JP2017014368A - Polycarbonate resin composition and molded body thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in transparency and having biogenic material percentage content, heat resistance and impact resistance at high level with good balance and a molded body thereof.SOLUTION: There is provided a polycarbonate resin composition containing a polycarbonate resin containing a structural unit derived from an isosorbide derivative (A), an aromatic polycarbonate resin (B) and an epoxy compound represented by the formula (2) (C). There is provided a polycarbonate resin composition having the content of (C) is 0.5 pts.wt. to 5 pts.wt. based on total 100 pts.wt. of the (A) and (B). (2), where n is an integer of 0 to 3.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition that is excellent in transparency and has a good balance of biogenic material content, heat resistance, and impact resistance, and a molded body formed by molding the resin composition.

  Conventional aromatic polycarbonate resins containing structures derived from bisphenol A and the like are manufactured using raw materials derived from petroleum resources. However, in recent years, there is a concern about the depletion of petroleum resources. There is a demand for providing a polycarbonate resin using the obtained raw material. In addition, since there is concern that global warming due to an increase and accumulation of carbon dioxide emissions will lead to climate change, polycarbonate resin made from carbon-neutral plant-derived monomers as raw materials even after disposal after use Development is required.

  Under such circumstances, a method of obtaining a polycarbonate resin by using isosorbide (ISB), which is a dihydroxy compound obtained from biomass resources, as a monomer component, and distilling off a by-product monohydroxy compound under reduced pressure by transesterification with a carbonic acid diester. Has been proposed (see, for example, Patent Documents 1 to 7).

  However, dihydroxy compounds such as ISB have lower thermal stability than bisphenol compounds used in conventional aromatic polycarbonate resins, and are thermally decomposed during polycondensation reactions, molding, and processing at high temperatures. There was a problem that the resin was colored. Furthermore, the copolymer of ISB and bisphenol compound described in Patent Documents 3 to 6 can provide a polymer having a high glass transition temperature, but the polymer has a difference in the reactivity of ISB and the reactivity of bisphenol compound. If the polymerization temperature is lower than the polymerization temperature of the aromatic polycarbonate resin in consideration of the color tone and the thermal stability of ISB, the end will be a bisphenol compound, resulting in a kind of end-capping and a sufficient degree of polymerization. May not be improved and the polymer may have poor impact resistance. In particular, it becomes remarkable when the copolymerization amount of the bisphenol compound in the polymer is 20 mol% or more.

  Further, Patent Document 7 discloses a polycarbonate copolymer containing a structural unit derived from ISB, a structural unit derived from an aliphatic dihydroxy compound, and a structural unit derived from an aromatic bisphenol compound. Although the polymer is also excellent in heat resistance, moldability and mechanical strength, it contains a structural unit derived from a bisphenol compound, so that the degree of polymerization is not sufficiently increased and the polymer may have poor impact resistance. In addition, the content of biogenic substances is low, which is not preferable from the viewpoint of the environment.

  Polycarbonate resin composed of dihydroxy compounds such as isosorbide (ISB), which is a dihydroxy compound obtained from biomass resources, has high glass transition temperature and excellent heat resistance, but is rigid and has high melt viscosity at the time of melt polymerization and high molecular weight. This polymer has a disadvantage that it has poor impact resistance. In order to improve this toughness, an attempt has been made to copolymerize an aliphatic dihydroxy compound or an aromatic bisphenol compound.

  Specifically, Patent Document 8 discloses a polycarbonate resin containing a structural unit derived from ISB and an aliphatic hydrocarbon dihydroxy compound, and the structural unit derived from the aliphatic hydrocarbon dihydroxy compound is 45 mol%. A polycarbonate resin composition containing the above polycarbonate resin and aromatic polycarbonate resin is disclosed. Patent Document 9 discloses a polycarbonate resin composition having excellent pencil hardness by mixing a polycarbonate resin containing a structural unit derived from ISB and an aliphatic hydrocarbon dihydroxy compound into an aromatic polycarbonate resin. Has been.

International Publication No. 2004/111106 Pamphlet International Publication No. 2007/063823 Pamphlet International Publication No. 2005/066239 Pamphlet International Publication No. 2006/041190 Pamphlet JP 2009-062501 A JP 2009-020963 A JP 2011-127108 A International Publication No. 2011/071162 Pamphlet International Publication No. 2012/1117212 Pamphlet

  However, the aliphatic dihydroxy compound copolymer has insufficient heat resistance, and the aromatic bisphenol compound copolymer has high heat resistance, but there is a problem that a polycarbonate resin having a sufficient molecular weight cannot be obtained due to reactivity problems. is there. Therefore, as described in Patent Document 8, the above-described resin composition containing an ISB copolymer polycarbonate resin containing 45 mol% or more of an aliphatic dihydroxy compound and an aromatic polycarbonate resin has transparency, hue, thermal stability, moldability and Although it is excellent in mechanical strength, for example, in order to obtain a composition having a glass transition temperature of 120 ° C. or higher in order to further improve heat resistance, the content of the aromatic polycarbonate resin in the polycarbonate resin composition is 50% by weight or more. The need to increase to This means that the biogenic substance content is reduced, which is not preferable from the environmental viewpoint. Further, as in Patent Document 9, a polycarbonate resin composition in which a polycarbonate resin containing a structural unit derived from ISB and a dihydroxy compound of an aliphatic hydrocarbon is mixed with an aromatic polycarbonate resin has a substantial total light transmittance. There is a problem that it is less than 20% and inferior in transparency.

