基、环己基、羟基、含有卤素等的1价基团，可以相同也可以不同。另外，X5表示硫或氧原子。)(In the formula, R represents an alkyl group or an aryl group having 1 to 15 carbon atoms, and X1 to X4 represent an alkyl group having 1 to 15 carbon atoms, an aryl group, an allyloxy group, a cyclohexyl group, a hydroxyl group, or a halogen-containing compound. The monovalent group may be the same or different. In addition, X5 represents a sulfur or an oxygen atom.
具体而言，可以举出：二丁基氧化锡、甲基苯基氧化锡、四乙基氧化锡、六乙基氧化锡、环六己基氧化锡、二十二烷基氧化锡、三乙基氢氧化锡、三苯基氢氧化锡、三异丁基乙酸锡、二丁基二乙酸锡、二丁基二月桂酸锡、二辛基二月桂酸锡、二苯基二月桂酸锡、单丁基三氯化锡、二丁基二氯化锡、三丁基氯化锡、二丁基硫化锡及单丁基氢氧化锡等。可优选举出二丁基二月桂酸锡。Specific examples thereof include dibutyltin oxide, methylphenyltin oxide, tetraethyltin oxide, hexaethyltin oxide, cyclohexyltin oxide, behenyltin oxide, and triethylamine. Tin hydroxide, tin triphenyl hydroxide, tin triisobutyl acetate, tin dibutyl diacetate, tin dibutyl dilaurate, tin dioctyl dilaurate, tin diphenyl dilaurate, single Butyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and monobutyltin hydroxide. Preferably, dibutyltin dilaurate is mentioned.
此外，作为化合物(D)，也可以使用锡酸，此时，可以举出：甲基锡酸、乙基锡酸及丁基锡酸等烷基锡酸。Further, as the compound (D), stannic acid may be used, and in this case, an alkylstannic acid such as methyl stannic acid, ethyl stannic acid or butyl stannic acid may be mentioned.
用作上述化合物(D)的锡系化合物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0.001重量份以上且5重量份以下。优选为0.01重量份以上，进一步优选为0.05重量份以上。另外，优选为3重量份以下，进一步优选为2重量份以下。添加量低于0.001重量份时，透明化的效果不充分，若多于5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。 The amount of the tin-based compound to be used as the compound (D) is 0.001 part by weight or more and 5 parts by weight based on 100 parts by weight of the resin composition containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). the following. It is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. Further, it is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less. When the amount is less than 0.001 part by weight, the effect of the transparency is insufficient. When the amount is more than 5 parts by weight, the coloring is remarkable, but the coloring is remarkable, the molecular weight is lowered, and the mechanical strength is insufficient.
＜碱性含氮化合物＞<Basic nitrogenous compounds>
用作酯交换反应催化剂(D)的碱性含氮化合物可以举出碱性铵化合物或胺系化合物。作为碱性铵化合物，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。The basic nitrogen-containing compound used as the transesterification catalyst (D) may, for example, be a basic ammonium compound or an amine compound. As the basic ammonium compound, for example, the following compounds can be used. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylhydrogen Ammonium Oxide, Triethylmethylammonium Hydroxide, Triethylbenzylammonium Hydroxide, Triethylphenylammonium Hydroxide, Tributylbenzylammonium Hydroxide, Tributylphenylammonium Hydroxide, Tetraphenyl Examples of ammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide.
作为胺系化合物，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。As the amine compound, for example, 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.
用作上述化合物(D)的碱性含氮化合物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0.001重量份以上且5重量份以下。优选为0.01重量份以上，进一步优选为0.05重量份以上。另外，优选为3重量份以下，进一步优选为2重量份以下。添加量低于0.001重量份时，透明化的效果不充分，若多于5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。The amount of the basic nitrogen-containing compound to be used as the compound (D) is 0.001 parts by weight or more and 5 parts by weight based on 100 parts by weight of the resin composition containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). Parts by weight or less. It is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. Further, it is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less. When the amount is less than 0.001 part by weight, the effect of the transparency is insufficient. When the amount is more than 5 parts by weight, the coloring is remarkable, but the coloring is remarkable, the molecular weight is lowered, and the mechanical strength is insufficient.
对上述酯交换反应催化剂(D)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。In the method of adding the above-mentioned transesterification catalyst (D), the solid compound 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.
[酸性化合物(E)][Acid Compound (E)]
作为相对于聚碳酸酯树脂组合物配合的酸性化合物(E)，可使用与上述的催化剂失活剂同样的物质。As the acidic compound (E) to be blended with the polycarbonate resin composition, the same ones as the catalyst deactivator described above can be used.
酸性化合物(E)的添加量优选相对于聚碳酸酯树脂组合物中所含的化合物(D)1摩尔当量为0.5摩尔当量以上且5摩尔当量以下。此时，可更进一步提高耐湿热性，并且可更进一步提高成形时等的热稳定性。从同样的观点考虑，酸性化合物(E)的添加量更优选相对于化合物(D)1摩尔当量为0.6摩尔当量～2摩尔当量，进一步优选为0.7摩尔当量～1摩尔当量。 The amount of the acidic compound (E) to be added is preferably 0.5 molar equivalent or more and 5 molar equivalent or less with respect to 1 molar equivalent of the compound (D) contained in the polycarbonate resin composition. At this time, the moist heat resistance can be further improved, and the thermal stability during molding or the like can be further improved. From the same viewpoint, the amount of the acidic compound (E) to be added is more preferably 0.6 to 2 molar equivalents per 1 molar equivalent of the compound (D), and still more preferably 0.7 to 1 molar equivalent.
[聚碳酸酯树脂组合物(X)][Polycarbonate Resin Composition (X)]
包含上述聚碳酸酯树脂组合物(X)的树脂复合物优选将其成形而成的厚度1mm的成形体的厚度方向的平均光线透过率为50％以上。另外，从在透明用途中的适用性和染色时的鲜映性良好的观点考虑，上述平均光线透过率更优选65％以上，进一步优选70％以上。另外，平均光线透过率的测定方法在后述的实施例中进行说明。The resin composite containing the polycarbonate resin composition (X) is preferably a molded article having a thickness of 1 mm and having an average light transmittance of 50% or more in the thickness direction. In addition, the average light transmittance is more preferably 65% or more, and still more preferably 70% or more from the viewpoints of suitability for use in a transparent use and good image clarity at the time of dyeing. In addition, the method of measuring the average light transmittance will be described in the examples to be described later.
另外，在聚碳酸酯树脂组合物中，优选以DSC法测得的玻璃化温度的峰单一。另外，聚碳酸酯树脂组合物的玻璃化温度优选100℃以上且200℃以下。此时，由于可进一步提高耐热性，因此，可进一步防止成形品的变形。另外，在该情况下，可更进一步抑制树脂组合物的制造时的聚碳酸酯树脂(A)的热劣化，可进一步提高耐冲击性。进而，可更进一步抑制成形时的树脂组合物的热劣化。从同样的观点考虑，聚碳酸酯树脂组合物的玻璃化温度更优选110℃以上且190℃以下，进一步优选120℃以上且180℃以下。Further, in the polycarbonate resin composition, the peak of the glass transition temperature measured by the DSC method is preferably single. Further, the glass transition temperature of the polycarbonate resin composition is preferably 100 ° C or more and 200 ° C or less. At this time, since heat resistance can be further improved, deformation of the molded article can be further prevented. In addition, in this case, thermal deterioration of the polycarbonate resin (A) at the time of production of the resin composition can be further suppressed, and impact resistance can be further improved. Further, thermal deterioration of the resin composition at the time of molding can be further suppressed. From the same viewpoint, the glass transition temperature of the polycarbonate resin composition 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.
上述树脂组合物(X)包含含有源自上述式(1)所示的化合物的构成单元的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)，可通过将聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)调整在规定的范围来实现。The resin composition (X) contains a polycarbonate resin (A) and an aromatic polycarbonate resin (B) containing a constituent unit derived from the compound represented by the above formula (1), and can be obtained by using a polycarbonate resin ( A) and the aromatic polycarbonate resin (B) are adjusted to a predetermined range.
上述树脂组合物(X)中的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的配合比优选以树脂组合物(X)和玻璃填料(C)单一物质的折射率之差为0.01以下的方式进行调节。优选为0.005以下，特别优选为0.003以下。若折射率差大于0.01，则平均光线透过率降低，透明性差。The mixing ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the above resin composition (X) is preferably a difference in refractive index between a single substance of the resin composition (X) and the glass filler (C). Adjust to 0.01 or less. It is preferably 0.005 or less, and particularly preferably 0.003 or less. When the refractive index difference is more than 0.01, the average light transmittance is lowered and the transparency is poor.