  The present invention has been made in view of such a background, and is a polycarbonate resin composition that is excellent in transparency and has a high balance of biogenic material content, heat resistance, and impact resistance, and molding thereof. Is intended to provide a body.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a polycarbonate resin composition containing a specific polycarbonate resin (A), an aromatic polycarbonate resin (B), and an epoxy compound (C) at a predetermined ratio. The present invention has been found to be excellent in transparency and has a high balance of biogenic material content, heat resistance, and impact resistance, leading to the present invention. That is, the gist of the present invention resides in the following [1] to [5].

[1] A polycarbonate resin (A) containing a structural unit derived from a compound represented by the following formula (1);
An aromatic polycarbonate resin (B);
An epoxy compound (C) represented by the following formula (2),
The polycarbonate whose content of this epoxy compound (C) is 0.5 weight part or more and 5 weight part or less with respect to a total of 100 weight part of the said polycarbonate resin (A) and the said aromatic polycarbonate resin (B). Resin composition.

（式（２）中、ｎは０〜３の整数を表す。）

(In formula (2), n represents an integer of 0 to 3)

[2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin composition measured by differential scanning calorimetry has a single glass transition temperature.

[3] The polycarbonate resin composition according to [1] or [2], wherein a 2 mm-thick molded product obtained by molding the polycarbonate resin composition has a total light transmittance of 80% or more.

[4] The polycarbonate resin composition according to any one of [1] to [3], wherein a glass transition temperature of the polycarbonate resin composition measured by differential scanning calorimetry is 90 ° C. or higher and 200 ° C. or lower.

[5] A molded product obtained by molding the polycarbonate resin composition according to any one of [1] to [4].

  The polycarbonate resin composition and molded product thereof of the present invention are excellent in transparency and have a high balance of biogenic material content, heat resistance, and impact resistance at a high level.

  DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.

[Polycarbonate resin (A)]
The polycarbonate resin (A) includes a structural unit derived from a dihydroxy compound represented by the following formula (1) (this is appropriately referred to as “structural unit (a)”). The polycarbonate resin (A) may be a homopolycarbonate resin of the structural unit (a) or a polycarbonate resin obtained by copolymerizing structural units other than the structural unit (a). From the viewpoint of superior impact resistance, a copolymer polycarbonate resin is preferred.

  Examples of the dihydroxy compound represented by the formula (1) include isosorbide (ISB), isomannide, and isoidet which are in a stereoisomeric relationship. These may be used individually by 1 type and may be used in combination of 2 or more type.

  Among the dihydroxy compounds represented by the formula (1), isosorbide (ISB) obtained by dehydrating condensation of sorbitol produced from various starches that are abundantly present as plant-derived resources, Most preferred from the standpoints of availability and production, weather resistance, optical properties, moldability, heat resistance and carbon neutral.

  In addition, the dihydroxy compound represented by the formula (1) is easily oxidized by oxygen. Therefore, during storage or handling during production, it is preferable to prevent moisture from entering in order to prevent decomposition by oxygen, and to use an oxygen scavenger or in a nitrogen atmosphere.

  The polycarbonate resin (A) includes a structural unit (a) derived from the dihydroxy compound represented by the formula (1), an aliphatic hydrocarbon dihydroxy compound, an alicyclic hydrocarbon dihydroxy compound, and an ether-containing dihydroxy. A copolymer polycarbonate resin containing a structural unit derived from one or more dihydroxy compounds selected from the group consisting of compounds (hereinafter referred to as “structural unit (b)” as appropriate) is preferred. Since these dihydroxy compounds have a flexible molecular structure, the toughness of the obtained polycarbonate resin can be improved by using these dihydroxy compounds as raw materials. Among these dihydroxy compounds, it is preferable to use an aliphatic hydrocarbon dihydroxy compound or an alicyclic hydrocarbon dihydroxy compound having a large effect of improving toughness, and most preferable to use an alicyclic hydrocarbon dihydroxy compound. . Specific examples of the aliphatic hydroxy dihydroxy compound, the alicyclic hydrocarbon dihydroxy compound, and the ether-containing dihydroxy compound are as follows.

  As the aliphatic hydrocarbon dihydroxy compound, for example, the following dihydroxy compounds can be employed. Ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-heptanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decane Linear aliphatic dihydroxy compounds such as diol and 1,12-dodecanediol; aliphatic dihydroxy compounds having a branched chain such as 1,3-butanediol, 1,2-butanediol, neopentyl glycol and hexylene glycol.

  Examples of the alicyclic hydrocarbon dihydroxy compound include the following dihydroxy compounds. 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, 2,6-decalin dimethanol, 1,5-decalindi Examples include dihydroxy compounds derived from terpene compounds such as methanol, 2,3-decalin dimethanol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 1,3-adamantane dimethanol and limonene. Dihydroxy compounds that are primary alcohols of alicyclic hydrocarbons; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,3-adamantanediol, hydrogenated bisphenol A, 2,2,4,4- Tetramethyl-1,3-cyclobutane Illustrated in ol, secondary alcohols or dihydroxy compound is a tertiary alcohol of the alicyclic hydrocarbon.

Examples of the ether-containing dihydroxy compound include oxyalkylene glycols and dihydroxy compounds containing an acetal ring.
Examples of oxyalkylene glycols that can be used include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and polypropylene glycol.

  As the dihydroxy compound containing an acetal ring, for example, spiro glycol represented by the following structural formula (3), dioxane glycol represented by the following structural formula (4), and the like can be employed.

  In the polycarbonate resin (A), the content ratio of the structural unit (a) with respect to 100 mol% of the structural units derived from all dihydroxy compounds is preferably more than 50 mol%, and is 55 mol% or more and 95 mol% or less. More preferably, it is more preferably 60 mol% or more and 90 mol% or less, and particularly preferably 65 mol% or more and 85 mol% or less. In these cases, the biogenic substance content can be further increased, and the heat resistance can be further improved. The content ratio of the structural unit (a) in the polycarbonate resin (A) may be 100 mol%. However, from the viewpoint of further increasing the molecular weight and improving the impact resistance, the structural unit in the polycarbonate resin is It is preferable that structural units other than (a) are copolymerized.

  Moreover, the said polycarbonate resin (A) may further contain structural units other than the said structural unit (a) and the said structural unit (b). As such a structural unit (other dihydroxy compound), for example, a dihydroxy compound containing an aromatic group can be employed. However, when the polycarbonate resin (A) contains a large number of structural units derived from a dihydroxy compound containing an aromatic group, a polycarbonate resin having a high molecular weight cannot be obtained for the reasons described above, and the impact resistance is improved. May decrease. Therefore, from the viewpoint of further improving the impact resistance, the content of the structural unit derived from the dihydroxy compound containing an aromatic group is 10 mol% with respect to 100 mol% of the structural unit derived from the entire dihydroxy compound. Or less, more preferably 5 mol% or less.

  As the dihydroxy compound containing an aromatic group, for example, the following dihydroxy compounds can be adopted, but dihydroxy compounds other than these can also be adopted. 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) 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) decane, bis (4-hydroxy-3-nitro Phenyl) methane, 3,3-bis (4-hydroxyphenyl) pentane, 1,3-bis (2- (4-hydroxyphenyl) -2-propyl) benzene, 1,3-bis (2- (4-hydroxy) Phenyl) -2-propyl) benzene, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) sulfone, 2,4 ′ -Dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy) Aromatic bisphenol compounds such as -3-methylphenyl) sulfide, bis (4-hydroxyphenyl) disulfide, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dichlorodiphenyl ether; Bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxyethoxy) benzene, 4,4′- Dihydroxy compounds having an ether group bonded to an aromatic group such as bis (2-hydroxyethoxy) biphenyl and bis (4- (2-hydroxyethoxy) phenyl) sulfone; 9,9-bis (4- (2-hydroxyethoxy) ) Phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene Len, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxypropoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) ) -3-Methylphenyl) fluorene, 9,9-bis (4- (2-hydroxypropoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl ) Fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-isobutylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert-butylphenyl) fluorene, 9 , 9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-bis (4- (2-hydroxy) Ethoxy) -3-phenylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3 -Dihydroxy compounds having a fluorene ring such as -tert-butyl-6-methylphenyl) fluorene and 9,9-bis (4- (3-hydroxy-2,2-dimethylpropoxy) phenyl) fluorene.

  The other dihydroxy compound can be appropriately selected according to the properties required for the polycarbonate resin. Moreover, the said other dihydroxy compound may use only 1 type, and may use multiple types together. By using the other dihydroxy compound together with the dihydroxy compound represented by the formula (1), it is possible to obtain effects such as improvement of flexibility and mechanical properties of the polycarbonate resin (A) and improvement of moldability. It is.

  The dihydroxy compound used as a raw material of the polycarbonate resin (A) may contain a stabilizer such as a reducing agent, an antioxidant, an oxygen scavenger, a light stabilizer, an antacid, a pH stabilizer or a heat stabilizer. . In particular, the dihydroxy compound represented by the formula (1) has a property of easily changing in an acidic state. Therefore, the use of a basic stabilizer in the synthesis process of the polycarbonate resin (A) can suppress the alteration of the dihydroxy compound represented by the formula (1), and thus the quality of the obtained polycarbonate resin composition. Can be further improved.

  As the basic stabilizer, for example, the following compounds can be employed. Hydroxides, carbonates, phosphates, phosphites, hypophosphites, borates and fatty acid salts of Group 1 or 2 metals in the Long Periodic Table (Nomenclature of Inorganic Chemistry IUPAC Recommendations 2005); Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium Hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, Basic ammonium compounds such as traphenylammonium 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-diethylamino Pyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2 Methoxy, imidazole, 2-mercaptoimidazole, 2-methylimidazole and the amine-based compounds such as amino quinoline, and di - (tert-butyl) hindered amine compounds such as amine and 2,2,6,6-tetramethyl piperidine.

  Although there is no restriction | limiting in particular in content of the said basic stabilizer in the said dihydroxy compound, Since the dihydroxy compound represented by the said Formula (1) is unstable in an acidic state, of the dihydroxy compound containing a basic stabilizer It is preferable to set the content of the basic stabilizer so that the pH of the aqueous solution is around 7.

  The content of the basic stabilizer with respect to the dihydroxy compound represented by the formula (1) is preferably 0.0001 to 1% by mass. In this case, the effect of preventing the alteration of the dihydroxy compound represented by the formula (1) is sufficiently obtained. From the viewpoint of further enhancing this effect, the content of the basic stabilizer is more preferably 0.001 to 0.1% by mass.