另外，上述树脂组合物(X)中的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的配合比优选以上述树脂组合物(X)的阿贝数和玻璃填料(C)单一物质的阿贝数之差为25以下的方式进行调节。优选为24以下，特别优选为23以下。Further, the compounding ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the above resin composition (X) is preferably an Abbe number of the above resin composition (X) and a glass filler (C). The difference between the Abbe numbers of the single substances is adjusted to be 25 or less. It is preferably 24 or less, and particularly preferably 23 or less.
[其它的添加剂][Other additives]
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、除玻璃填料以外的无机填充剂、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。Various additives can be added to the above polycarbonate resin composition. As the above additives, there are antioxidants, UV absorbers, light stabilizers, mold release agents, heat stabilizers, flame retardants, flame retardant aids, inorganic fillers other than glass fillers, impact modifiers, hydrolysis inhibitors, For the foaming agent, the nucleating agent, and the like, an additive which is usually used in a polycarbonate resin can be used.
“抗氧化剂”"Antioxidants"
作为抗氧化剂，可使用树脂中所使用的一般的抗氧化剂，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，抗氧化剂的添加量优选相对于树脂组合物(X)100重量份为5重量份以下。此时，可更可靠地防止成形时的模具的污染，得到表面外观更优异的成形品。从同样的观点考虑，抗氧化剂的添加量更优选相对于树脂组合物(X)100重量份为3重量份以下，进一步优选2重量份以下。另外，抗氧化剂的添加量优选相对于树脂组合物(X)100重量份为0.001重量份以上。此时，可充分地得到相对于成形稳定性的改良效果。从同样的观点考虑，抗氧化剂的添加量更优选相对于树脂组合物(X)100重量份为0.002重量份以上，进一步优选0.005重量份以上。As the antioxidant, a general antioxidant used in the resin can be used, but from oxidation stability, heat From the viewpoint of stability, a phosphite-based antioxidant, a sulfur-based antioxidant, and a phenol-based antioxidant are preferable. Here, the amount of the antioxidant added is preferably 5 parts by weight or less based on 100 parts by weight of the resin composition (X). At this time, it is possible to more reliably prevent contamination of the mold at the time of molding, and to obtain a molded article having a more excellent surface appearance. From the same viewpoint, the amount of the antioxidant added is more preferably 3 parts by weight or less, still more preferably 2 parts by weight or less based on 100 parts by weight of the resin composition (X). In addition, the amount of the antioxidant added is preferably 0.001 part by weight or more based on 100 parts by weight of the resin composition (X). At this time, the improvement effect with respect to the formation stability can be fully obtained. From the same viewpoint, the amount of the antioxidant added is more preferably 0.002 parts by weight or more, and still more preferably 0.005 parts by weight or more based on 100 parts by weight of the resin composition (X).
(亚磷酸酯系抗氧化剂)(phosphite antioxidants)
作为亚磷酸酯系抗氧化剂，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。Examples of the phosphite-based antioxidant include triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and trisphosphonium phosphite. Ester, trioctyl phosphite, tris(octadecyl) phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, Monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol II Phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di Tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
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。Among them, it is preferred to use tridecyl phenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and double (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite. These compounds may be used alone or in combination of two or more.
(硫系抗氧化剂)(sulfur antioxidant)
作为硫系抗氧化剂，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。Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and dimyristyl- 3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra ( 3-laurylthiopropionate), bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl] sulfide, octadecyl disulfide Ether, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1'-thiobis(2-naphthol), and the like. Among the above, pentaerythritol tetrakis(3-laurylthiopropionate) is preferred. These compounds may be used alone or in combination of two or more.
(酚系抗氧化剂)(phenolic antioxidants)
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。Examples of the phenolic antioxidant include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), glycerol-3-stearylthiopropionate, and trisole. Glycol-bis[3-(3-tert-butyl-5-) Methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-four [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5- Di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris(3,5-di-tert-butyl-4 -hydroxybenzyl)isocyanurate, 4,4'-biphenylene diphosphonic acid tetrakis(2,4-di-tert-butylphenyl) ester, 3,9-double {1,1-di Methyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethyl}-2,4,8,10-tetraoxaspiro (5, 5) A compound such as undecane, 2,6-di-tert-butyl-p-cresol or 2,6-di-tert-butyl-4-ethylphenol.
这些化合物中，优选被1个以上碳原子数5以上的烷基取代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。Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable, and specifically, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyl is preferable. 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.
“UV吸收剂”"UV absorber"
作为紫外线吸收剂，可以举出：苯并***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。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. These may be used alone or in combination of two or more.
作为苯并***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***、2-(2’-羟基-3’-叔丁基-5’-己基苯基)苯并***、2-(2’-羟基-3’,5’-二叔丁基苯基)苯并***、2-(2’-羟基-3’-甲基-5’-叔辛基苯基)苯并***、2-(2’-羟基-5’-叔十二烷基苯基)苯并***、2-(2’-羟基-3’-甲基-5’-叔十二烷基苯基)苯并***、2-(2’-羟基-5’-叔丁基苯基)苯并***、甲基-3-(3-(2H-苯并***-2-基)-5-叔丁基-4-羟苯基)丙酸酯等。More specific examples of the benzotriazole-based compound include 2-(2'-hydroxy-3'-methyl-5'-hexylphenyl)benzotriazole and 2-(2'-hydroxyl group). -3'-tert-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2 '-Hydroxy-3'-methyl-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-dodecylphenyl)benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-tert-dodecylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, Methyl-3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate or the like.
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。 Examples of the triazine-based compound 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.
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。Examples of the hydroxybenzophenone-based compound include 2,2'-dihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-octyloxy Benzophenone and the like.
作为氰基丙烯酸酯系化合物，可以举出：2-氰基-3,3-二苯基丙烯酸乙酯、2’-乙基己基-2-氰基-3,3-二苯基丙烯酸酯等。Examples of the cyanoacrylate-based compound include ethyl 2-cyano-3,3-diphenylacrylate and 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate. .
作为丙二酸酯系化合物，可以举出：2-(1-芳基次烷基)丙二酸酯类等。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。Examples of the malonic ester-based compound 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.
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。The oxalic acid anilide compound may, for example, be 2-ethyl-2'-ethoxy-oxaloanilide (made by Clariant Co., Ltd., Sanduvor VSU).
其中，优选2-(2’-羟基-3’-叔丁基-5’-己基苯基)苯并***、2-(2’-羟基-5’-叔丁基苯基)苯并***、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。Among them, 2-(2'-hydroxy-3'-tert-butyl-5'-hexylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriene is preferred. Oxazole, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl) -1,3,5-triazine, 2,2',4,4'-tetrahydroxybenzophenone.
“光稳定剂”"light stabilizer"