  As the carbonic acid diester used as a raw material for the polycarbonate resin [A], a compound represented by the following general formula (5) can be usually employed. These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (5), A ¹ and A ² are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A ¹ and A ² may be the same or different. As A ¹ and A ² , it is preferable to employ a substituted or unsubstituted aromatic hydrocarbon group, and it is more preferable to employ an unsubstituted aromatic hydrocarbon group.

  As the carbonic acid diester represented by the general formula (5), for example, substituted diphenyl carbonate such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate may be employed. it can. Among these carbonic acid diesters, it is preferable to use diphenyl carbonate or substituted diphenyl carbonate, and it is particularly preferable to use diphenyl carbonate. Carbonic acid diesters may contain impurities such as chloride ions, and impurities may inhibit the polycondensation reaction or deteriorate the color tone of the resulting polycarbonate resin. It is preferable to use one purified by the above.

  The polycarbonate resin (A) can be synthesized by polycondensing the above-described dihydroxy compound and carbonic acid diester by an ester exchange reaction. More specifically, it can be obtained by removing the monohydroxy compound and the like by-produced in the transesterification reaction from the system together with the polycondensation.

  The transesterification proceeds in the presence of a transesterification catalyst (hereinafter, the transesterification catalyst is referred to as “polymerization catalyst”). The type of the polymerization catalyst can have a great 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 can satisfy the transparency, color tone, heat resistance, weather resistance, and mechanical strength of the obtained polycarbonate resin (A). Examples of the polymerization catalyst include metal compounds of Group I or Group II (hereinafter simply referred to as “Group 1” and “Group 2”) in the long-period periodic table, as well as basic boron compounds and basic compounds. Basic compounds such as phosphorus compounds, basic ammonium compounds and amine compounds can be used, among which group 1 metal compounds and / or group 2 metal compounds are preferred.

As the group 1 metal compound, for example, the following compounds can be employed. Sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, Lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, sodium borohydride, boron phenyl Potassium, lithium borohydride, cesium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, phosphorus 2 lithium hydrogen, 2 cesium hydrogen phosphate, 2 sodium phenyl phosphate, 2 potassium phenyl phosphate, 2 lithium phenyl phosphate, 2 cesium phenyl phosphate, sodium, potassium, lithium, cesium alcoholate, phenolate, bisphenol A Disodium salt, dipotassium salt, dilithium salt and dicesium salt.
As the Group 1 metal compound, a lithium compound is preferable from the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin.

As the group 2 metal compound, for example, the following compounds can be employed. Calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, Magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and strontium stearate.
As the group 2 metal compound, a magnesium compound, a calcium compound or a barium compound is preferable. From the viewpoint of polymerization activity and the color tone of the obtained polycarbonate resin, a magnesium compound and / or a calcium compound is further preferable, and a calcium compound is most preferable.

  In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, and an amine compound can be used in combination with the above-mentioned Group 1 metal compound and / or Group 2 metal compound. However, it is particularly preferred to use only Group 1 metal compounds and / or Group 2 metal compounds.

  As said basic phosphorus compound, the following compounds are employable, for example. Triethylphosphine, tri-n-propylphosphine, triisopropylphosphine, tri-n-butylphosphine, triphenylphosphine, tributylphosphine, quaternary phosphonium salt and the like.

  As said basic ammonium compound, the following compounds are employable, for example. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide, triethylbenzylammonium Hydroxide, triethylphenylammonium hydroxide, tributylbenzylammonium hydroxide, tributylphenylammonium hydroxide, tetraphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide and butyltriphenylammonium hydroxide Rokishido like.

  As said amine compound, the following compounds are employable, for example. 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4-methoxypyridine, 2-dimethylaminoimidazole, 2-methoxy Imidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole, aminoquinoline, guanidine and the like.

  The amount of the polymerization catalyst used is preferably 0.1 to 300 μmol, more preferably 0.5 to 100 μmol, and particularly preferably 1 to 50 μmol per 1 mol of all dihydroxy compounds used in the reaction.

  When a compound containing at least one metal selected from the group consisting of Group 2 metals and lithium in the long-period periodic table is used as the polymerization catalyst, particularly when a magnesium compound and / or a calcium compound is used, the polymerization catalyst 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 all dihydroxy compounds used in the reaction, as the amount of metal atoms of the compound containing the metal. The upper limit is preferably 10 μmol or less, more preferably 5 μmol or less, and particularly preferably 3 μmol or less.

  Since the polymerization rate can be increased by adjusting the amount of the polymerization catalyst used within the above range, a polycarbonate resin having a desired molecular weight can be obtained without necessarily increasing the polymerization temperature. The deterioration of the color tone of A) can be suppressed. Moreover, since it can prevent that the unreacted raw material volatilizes in the middle of superposition | polymerization and the molar ratio of a dihydroxy compound and a carbonic acid diester collapse | crumbles, resin of a desired molecular weight can be obtained more reliably. Furthermore, since side reactions can be suppressed, deterioration of the color tone of the polycarbonate resin (A) or coloring during molding can be further prevented.

  Considering the adverse effect of sodium, potassium, or cesium on the color tone of the polycarbonate resin among the Group 1 metals and the adverse effect of iron on the color tone of the polycarbonate resin, sodium, potassium, cesium, and iron in the polycarbonate resin (A) The total content is preferably 1 mass ppm or less. In this case, the deterioration of the color tone of the polycarbonate resin can be further prevented, 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 mass ppm or less. In addition, these metals may mix not only from the catalyst to be used but also from a raw material or a reaction apparatus. Regardless of the source, the total amount of these metal compounds in the polycarbonate resin (A) is preferably in the above-mentioned range as the total content of sodium, potassium, cesium and iron.

(Synthesis of polycarbonate resin (A))
The polycarbonate resin (A) is obtained by polycondensing a dihydroxy compound used as a raw material such as the dihydroxy compound represented by the above formula (1) and a carbonic acid diester by an ester exchange reaction in the presence of a polymerization catalyst. can get.

  The raw material dihydroxy compound and carbonic acid diester are preferably mixed uniformly before the transesterification reaction. The mixing temperature is usually 80 ° C. or higher, preferably 90 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, with 100 ° C. or higher and 120 ° C. or lower being preferred. In this case, the dissolution rate can be increased or the solubility can be sufficiently improved, and problems such as solidification can be sufficiently avoided. Furthermore, in this case, the thermal degradation of the dihydroxy compound can be sufficiently suppressed, and the resulting polycarbonate resin (A) can be further improved in color tone and improved in weather resistance. Is also possible.

  The operation of mixing the raw material dihydroxy compound and the carbonic acid diester is performed in an atmosphere having an oxygen concentration of 10 vol% or less, further 0.0001 to 10 vol%, particularly 0.0001 to 5 vol%, and particularly 0.0001 to 1 vol%. It is preferable. In this case, the color tone can be improved and the reactivity can be increased.

  In order to obtain the polycarbonate resin (A), it is preferable to use a carbonic acid diester in a molar ratio of 0.90 to 1.20 with respect to all dihydroxy compounds used in the reaction. In this case, since the increase in the amount of terminal hydroxyl groups of the polycarbonate resin (A) can be suppressed, the thermal stability of the polymer can be improved. Therefore, coloring at the time of shaping | molding can be prevented further, or the speed | rate of transesterification can be improved. Moreover, it becomes possible to obtain a desired high molecular weight body more reliably. Furthermore, by adjusting the usage-amount of carbonic acid diester in the said range, the fall of the rate of transesterification can be suppressed, and more reliable manufacture of polycarbonate resin (A) of a desired molecular weight is attained. Further, in this case, since an increase in heat history during the reaction can be suppressed, the color tone and weather resistance of the polycarbonate resin (A) can be further improved. Furthermore, in this case, the amount of carbonic acid diester in the polycarbonate resin (A) can be reduced, and generation of dirt and odor during molding can be avoided or alleviated. From the same viewpoint as above, the amount of carbonic acid diester used relative to all dihydroxy compounds is more preferably 0.95 to 1.10.

  The method of polycondensing a dihydroxy compound and a carbonic acid diester is performed in multiple stages using a plurality of reactors in the presence of the above-mentioned catalyst. There are batch, continuous or batch / continuous methods of reaction, but it is possible to obtain a polycarbonate resin with less heat history and adopt a continuous method with excellent productivity. preferable.

  From the viewpoint of controlling 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 according to the reaction stage. Specifically, it is preferable to obtain a prepolymer at a relatively low temperature and low vacuum in the early stage of the polycondensation reaction and to increase the molecular weight to a predetermined value at a relatively high temperature and high vacuum in the latter stage of the reaction. In this case, distillation of unreacted monomers is suppressed, and the molar ratio of the dihydroxy compound and the carbonic acid diester can be easily adjusted to a desired ratio. As a result, a decrease in the polymerization rate can be suppressed. In addition, a polymer having a desired molecular weight and terminal group can be obtained more reliably.

  In addition, the polymerization rate in the polycondensation reaction is controlled by the balance between the hydroxy group terminal and the carbonate group terminal. Therefore, if the balance of the end groups varies due to the distillation of the unreacted monomer, it becomes difficult to control the polymerization rate to be constant, and the molecular weight of the resulting resin may vary greatly. Since the molecular weight of the resin correlates with the melt viscosity, when the resulting resin is melt processed, the melt viscosity varies, and it may be difficult to keep the quality of the molded product constant. Such a problem is likely to occur particularly when the polycondensation reaction is carried out continuously.

  In order to suppress the amount of unreacted monomer to be distilled off, it is effective to use a reflux condenser for the polymerization reactor, and shows a high effect particularly in the initial stage of the reaction with a large amount of unreacted monomer. The temperature of the refrigerant introduced into the reflux condenser can be appropriately selected according to the monomer used, but the temperature of the refrigerant introduced into the reflux condenser is usually 45 to 180 ° C. at the inlet of the reflux condenser. Yes, preferably 80 to 150 ° C, particularly preferably 100 to 130 ° C. By adjusting the refrigerant temperature within these ranges, the reflux amount can be sufficiently increased, the effect can be sufficiently obtained, and the distillation efficiency of the monohydroxy compound to be distilled off can be sufficiently improved. As a result, a decrease in the reaction rate can be prevented, and coloring of the resulting resin can be further prevented. As the refrigerant, hot water, steam, heat medium oil or the like is used, and steam or heat medium oil is preferable.