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。此时，可进一步提高成形品的耐气候性。从同样的观点考虑，光稳定剂的分子量更优选900以下。另外，光稳定剂的分子量优选300以上。此时，可提高耐热性，可更可靠地防止成形时的模具的污染。其结果，可得到表面外观更优异的成形品。从同样的观点考虑，光稳定剂的分子量更优选400以上。进而，光稳定剂优选为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。The light stabilizer is a hindered amine light stabilizer, and its molecular weight is preferably 1,000 or less. At this time, the weather resistance of the molded article can be further improved. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 900 or less. Further, the molecular weight of the light stabilizer is preferably 300 or more. At this time, heat resistance can be improved, and contamination of the mold at the time of molding can be prevented more reliably. As a result, a molded article having a more excellent surface appearance can be obtained. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 400 or more. Further, the light stabilizer is preferably a compound having a piperidine structure. 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.
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-4-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、三癸醇和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、及十二烷醇和十二烷基-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)酰亚胺}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2,4,6-三环-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-氨基丙级)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。As such a light stabilizer, 4-piperidinol-2,2,6,6-tetramethyl-4-benzoate, bis(2,2,6,6-tetramethyl-) 4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl Piperidine-4-carboxylic acid)-1,2,3,4-butanetetrayl, 2,2,6,6-tetramethyl-piperidinol, triterpene alcohol and 1,2,3,4- a condensate of butane tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinyl, and dodecanol and dodecyl-1,2,3,4-butane IV Carboxylic acid ester, bis(1,2,3,6,6-pentamethyl-4-piperidinyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl Methyl]butyl malonate, bis(2,2,26,6-tetramethyl-1-(octyloxy)-4-piperidyl) sebacate, 1,1-dimethyl Reaction product of ethyl ethyl hydrogen peroxide and octane, 1-[2-[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propanoyloxy]ethyl]-4-[3-(3,5-di-tert-butyl-4-4-hydroxyphenyl)propanoyloxy]ethyl -2,2,6,6-tetramethylpiperidine, tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylate Acid ester, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6 -tetramethyl-4-piperidinyl)imide}hexamethylene {(2,2,6,6-tetramethyl-4-piperidinyl)imino}], N,N'-double (2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexanediamine polymer and 2,4,6-tricyclo-1,3,5-triazine, 1, 2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and β,β,β,β-tetramethyl-3,9-(2,4, Condensate of 8,10-tetraoxaspiro[5,5]undecane-diethanol, N,N'-bis(3-aminopropyl)ethylenediamine-2,4-bis[N-butyl -N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-6-chloro-1,3,5-triazine condensate, dimethyl succinate-1- (2-Hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, and the like.
光稳定剂的含量优选相对于树脂组合物(X)100重量份为0.001重量份以上且5重量份以下。此时，可更进一步防止聚碳酸酯树脂组合物的着色。其结果，例如在添加着色剂的情况下，可得到有深度和澄清感的漆黑。另外，在该情况下，可进一步提高聚碳酸酯树脂组合物的耐光性，即使将聚碳酸酯树脂组合物应用于例如汽车内外装饰品用途也可发挥优异的耐光性。光稳定剂的含量相对于树脂组合物(X)100重量份更优选为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。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，优选少量地设定光稳定剂的添加量。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 resin composition (X). At this time, the coloring of the polycarbonate resin composition can be further prevented. As a result, for example, in the case where a coloring agent is added, a darkness having a deep and clear feeling can be obtained. In addition, in this case, the light resistance of the polycarbonate resin composition can be further improved, and the polycarbonate resin composition can exhibit excellent light resistance even when applied to, for example, automotive interior and exterior decoration applications. The content of the light stabilizer 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 based on 100 parts by weight of the resin composition (X). Further, the aromatic polycarbonate resin (B) tends to be easily decomposed by the hindered amine light stabilizer. Therefore, in the case where the ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is increased, the amount of the aromatic polycarbonate resin (B) is preferably small, and it is preferable to set the light stabilizer in a small amount. The amount added.
“脱模剂”"release agent"
对聚碳酸酯树脂复合物而言，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。通过将多元醇的脂肪酸酯的量调整在该范围，可充分地得到添加效果，在成形加工中的脱模时，可更可靠地防止因脱模不良而导致成形品开裂。进而，在该情况下，可更进一步抑制树脂复合物的白浊或在成形加工时附着于模具的附着物的增大。多元醇的脂肪酸酯的含量更优选为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。In the polycarbonate resin composite, 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. When the amount of the fatty acid ester of the polyol is adjusted within this range, the effect of addition can be sufficiently obtained, and during the mold release during the molding process, cracking of the molded article due to mold release failure can be more reliably prevented. Further, in this case, it is possible to further suppress the white turbidity of the resin composite or the increase in the adhering matter adhering to the mold during the forming process. 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, still more preferably 0.1 parts by weight or more and 1 part by weight or less.
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。作为这种多元醇和硬脂酸的偏酯或全酯，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。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 stearic acid include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, and stearic acid single sorbitol. Alcohol ester, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, pentaerythritol tetradecanoate, propylene glycol monostearate, isopropyl palmitate, Sorbitol monostearate and the like. Among them, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used.
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。Further, from the viewpoint of heat resistance and moisture resistance, a full ester is more preferable as the fatty acid ester of the polyol.
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。As the fatty acid, a higher fatty acid is preferable, and a saturated fatty acid having 10 to 30 carbon atoms is more preferable. Examples of such a fatty acid include myristic acid, lauric acid, palmitic acid, stearic acid, and behenic acid.
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，可在不降低树脂的透明性的情况下提高脱模性。Further, in the fatty acid ester of a polyhydric alcohol, the polyhydric alcohol is preferably ethylene glycol. At this time, when added to the resin, the mold release property can be improved without lowering the transparency of the resin.
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。Further, the fatty acid ester of the above polyol is preferably a fatty acid diester of a glycol. At this time, when added to the resin, the decrease in the molecular weight of the resin composition in a hot and humid environment can be suppressed.
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。In the present embodiment, 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. When 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.
“其它的树脂”"Other resins"
另外，上述聚碳酸酯树脂组合物也可在不降低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、聚苯乙烯琥珀酸酯等生物降解性树脂等的1种或2种以上进行混炼而用作聚合物合金。Further, the above polycarbonate resin composition can also be, for example, an aromatic polyester, an aliphatic polyester, a polyamide, a polystyrene, a polyolefin, an acrylic, an amorphous polyolefin, or the like without deteriorating the effects of the present invention. One or two or more kinds of biodegradable resins such as ABS and AS, such as a synthetic resin, a polylactic acid, and a polystyrene succinate, are kneaded and used as a polymer alloy.
“无机填充剂、有机填充剂”"Inorganic fillers, organic fillers"