  In order to maintain the polymerization rate appropriately and suppress the distillation of the monomer while maintaining the color tone of the obtained polycarbonate resin (A), it is important to select the type and amount of the polymerization catalyst described above. .

  The polycarbonate resin (A) is usually produced through two or more steps using a polymerization catalyst. The polycondensation reaction may be carried out in two or more stages by using a single polycondensation reactor and changing the conditions sequentially. However, from the viewpoint of production efficiency, a plurality of reactors are used and the respective conditions are changed. It is preferable to carry out in multiple stages.

  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 at the initial stage of the reaction in which a large amount of the monomer is contained in the reaction solution. In the later stage of the reaction, it is important to shift the equilibrium toward the polycondensation reaction side by sufficiently distilling off the by-produced monohydroxy compound. Therefore, the reaction conditions suitable for the early stage of the reaction are usually different from those suitable for the later stage of the reaction. Therefore, by using a plurality of reactors arranged in series, the respective conditions can be easily changed, and the production efficiency can be improved.

  As described above, the polymerization reactor used for the production of the polycarbonate resin (A) may be at least two or more, but from the viewpoint of production efficiency, etc., three or more, preferably 3 to 5, particularly Preferably four. If there are two or more polymerization reactors, a plurality of reaction stages with different conditions may be further performed in each polymerization reactor, or the temperature and pressure may be continuously changed.

  The polymerization catalyst can be added to the raw material preparation tank or the raw material storage tank, or can be added directly to the polymerization reactor. From the viewpoint of supply stability and control of the polycondensation reaction, it is preferable to install a catalyst supply line in the middle of the raw material line before being supplied to the polymerization reactor and supply the polymerization catalyst in an aqueous solution.

  By adjusting the temperature of the polycondensation reaction, it is possible to improve productivity and avoid an increase in the thermal history of the product. Furthermore, it is possible to further prevent the volatilization of the monomer and the decomposition and coloring of the polycarbonate resin (A). Specifically, the following conditions can be adopted as reaction conditions in the first stage reaction. That is, the maximum internal temperature of the polymerization reactor is usually set in the range of 150 to 250 ° C, preferably 160 to 240 ° C, and more preferably 170 to 230 ° C. Moreover, the pressure (henceforth an absolute pressure) of a polymerization reactor is 1-110 kPa normally, Preferably it is 5-70 kPa, More preferably, it sets in the range of 7-30 kPa. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 3 hours. The first stage reaction is preferably carried out while distilling off the generated monohydroxy compound out of the reaction system.

  In the second and subsequent stages, the pressure in the reaction system is gradually reduced from the pressure in the first stage, and the monohydroxy compound that is subsequently generated is removed from the reaction system. It is preferable to make it 1 kPa or less. Moreover, the maximum temperature of the internal temperature of a polymerization reactor is normally set in the range of 200-260 degreeC, Preferably it is 210-250 degreeC. 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.

  From the viewpoint of further suppressing coloration and thermal deterioration of the polycarbonate resin (A) and obtaining a polycarbonate resin (A) with a better color tone, the maximum internal temperature of the polymerization reactor in all reaction stages is 210 to 210. It is preferable to set it as 240 degreeC. In addition, in order to suppress a decrease in polymerization rate in the second half of the reaction and minimize deterioration due to thermal history, use a horizontal reactor with excellent plug flow and interface renewability at the final stage of the polycondensation reaction. Is preferred.

  In continuous polymerization, in order to control the molecular weight of the finally obtained polycarbonate resin (A) to a certain level, it is preferable to adjust the polymerization rate as necessary. In that case, adjusting the pressure in the final stage polymerization reactor is a method with good operability.

  In addition, as described above, the polymerization rate varies depending on the ratio of the hydroxyl group terminal to the carbonate group terminal, so one end group is intentionally reduced to suppress the polymerization rate, and the pressure in the final stage polymerization reactor is reduced accordingly. By maintaining a high vacuum, it is possible to reduce residual low molecular components in the resin including the monohydroxy compound. However, in this case, if the number of ends on one side is too small, the end group balance is slightly changed and the reactivity is extremely lowered, and the molecular weight of the obtained polycarbonate resin (A) does not reach the desired molecular weight. There is a fear. In order to avoid such a problem, the polycarbonate resin (A) obtained in the final stage polymerization reactor preferably contains 10 mol / ton or more of both the hydroxyl group terminal and the carbonate group terminal. On the other hand, when both terminal groups are too many, the polymerization rate increases and the molecular weight becomes too high. Therefore, one terminal group is preferably 60 mol / ton or less.

  Thus, the residual amount of the monohydroxy compound in the resin can be reduced at the outlet of the polymerization reactor by adjusting the amount of terminal groups and the pressure in the final stage polymerization reactor to a preferable range. The residual amount of the monohydroxy compound in the resin at the outlet of the polymerization reactor is preferably 2000 ppm by mass or less, more preferably 1500 ppm by mass or less, and further preferably 1000 ppm by mass or less. In this way, by reducing the content of the monohydroxy compound at the outlet of the polymerization reactor, the monohydroxy compound and the like can be easily devolatilized in a later step.

  Although it is preferable that the residual amount of the monohydroxy compound is small, if it is attempted to reduce it to less than 100 ppm by mass, the operating conditions are such that the amount of one end group is extremely reduced and the pressure of the polymerization reactor is kept at a high vacuum. I need to take it. In this case, as described above, it is difficult to keep the molecular weight of the obtained polycarbonate resin (A) at a constant level, and therefore it is usually 100 ppm by mass or more, preferably 150 ppm by mass or more.