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除上述的玻璃填料(C)以外的二氧化硅、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、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。In the polycarbonate resin composition, silica, alumina, titania, calcium sulfate powder, gypsum, gypsum whisker other than the above-mentioned glass filler (C) may be added in a range in which designability can be maintained. Calcium silicate such as barium sulfate, talc, mica or wollastonite; carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber , inorganic fillers such as stainless steel fiber, potassium titanate fiber, their whiskers, powdered organic fillers such as wood powder, bamboo powder, coconut starch, softwood powder, pulp powder; crosslinked polyester, polystyrene, styrene ·Saccular/spherical organic filler such as acrylic copolymer or urea resin; carbon Fibrous organic fillers such as fibers, synthetic fibers, and natural fibers.
聚碳酸酯树脂复合物可如下制造：使用转鼓混合机、V型混合机、诺塔混合器、班伯里混炼机、混炼辊或挤出机等混合机将上述成分按一定比例同时或者以任意顺序进行混合，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。The polycarbonate resin composite can be produced by using a mixer such as a tumbler mixer, a V-type mixer, a Nauta mixer, a Banbury mixer, a kneading roll or an extruder to simultaneously apply the above components in a certain ratio. Alternatively, the mixing may be carried out in any order to perform the production. Among them, in the case of melt mixing, a substance which can be mixed under reduced pressure is more preferable.
聚碳酸酯树脂复合物的制造方法优选在预先制造含有聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)的树脂组合物(X)后添加玻璃填料(C)。在利用挤出机的情况下，优选在挤出机内制造树脂组合物(X)后，利用侧面进料器将玻璃填料(C)导入挤出机内来制造。In the method for producing a polycarbonate resin composite, it is preferred to add a glass filler (C) after previously preparing the resin composition (X) containing the polycarbonate resin (A) and the aromatic polycarbonate resin (B). In the case of using an extruder, it is preferred to produce the resin composition (X) in an extruder, and then introduce the glass filler (C) into an extruder by a side feeder.
[成形体][formed body]
聚碳酸酯树脂复合物可通过注射成形法、挤出成形法、压缩成型法等通常已知的方法来成形。通过成形得到的成形体的色调、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，适于车辆用内装饰部件。The polycarbonate resin composite 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. Therefore, it is suitable for interior parts for vehicles.
上述聚碳酸酯树脂复合物的色相、透明性、机械强度等优异，进而湿热下的色相和光学特性的稳定性也优异，因此，可应用于电气电子部件、汽车用部件、玻璃代替用途等注射成形领域；膜、片材领域；瓶、容器领域等挤出成形领域；照相机镜头、取景器镜头、CCD或CMOS用透镜等透镜用途等广泛的领域。The polycarbonate resin composite is excellent in hue, transparency, mechanical strength, and the like, and is excellent in stability in hue and optical properties under moist heat. Therefore, it can be applied to injection of electric and electronic parts, parts for automobiles, and applications for glass replacement. Forming field; film, sheet material; extrusion molding in the field of bottles and containers; lens applications such as camera lenses, viewfinder lenses, CCD or CMOS lenses, etc.
上述聚碳酸酯树脂复合物由于透明性、机械强度等优异，因此，即使用着色剂等进行着色，鲜映性也优异，因此，可应用于汽车内外装饰部件或电气电子部件、框体等用途。作为汽车外装部件，例如有挡泥板、保险杠、仪表板、门板、侧装饰件、支柱、散热器格栅、侧保护器、侧镶条、后保护器、后镶条、各种扰流器、发动机罩、车顶面板、行李箱盖、可拆卸顶部、车窗反射器、镜子外壳、外门拉手等。作为汽车内装饰部件，例如有仪表板、中控台面板、仪表部件、各种开关类、汽车导航部件、汽车音频视频部件、自动移动计算机部件等。作为电气电子部件、框体，例如有台式电脑、笔记本电脑等电脑类的外装置部件、打印机、复印机、扫描器及传真机(包含它们的复合机)等OA设备的外装饰部件、显示器装置(CRT、液晶、等离子体、投影仪、及有机EL等)的外装饰部件、鼠标等外装饰部件、键盘的键或各种开关等开关机构部件、游戏机(家庭用游戏机、营业用游戏机及弹球机及***等)的外装饰部件等。进而，可以举出：便携信息终端(所谓PDA)、移动电话、便携书籍(辞典类等)、便携电 视、记录介质(CD、MD、DVD、下一代高密度盘、硬盘等)的驱动器、记录介质(IC卡、人工智能媒体、存储棒等)的读取装置、光学相机、数码相机、抛物面天线、电动工具、VTR、熨斗、吹风机、煮饭器、微波炉、热板、音响设备、照明设备、冰箱、空调、空气净化器、负离子发生器及时钟等电气·OA设备、家庭用电器产品。Since the polycarbonate resin composite is excellent in transparency, mechanical strength, and the like, it is colored by using a coloring agent or the like, and is excellent in image clarity. Therefore, it can be applied to interior and exterior decorative parts for automobiles, electrical and electronic parts, frames, and the like. . As automotive exterior parts, such as fenders, bumpers, instrument panels, door panels, side trims, pillars, radiator grilles, side protectors, side trims, rear protectors, rear trims, various spoilers , hood, roof panel, trunk lid, detachable top, window reflector, mirror housing, outer door handle, etc. As interior trim parts of automobiles, there are, for example, instrument panels, center console panels, instrument components, various switches, car navigation components, car audio and video components, and automatic mobile computer components. As an electric and electronic component or a housing, for example, an external component such as a desktop computer or a notebook computer, an external component of a printer, a copying machine, a scanner, and a facsimile machine (a multifunction peripheral including the same), and an external decorative component and display device (for a OA device) Exterior decorative parts such as CRT, liquid crystal, plasma, projector, and organic EL, external decorative parts such as a mouse, keyboard keys, switch mechanism components such as various switches, and game machines (home game machines, business game machines) And exterior parts such as pinball machines and slot machines. Further, a portable information terminal (so-called PDA), a mobile phone, a portable book (a dictionary, etc.), and a portable battery can be cited. A device for reading and recording media (CD, MD, DVD, next-generation high-density disk, hard disk, etc.), reading device (IC card, artificial intelligence media, memory stick, etc.), optical camera, digital camera, parabolic antenna , electric tools, VTR, iron, hair dryer, rice cooker, microwave oven, hot plate, audio equipment, lighting equipment, refrigerator, air conditioner, air purifier, negative ion generator and clock, etc. Electrical OA equipment, household electrical products.
本发明的成形体随着聚碳酸酯树脂复合物中的玻璃填料(C)的量增加，有时成形体的表面变差，使透明性降低。为了提高透明性及提高表面外观，优选提高成形时的模具温度，或使用隔热模具成形或在成形体的表面层叠至少1层透明树脂层。作为层叠的透明树脂层，可以为硬涂层、透明涂层这样的固化型树脂层，也可以通过模内成形将透明热塑性树脂膜层叠化。In the molded article of the present invention, as the amount of the glass filler (C) in the polycarbonate resin composite increases, the surface of the molded body may be deteriorated to lower the transparency. In order to improve transparency and to improve the surface appearance, it is preferred to increase the mold temperature during molding, or to form at least one transparent resin layer on the surface of the molded body by using a heat insulating mold. The laminated transparent resin layer may be a curable resin layer such as a hard coat layer or a clear coat layer, or a transparent thermoplastic resin film may be laminated by in-mold molding.
[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。[Examples] Hereinafter, the present invention will be described in more detail by way of Examples. However, the present invention is not limited to the examples below, unless the point is exceeded.
[评价方法][Evaluation method]
以下，聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)及树脂复合物的物性或特性的评价通过以下方法进行。Hereinafter, the evaluation of the physical properties or characteristics of the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the resin composite was carried out by the following method.
(1)还原粘度的测定(1) Determination of reduced viscosity
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。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 η 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. Next, the specific viscosity η sp is obtained from the relative viscosity η rel based on the following formula (ii).
ηrel＝t/t0···(i)η rel =t/t 0 ···(i)
ηsp＝ηrel-1···(ii)η sp =η rel -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。The obtained specific viscosity ηsp was divided by the concentration c (g/dL) of the solution, whereby the reduced viscosity (η sp /c) was determined. The higher the value of the reduced viscosity, the larger the molecular weight.
(2)玻璃化温度(Tg)的测定(2) Determination of glass transition temperature (Tg)
聚碳酸酯树脂组合物的Tg为使用Perkinelmer公司制差示扫描量热仪“DSC7”在氮气气氛下，以加热速度20℃/分钟从25℃升温至200℃，在200℃下保持3分钟后，以冷却速度20℃/分钟降温至25℃，在25℃下保持3分钟后，再次以加热速度5℃/分钟升温至200℃时，由得到的DSC曲线依据JIS-K7121的方法求得的Tmg的值。另外，进行玻璃化温度的单一性的评价。具体而言，将DSC曲线的峰单一的情况评价 为单一性为“○”，将DSC曲线的峰为多个的情况评价为单一性为“×”。The Tg of the polycarbonate resin composition was raised from 25 ° C to 200 ° C at a heating rate of 20 ° C / min under a nitrogen atmosphere using a differential scanning calorimeter "DSC7" manufactured by Perkinelmer Co., Ltd., and held at 200 ° C for 3 minutes. The temperature was lowered to 25 ° C at a cooling rate of 20 ° C / min, and after maintaining at 25 ° C for 3 minutes, and then raised to 200 ° C at a heating rate of 5 ° C / min, the obtained DSC curve was obtained according to the method of JIS-K7121. The value of Tmg. In addition, the evaluation of the singularity of the glass transition temperature was performed. Specifically, the case where the peak of the DSC curve is single is evaluated. When the singularity is "○" and the peak of the DSC curve is plural, the singularity is "x".
(3)平均光线透过率的测定：(3) Determination of average light transmittance:
将聚碳酸酯树脂复合物的颗粒使用热风干燥机在90℃下干燥4小时以上。接着，将干燥的颗粒供给于成形机(海天塑料集团，HTF861TJ)，在树脂温度240℃、模具温度60℃、成形循环50秒的条件下进行成形，由此得到成形板(宽度100mm×长度100mm×厚度1mm)。依据中国工业标准(2000年)。对于聚碳酸酯/玻纤复合物，在240℃热压(BL-6170-A-25J，宝轮精密检测仪器有限公司)成30mm*20mm*1mm的薄片。使用UV/vis分光光度计(SHIMADZU，UV2550)测定波长在300nm到800nm范围内光线透过率，据此计算试样的平均光线透过率。另外，平均光线透过率将50％以上设为合格。The pellet of the polycarbonate resin composite was dried at 90 ° C for 4 hours or more using a hot air dryer. Then, the dried pellets were supplied to a molding machine (Haitian Plastics Group, HTF861TJ), and molded at a resin temperature of 240 ° C, a mold temperature of 60 ° C, and a molding cycle of 50 seconds, thereby obtaining a formed plate (width 100 mm × length 100 mm). × thickness 1mm). According to Chinese Industrial Standards (2000). For the polycarbonate/glass fiber composite, it was hot pressed at 240 ° C (BL-6170-A-25J, Baolun Precision Testing Instrument Co., Ltd.) into a sheet of 30 mm * 20 mm * 1 mm. The light transmittance of the wavelength in the range of 300 nm to 800 nm was measured using a UV/vis spectrophotometer (SHIMADZU, UV2550), and the average light transmittance of the sample was calculated therefrom. In addition, the average light transmittance is set to 50% or more.
(4)折射率及阿贝数的测定：(4) Determination of refractive index and Abbe number:
a)树脂组合物(X)以及树脂复合物的测定法a) Determination of Resin Composition (X) and Resin Composite
在宝石折射仪(GI-RZ6,BGI(宝光仪器))上滴一滴二碘甲烷,放上10mm*10mm*1mm的聚碳酸酯树脂组合物(X),使其充分接触,在钠光源(589nm)下读出折射率。A drop of diiodomethane was placed on a gem refractometer (GI-RZ6, BGI), and a 10 mm*10 mm*1 mm polycarbonate resin composition (X) was placed to make it fully contacted with the sodium source ( The refractive index was read at 589 nm).
在阿贝折光仪(2WAJ,Shanghai Optical Instrument Factory)上滴一滴溴代萘，放上10mm*10mm*1mm的聚碳酸酯树脂组合物(X),使其充分接触，在日光下读出其阿贝数。A drop of bromo naphthalene was dropped on a 2WAJ, Shanghai Optical Instrument Factory, and a polycarbonate resin composition (X) of 10 mm * 10 mm * 1 mm was placed to make it fully contacted, and it was read in sunlight. Number of shells.
b)玻璃填料的物性值b) physical properties of glass filler
关于后述的玻璃填料的物性值，使用文献(D.Krug III,et al.,Composites Science and Technology,2013,77,95-100)记载的数值。Regarding the physical property values of the glass filler to be described later, the numerical values described in the literature (D. Krug III, et al., Composites Science and Technology, 2013, 77, 95-100) are used.
(5)刚性(DMA)的测定法：(5) Determination of rigidity (DMA):
17mm*7.5mm*0.4mm的聚碳酸酯/玻纤复合物试样采用DMA(Q800,TA)测定弹性模量。测试条件如下：振幅5μm，频率10HZ，温度30℃，薄膜拉伸模式。A 17 mm*7.5 mm*0.4 mm polycarbonate/glass fiber composite sample was measured for modulus of elasticity using DMA (Q800, TA). The test conditions were as follows: amplitude 5 μm, frequency 10 Hz, temperature 30 ° C, film stretching mode.
[使用原料][Use raw materials]
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。The abbreviations and manufacturers of the compounds used in the following examples and comparative examples are as follows.
＜二羟基化合物＞<dihydroxy compound>
·ISB：异山梨醇[Roquette Freres公司制]·ISB: Isosorbide [Roquette Freres]
·CHDM：1,4-环己烷二甲醇[SKChemical公司制]CHDM: 1,4-cyclohexane dimethanol [made by SK Chemical Co., Ltd.]
＜碳酸二酯＞ <Carbonate>
·DPC：碳酸二苯酯[三菱化学(株)制]DPC: Diphenyl carbonate [Mitsubishi Chemical Co., Ltd.]
＜催化剂失活剂(酸性化合物(D))＞<Catalyst deactivating agent (acid compound (D))>
·亚磷酸[太平化学产业(株)制](分子量82.0)·phosphoric acid [made by Taiping Chemical Industry Co., Ltd.] (molecular weight 82.0)
＜热稳定剂(抗氧化剂)＞<Heat stabilizer (antioxidant)>
·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]Irganox 1010: pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Corporation]
·AS2112：三(2,4-二叔丁基苯基)亚磷酸酯[(株)ADEKA制](分子量646.9)- AS2112: Tris(2,4-di-tert-butylphenyl) phosphite [manufactured by ADEKA Corporation] (molecular weight 646.9)
＜脱模剂＞<release agent>
·E-275：乙二醇二硬脂酸酯[日油(株)制]E-275: Ethylene glycol distearate [Nippon Oil Co., Ltd.]
[聚碳酸酯树脂(A)的制造例1][Production Example 1 of Polycarbonate Resin (A)]
使用由立式搅拌反应器3台和卧式搅拌反应器1台以及双螺杆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以相对于全部二羟基化合物1mol为1.5μmol的方式供给于第1立式搅拌反应器。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、第4卧式搅拌反应器：225℃、0.5kPa、90分钟。一边以得到的聚碳酸酯树脂的还原粘度为0.41dL/g～0.43dL/g的方式微调节第4卧式搅拌反应器的内压一边运行。The polymerization of the polycarbonate resin was carried out using a continuous polymerization apparatus consisting of three vertical stirred reactors, one horizontal stirred reactor, and a twin-screw extruder. Specifically, ISB, CHDM, and DPC were first melted in a tank, respectively, with ISB at 35.2 kg/hr, CHDM at 14.9 kg/hr, and DPC at 74.5 kg/hr (in molar ratio as ISB/CHDM/DPC). The flow rate of =0.700/0.300/1.010) was continuously supplied to the first vertical stirring reactor. At the same time, an aqueous solution of calcium acetate monohydrate as a catalyst was supplied to the first vertical stirring reactor so as to be 1.5 μmol per 1 mol of the total dihydroxy compound. 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, 90 minutes, and a second vertical stirred reactor: 195 ° C, 10 kPa, 45 minutes, and third standing Stirred reactor: 210 ° C, 3 kPa, 45 minutes, 4th horizontal stirred reactor: 225 ° C, 0.5 kPa, 90 minutes. The inside of the fourth horizontally stirred reactor was operated while finely adjusting the reduced viscosity of the obtained polycarbonate resin to 0.41 dL/g to 0.43 dL/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供给于排气型双螺杆挤出机[(株)日本制钢所制TEX30α、L/D：42.0、L(mm)：螺杆的长度、D(mm)：螺杆的直径]。将通过了挤出机的聚碳酸酯树脂在同样的熔融状态下通过网眼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。The polycarbonate resin was taken out from the fourth horizontally stirred reactor in an amount of 60 kg/hr, and then the resin was supplied to the exhaust type twin-screw extruder in a molten state [TEX30α, L manufactured by Nippon Steel Co., Ltd. /D: 42.0, L (mm): length of the screw, D (mm): diameter of the screw]. The polycarbonate resin that passed through the extruder was passed through a candle-type filter (manufactured by SUS316) having a mesh size of 10 μm in the same molten state, and the foreign matter was filtered. Then, 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%.
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排气口的近前相对于树脂添加2000质量ppm的水，进行注水脱挥。在第3排气口的近前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。相对于上述聚碳酸酯树脂添加0.65质量ppm的亚磷酸(以磷原子的量计为0.24质量ppm)。另外，亚磷酸如下添加。制备在制造例1中得到的聚碳酸酯树脂的颗粒上涂布混合亚磷酸的乙醇溶液的母料，从挤出机的第1排气口的近前(挤出机的树脂供给口侧)以相对于挤出机中的聚碳酸酯树脂100质量份，母料为1质量份的方式进行供给。The extruder has three vacuum exhaust ports, and the remaining low molecular components in the resin are removed by volatility. Water injection devolatilization was performed by adding 2000 mass ppm of water to the resin in the vicinity of the second exhaust port. 0.1 parts by mass, 0.05 parts by mass, and 0.3 parts, respectively, are added to 100 parts by mass of the polycarbonate resin in the vicinity of the third exhaust port. Parts by mass of Irganox 1010, AS 2112, E-275. Through the above operation, an ISB/CHDM copolymer polycarbonate resin was obtained. 0.65 mass ppm of phosphorous acid (0.24 mass ppm in terms of phosphorus atom) was added to the above polycarbonate resin. In addition, phosphorous acid was added as follows. The masterbatch of the ethanol solution in which the phosphorous acid was mixed was applied to the pellet of the polycarbonate resin obtained in Production Example 1, and was placed from the vicinity of the first exhaust port of the extruder (on the resin supply port side of the extruder). The master batch was supplied in an amount of 1 part by mass based on 100 parts by mass of the polycarbonate resin in the extruder.