  The by-produced monohydroxy compound is preferably reused as a raw material for other compounds after purification as necessary from the viewpoint of effective utilization of resources. For example, when the monohydroxy compound is phenol, it can be used as a raw material for diphenyl carbonate, bisphenol A and the like.

  The glass transition temperature of the polycarbonate resin (A) is preferably 90 ° C. or higher. In this case, the heat resistance and biogenic substance content of the polycarbonate resin composition can be improved in a well-balanced manner. From the same viewpoint, the glass transition temperature of the polycarbonate resin (A) is more preferably 100 ° C. or higher, further preferably 110 ° C. or higher, and particularly preferably 120 ° C. or higher. On the other hand, the glass transition temperature of the polycarbonate resin (A) is preferably 170 ° C. or lower. In this case, the melt viscosity can be reduced by the aforementioned melt polymerization, and a polymer having a sufficient molecular weight can be obtained. Further, when the molecular weight is to be increased by increasing the polymerization temperature and decreasing the melt viscosity, the heat resistance of the component (a) is not sufficient, and thus there is a possibility that it may be easily colored. From the viewpoint of improving the molecular weight and preventing coloring, 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.

  The molecular weight of the polycarbonate resin (A) can be represented by a reduced viscosity, and the higher the reduced viscosity, the higher the molecular weight. The reduced viscosity is usually 0.30 dL / g or more, preferably 0.33 dL / g or more. In this case, the mechanical strength of the molded product 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, and still more preferably 0.80 dL / g or less. In these cases, fluidity at the time of molding can be improved, and productivity and moldability can be further improved. Note that the reduced viscosity of the polycarbonate resin (A) was determined by using a solution in which the concentration of the resin composition was precisely adjusted to 0.6 g / dL using methylene chloride as a solvent, and at a temperature of 20.0 ° C. ± 0. The value measured under the condition of 1 ° C. is used. Details of the method for measuring the reduced viscosity will be described in Examples.

The melt viscosity of the polycarbonate resin (A) is preferably 400 Pa · s or more and 3000 Pa · s or less. In this case, the molded article of the resin composition can be prevented from becoming brittle, and the mechanical properties can be further improved. Furthermore, in this case, the fluidity at the time of molding can be improved, and the appearance of the molded product can be prevented from being deteriorated or the dimensional accuracy can be prevented from being deteriorated. Furthermore, in this case, coloring and foaming caused by the increase in the resin temperature due to shearing heat generation can be further prevented. From the same viewpoint, the melt viscosity of the polycarbonate resin (A) is more preferably 600 Pa · s to 2500 Pa · s, and still more preferably 800 Pa · s to 2000 Pa · s. In the present specification, the melt viscosity means 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.]. Details of the method for measuring the melt viscosity will be described in Examples 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 the polymerization catalyst. For example, phosphoric acid, trimethyl phosphate, triethyl phosphate, phosphorous acid, tetrabutyl octyl sulfonate Phosphonium salts such as phosphonium salt, benzenesulfonic acid tetramethylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, P-toluenesulfonic acid tetrabutylphosphonium salt; decylsulfonic acid tetramethylammonium salt; Ammonium salts such as tetrabutylammonium dodecylbenzenesulfonate; and methyl benzenesulfonate, butyl benzenesulfonate, methyl p-toluenesulfonate, butyl p-toluenesulfonate, hexadecyl And the like alkyl esters such as sulfonic acid ethyl.

  The catalyst deactivator includes a phosphorus compound (hereinafter referred to as “specific phosphorus compound”) including any of the partial structures represented by the following structural formula (6) or the following structural formula (7). It is preferable. The specific phosphorus-based compound is added after the polycondensation reaction is completed, that is, for example, in the kneading step or the pelletizing step, to deactivate the polymerization catalyst described later, and the polycondensation reaction is unnecessary thereafter. It is possible to suppress progress. As a result, it is possible to suppress the progress of polycondensation when the polycarbonate resin (A) is heated in the molding step or the like, and thus to suppress the elimination of the monohydroxy compound. Moreover, coloring of the polycarbonate resin (A) under high temperature can be suppressed by deactivating the polymerization catalyst.

  Specific phosphorus compounds containing the partial structure represented by the structural formula (6) or structural formula (7) include phosphoric acid, phosphorous acid, phosphonic acid, hypophosphorous acid, polyphosphoric acid, phosphonic acid ester, acidic Phosphate esters and the like can be employed. Among the specific phosphorus compounds, phosphorous acid, phosphonic acid, and phosphonic acid ester are more excellent in catalyst deactivation and coloring suppression effects, and phosphorous acid is particularly preferable.

  As the phosphonic acid, for example, the following compounds can be employed. Phosphonic acid (phosphorous acid), methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, aminomethylphosphonic acid, methylenediphosphonic acid, 1-hydroxyethane-1,1-diphosphone Acids, 4-methoxyphenylphosphonic acid, nitrilotris (methylenephosphonic acid), propylphosphonic anhydride, and the like.