将制造例1中得到的聚碳酸酯树脂(A)称为“PC-A1”。The polycarbonate resin (A) obtained in Production Example 1 is referred to as "PC-A1".
[聚碳酸酯树脂(A)的制造例2][Production Example 2 of Polycarbonate Resin (A)]
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。相对于上述聚碳酸酯树脂添加0.65质量ppm的亚磷酸(以磷原子的量计为0.24质量ppm)。另外，亚磷酸如下添加。制备在制造例1中得到的聚碳酸酯树脂的颗粒上涂布混合亚磷酸的乙醇溶液的母料，从挤出机的第1排气口的近前(挤出机的树脂供给口侧)以相对于挤出机中的聚碳酸酯树脂100质量份，母料为1质量份的方式进行供给。The supply amount of each raw material to the reactor was ISB 25.4 kg/hr, CHDM 25.0 kg/hr, and DPC 74.8 kg/hr (in terms of molar ratio, ISB/CHDM/DPC=0.500/0.500/ 1.006), the aqueous solution of calcium acetate monohydrate is set to 1.5 μmol with respect to 1 mol of all dihydroxy compounds, and the reduced viscosity of the obtained polycarbonate resin is changed from 0.60 dL/g to 0.63 dL/g, and In the same manner as in Production Example 1 described above, a resin was obtained to obtain a polycarbonate resin having a molar ratio of ISB/CHDM of 50/50 mol%. 0.65 mass ppm of phosphorous acid (0.24 mass ppm in terms of phosphorus atom) was added to the above polycarbonate resin. In addition, phosphorous acid was added as follows. The masterbatch of the ethanol solution in which the phosphorous acid was mixed was applied to the pellet of the polycarbonate resin obtained in Production Example 1, and was placed from the vicinity of the first exhaust port of the extruder (on the resin supply port side of the extruder). The master batch was supplied in an amount of 1 part by mass based on 100 parts by mass of the polycarbonate resin in the extruder.
[芳香族聚碳酸酯树脂(B)][Aromatic Polycarbonate Resin (B)]
PC-B：三菱工程塑料公司制NOVAREX 7022J(双酚A构成单元100摩尔％的芳香族聚碳酸酯树脂、聚碳酸酯树脂的还原粘度0.51dL/g)PC-B: NOVAREX 7022J manufactured by Mitsubishi Engineering Plastics Co., Ltd. (100 mol% aromatic polycarbonate resin of bisphenol A constituent unit, reduced viscosity of polycarbonate resin 0.51 dL/g)
[玻璃填料(C)][Glass filler (C)]
玻璃纤维(GF)：PPG，ChopVantage 3540(PPG Industries公司制、折射率1.558，阿贝数数55.5，纤维直径：10μm、纤维长度：3.2mm、表面处理剂：末端带胺基的硅烷偶联剂)Glass fiber (GF): PPG, ChopVantage 3540 (manufactured by PPG Industries, refractive index: 1.558, Abbe number: 55.5, fiber diameter: 10 μm, fiber length: 3.2 mm, surface treatment agent: amide coupling agent with amine group at the end) )
[实施例1]：[Example 1]:
将24.5g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂),50.5g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600),在240℃,80rpm,混炼3～4min,待体系透明化后，以所得到的树脂组合物作为树脂组合物(X)，加入14g玻纤(PPG,3540),继续混炼到10min后出 料,得到所需试样。24.5 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 50.5 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly. After that, it was added to a kneading machine (Haake, Rheotress 600), and kneaded at 240 ° C, 80 rpm for 3 to 4 minutes. After the system was made transparent, the obtained resin composition was used as the resin composition (X), and 14 g of glass fiber was added. PPG, 3540), continue to mix until 10min Material, to obtain the desired sample.
＜配合·混炼＞<Mixed and mixed>
＜试验片的成形＞<Formation of test piece>
使用这些试验片进行上述的评价，将其结果示于表1。The above evaluation was carried out using these test pieces, and the results are shown in Table 1.
[实施例2]：[Example 2]:
将24.5g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例1中得到的聚碳酸酯树脂)，50.5g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼3～4min,待体系透明化后，以所得到的树脂组合物作为树脂组合物(X)，加入14g玻纤(PPG，3540),继续混炼到10min后出料，得到所需试样。24.5 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 1 of polycarbonate resin (A)), 50.5 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly. After that, it was added to a kneading machine (Haake, Rheotress 600), and kneaded at 240 ° C, 80 rpm for 3 to 4 minutes. After the system was made transparent, the obtained resin composition was used as the resin composition (X), and 14 g of glass fiber was added. PPG, 3540), continue mixing until 10 min, and discharge to obtain the desired sample.
[实施例3]：[Example 3]:
将28g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂)，42g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼3～4min,待体系透明化后，以所得到的树脂组合物作为树脂组合物(X)，加入14g玻纤(PPG，3540),继续混炼到10min后出料，得到所需试样。28 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 42 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly and then added. The kneading machine (Haake, Rheotress 600) was kneaded at 240 ° C, 80 rpm for 3 to 4 minutes. After the system was made transparent, the obtained resin composition was used as the resin composition (X), and 14 g of glass fiber (PPG, 3540), continue to mix after 10 minutes to discharge, to obtain the desired sample.
[实施例4]：[Example 4]:
将21g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂)，49g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼3～4min，待体系透明化后，以所得到的树脂组合物作为树脂组合物(X)，加入14g玻纤(PPG，3540)，继续混炼到10min后出料，得到所需试样。21 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 49 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly and then added. The kneading machine (Haake, Rheotress 600) was kneaded at 240 ° C, 80 rpm for 3 to 4 minutes. After the system was made transparent, the obtained resin composition was used as the resin composition (X), and 14 g of glass fiber (PPG, 3540), continue to mix after 10 minutes to discharge, to obtain the desired sample.
[实施例5]：[Example 5]:
将24.5g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂)，50.5g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼3～4min，待体系透明化后，以所得到的树脂组合物作为树脂组合物(X)，加入21g玻纤(PPG，3540)，继续混炼到10min后出料，得到所需试样。24.5 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 50.5 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly. After that, it was added to a kneading machine (Haake, Rheotress 600), and kneaded at 240 ° C, 80 rpm for 3 to 4 minutes. After the system was made transparent, the obtained resin composition was used as the resin composition (X), and 21 g of glass fiber was added. PPG, 3540), continue mixing until 10 min, and discharge to obtain the desired sample.
[比较例1]： [Comparative Example 1]:
将35g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂)，35g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼8min，得到所需试样。35 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 35 g of bisphenol A polycarbonate (7022 J), and 2 mg of sodium methoxide powder were previously mixed uniformly and then added. A mixer (Haake, Rheotress 600) was kneaded at 240 ° C, 80 rpm for 8 min to obtain the desired sample.
[比较例2]：[Comparative Example 2]:
将24.5g的生物基聚碳酸酯(聚碳酸酯树脂(A)的制造例2中得到的聚碳酸酯树脂)，50.5g的双酚A聚碳酸酯(7022J)和2mg甲醇钠粉末预先混合均匀后加入混炼机(Haake,Rheotress 600)，在240℃，80rpm，混炼8min，得到所需试样。24.5 g of bio-based polycarbonate (polycarbonate resin obtained in Production Example 2 of polycarbonate resin (A)), 50.5 g of bisphenol A polycarbonate (7022 J) and 2 mg of sodium methoxide powder were previously mixed uniformly. Thereafter, it was added to a mixer (Haake, Rheotress 600), and kneaded at 240 ° C, 80 rpm for 8 minutes to obtain a desired sample.
[表1][Table 1]
Figure PCTCN2015085764-appb-000012
Figure PCTCN2015085764-appb-000012
由表1可知，实施例的聚碳酸酯树脂复合物包含含有源自上述的式(1)所示的化合物的构成单元的聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)和玻璃纤维(C)，这种聚碳酸酯树脂复合物的厚度1mm的成形体的平均光线透过率为50％以上。判明这样的聚碳酸酯树脂复合物的透明性优异，并且刚性优异。 As is clear from Table 1, the polycarbonate resin composite of the examples includes the polycarbonate resin (A) and the aromatic polycarbonate resin (B) containing the constituent units derived from the compound represented by the above formula (1). In the glass fiber (C), the molded article having a thickness of 1 mm of the polycarbonate resin composite had an average light transmittance of 50% or more. It was found that such a polycarbonate resin composite is excellent in transparency and excellent in rigidity.

Claims (6)

  1. 一种树脂复合物，其相对于树脂组合物(X)100重量份含有10重量份～150重量份的玻璃填料(C)，该树脂组合物(X)包含含有源自下述式(1)所示的化合物的构成单元的聚碳酸酯树脂(A)和芳香族聚碳酸酯树脂(B)，其特征在于，以厚度1mm的片材测得的平均光线透过率为50％以上，A resin composite containing 10 parts by weight to 150 parts by weight of a glass filler (C) per 100 parts by weight of the resin composition (X), the resin composition (X) comprising a compound derived from the following formula (1) The polycarbonate resin (A) and the aromatic polycarbonate resin (B), which are constituent units of the compound shown, have an average light transmittance of 50% or more as measured by a sheet having a thickness of 1 mm.
    Figure PCTCN2015085764-appb-100001
    Figure PCTCN2015085764-appb-100001
  2. 根据权利要求1所述的树脂复合物，其特征在于，相对于所述聚碳酸酯树脂(A)中的源自全部二醇的构成单元100摩尔％，以超过50摩尔％的比例含有源自下述式(1)所示的二羟基化合物的构成单元，The resin composite according to claim 1, which is contained in an amount of more than 50% by mole based on 100% by mole of the constituent units derived from all the diols in the polycarbonate resin (A). a constituent unit of the dihydroxy compound represented by the following formula (1),
    Figure PCTCN2015085764-appb-100002
    Figure PCTCN2015085764-appb-100002
  3. 根据权利要求1或2所述的树脂复合物，其特征在于，所述树脂组合物(X)含有聚碳酸酯树脂(A)、芳香族聚碳酸酯树脂(B)和酯交换反应催化剂(D)及/或酸性化合物(E)。The resin composite according to claim 1 or 2, wherein the resin composition (X) contains a polycarbonate resin (A), an aromatic polycarbonate resin (B), and a transesterification catalyst (D). And/or acidic compound (E).
  4. 根据权利要求1～3中任一项所述的树脂复合物，其特征在于，所述树脂组合物(X)以波长589nm测得的折射率和玻璃填料(C)单一物质以波长589nm测得的折射率之差为0.01以下。The resin composite according to any one of claims 1 to 3, wherein the resin composition (X) has a refractive index measured at a wavelength of 589 nm and a glass filler (C) single substance is measured at a wavelength of 589 nm. The difference in refractive index is 0.01 or less.
  5. 根据权利要求1～4中任一项所述的树脂复合物，其特征在于，所述玻璃填料(C)以波长589nm测得的折射率为1.550以上且1.560以下。The resin composite according to any one of claims 1 to 4, wherein the glass filler (C) has a refractive index measured at a wavelength of 589 nm of 1.550 or more and 1.560 or less.
  6. 根据权利要求1～5中任一项所述的树脂复合物，其特征在于，所述树脂组合物(X)的阿贝数和玻璃填料(C)单一物质的阿贝数之差为25以下。 The resin composite according to any one of claims 1 to 5, wherein a difference between an Abbe number of the resin composition (X) and an Abbe number of a single material of the glass filler (C) is 25 or less .
PCT/CN2015/085764 2015-07-31 2015-07-31 Polycarbonate resin composite WO2017020185A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2015/085764 WO2017020185A1 (en) 2015-07-31 2015-07-31 Polycarbonate resin composite
CN201580081573.4A CN107849344B (en) 2015-07-31 2015-07-31 Polycarbonate resin compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2015/085764 WO2017020185A1 (en) 2015-07-31 2015-07-31 Polycarbonate resin composite

Publications (1)

Publication Number Publication Date
WO2017020185A1 true WO2017020185A1 (en) 2017-02-09

Family

ID=57942144

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2015/085764 WO2017020185A1 (en) 2015-07-31 2015-07-31 Polycarbonate resin composite

Country Status (2)

Country Link
CN (1) CN107849344B (en)
WO (1) WO2017020185A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110997807A (en) * 2017-08-02 2020-04-10 出光兴产株式会社 Method for producing polycarbonate resin composition

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112646340A (en) * 2020-09-27 2021-04-13 武汉顺威赛特工程塑料有限公司 High-temperature oil-resistant flame-retardant bio-based polycarbonate material and preparation method thereof
CN114790328B (en) * 2022-05-10 2024-03-22 华东理工大学 Alicyclic polycarbonate composition

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148604A1 (en) * 2006-06-19 2007-12-27 Mitsubishi Chemical Corporation Polycarbonate copolymer and process for production thereof
CN101896536A (en) * 2007-12-12 2010-11-24 三菱化学株式会社 Process for production of polycarbonate and moldings of polycarbonate
CN102656231A (en) * 2009-12-10 2012-09-05 三菱化学株式会社 Polycarbonate resin composition and molded body, film, plate and injection-molded article obtained by molding same
TW201425463A (en) * 2012-11-05 2014-07-01 Idemitsu Kosan Co Polycarbonate resin composition and molded article

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007148604A1 (en) * 2006-06-19 2007-12-27 Mitsubishi Chemical Corporation Polycarbonate copolymer and process for production thereof
CN101896536A (en) * 2007-12-12 2010-11-24 三菱化学株式会社 Process for production of polycarbonate and moldings of polycarbonate
CN102656231A (en) * 2009-12-10 2012-09-05 三菱化学株式会社 Polycarbonate resin composition and molded body, film, plate and injection-molded article obtained by molding same
TW201425463A (en) * 2012-11-05 2014-07-01 Idemitsu Kosan Co Polycarbonate resin composition and molded article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110997807A (en) * 2017-08-02 2020-04-10 出光兴产株式会社 Method for producing polycarbonate resin composition
EP3663356A4 (en) * 2017-08-02 2021-05-12 Idemitsu Kosan Co., Ltd. Method for producing polycarbonate resin composition
US11555114B2 (en) 2017-08-02 2023-01-17 Idemitsu Kosan Co., Ltd. Method for producing polycarbonate resin composition
TWI799433B (en) * 2017-08-02 2023-04-21 日本商出光興產股份有限公司 Method for producing polycarbonate resin composition

Also Published As

Publication number Publication date
CN107849344B (en) 2020-07-10
CN107849344A (en) 2018-03-27

Similar Documents

Publication Publication Date Title
JP6714877B2 (en) Polycarbonate resin composition and molded article thereof
WO2011071162A1 (en) Polycarbonate resin composition and molded body, film, plate and injection-molded article obtained by molding same
US10526446B2 (en) Polycarbonate resin composition, method for producing same, and molded object
WO2017020185A1 (en) Polycarbonate resin composite
KR102200887B1 (en) Impact modified eco-friendly polyester carbonate resin compositions and method for preparing same
JP6671114B2 (en) Polycarbonate resin composition, method for producing the same, molded article, and method for producing the same
JP6950234B2 (en) Polycarbonate resin composition, its manufacturing method, molded article
JP6782576B2 (en) Polycarbonate resin composition
JP7095358B2 (en) Polycarbonate resin composition and its molded product
CN113383035B (en) Molding material comprising carbon fiber-reinforced polycarbonate resin composition
JP6642212B2 (en) Polycarbonate resin composition and molded article
JP6956860B2 (en) Phosphorus-containing thermoplastic resin, flame-retardant resin composition and molded product
CN107709459B (en) Polycarbonate resin composition, method for producing same, and molded article
CN107709458B (en) Polycarbonate resin composition, method for producing same, and molded article
CN107922720B (en) Polycarbonate resin composition, method for producing same, and molded article
JP2018150480A (en) Polycarbonate resin composition and molding
JP6693232B2 (en) Polycarbonate resin composition and molded article
JP6693231B2 (en) Polycarbonate resin composition and molded article
JP2023133987A (en) Polycarbonate resin composition and molding

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: 15899961

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: 15899961

Country of ref document: EP

Kind code of ref document: A1