  As the phosphonic acid ester, for example, the following compounds can be employed. Dimethyl phosphonate, diethyl phosphonate, bis (2-ethylhexyl) phosphonate, dilauryl phosphonate, dioleyl phosphonate, diphenyl phosphonate, dibenzyl phosphonate, dimethyl methylphosphonate, diphenyl methylphosphonate, diethyl ethylphosphonate, diethyl benzylphosphonate Dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, diethyl (methoxymethyl) phosphonate, diethyl vinylphosphonate, diethyl hydroxymethylphosphonate, dimethyl (2-hydroxyethyl) phosphonate, p-methylbenzylphosphonic acid Diethyl, diethylphosphonoacetic acid, diethylphosphonoacetic acid ethyl, diethylphosphonoacetic acid tert-butyl, (4-chlorobenzyl) phosphonic acid die Le, diethyl cyanophosphonate, diethyl cyanomethylphosphonate, 3,5-di -tert- butyl-4-hydroxybenzyl phosphonic acid diethyl, diethyl phosphonoacetate diethyl acetal, (methylthiomethyl) diethyl phosphonic acid.

  As the acidic phosphate ester, for example, the following compounds can be employed. Dimethyl phosphate, diethyl phosphate, divinyl phosphate, dipropyl phosphate, dibutyl phosphate, bis (butoxyethyl) phosphate, bis (2-ethylhexyl) phosphate, diisotridecyl phosphate, dioleyl phosphate, distearyl phosphate, Phosphoric diesters such as diphenyl phosphate and dibenzyl phosphate, or a mixture of diester and monoester, diethyl chlorophosphate, zinc stearyl phosphate, and the like.

  The said specific phosphorus type compound may be used individually by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio.

  The content of the specific phosphorus compound in the polycarbonate resin (A) is preferably 0.1 mass ppm or more and 5 mass ppm or less as a phosphorus atom. In this case, the effects of catalyst deactivation and coloring suppression by the specific phosphorus compound can be sufficiently obtained. In this case, the polycarbonate resin (A) can be further prevented from being colored, particularly in an endurance test at high temperature and high humidity.

  Further, by adjusting the content of the specific phosphorus compound according to the amount of the polymerization catalyst, it is possible to more reliably obtain the effects of catalyst deactivation and coloring suppression. The content of the specific phosphorus compound is preferably 0.5 times mol or more and 5 times mol or less, and 0.7 times mol or more and 4 times mol as the amount of phosphorus atoms with respect to 1 mol of the metal atom of the polymerization catalyst. More preferably, it is more preferably 0.8 times mol or more and 3 times mol or less.

[Aromatic polycarbonate resin (B)]
As said aromatic polycarbonate resin (B), there exists a polycarbonate resin which uses the structural unit derived from the aromatic dihydroxy compound represented, for example by following General formula (8) as a main structural unit.

R ^{1 to} R ⁸ in the general formula (8) each independently represent a hydrogen atom or a substituent. Y represents a single bond or a divalent group. Examples of the substituent of R ¹ to R ⁸ in the general formula (8), an alkyl group having 1 to 10 carbon atoms which may have a substituent group, carbon atoms which may have a substituent 1 to 10 An alkoxy group, a halogen 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 these, the C1-C10 alkyl group which may have a substituent, or the C6-C20 aromatic group which may have a substituent is preferable. As a bivalent group of Y in General formula (8), the alkylene group of the C1-C6 chain structure which may have a substituent, and C1-C1 which may have a substituent. An alkylidene group having a chain structure of 6; an alkylene group having a cyclic structure having 3 to 6 carbon atoms which may have a substituent; and an alkylidene group having a cyclic structure having 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 effects of the present invention are not inhibited, but usually has a molecular weight of 200 or less. Moreover, as a substituent which the alkylene group of a C1-C6 chain structure has, an aryl group is preferable and especially a phenyl group is preferable.

  The aromatic polycarbonate resin (B) may be a homopolymer or a copolymer. When the aromatic polycarbonate resin (B) is a copolymer, the general formula (8) in all structural units derived from the dihydroxy compound. It is preferable that it is a polycarbonate resin with the most structural units derived from the dihydroxy compound represented by these. In aromatic polycarbonate resin (B), the content rate of the structural unit derived from the dihydroxy compound represented by the said General formula (8) with respect to 100 mol% of all the structural units derived from all the dihydroxy compounds is 50 mol% or more. Is more preferably 70 mol% or more, and particularly preferably 90 mol% or more.

  The aromatic polycarbonate resin (B) may have a branched structure, a linear structure, or a mixture of a branched structure and a linear structure. Furthermore, the aromatic polycarbonate resin (B) may contain a structural unit derived from a dihydroxy compound having a site represented by the formula (1). However, when it contains the structural unit derived from the dihydroxy compound which has a site | part represented by said Formula (1), the polycarbonate resin of a structural unit different from polycarbonate resin (A) is used.

The structural unit derived from the dihydroxy compound constituting the aromatic polycarbonate resin (B) is obtained by removing a hydrogen atom from the hydroxyl group of the dihydroxy compound. Specific examples of the corresponding dihydroxy compound include the following.
4,4′-biphenol, 2,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-dimethyl-2,4′-dihydroxy-1 , 1′-biphenyl, 3,3′-di- (t-butyl) -4,4′-dihydroxy-1,1′-biphenyl, 3,3 ′, 5,5′-tetramethyl-4,4 ′ -Dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra- (t-butyl) -4,4'-dihydroxy-1,1'-biphenyl, 2,2', 3,3 Biphenyl compounds such as', 5,5'-hexamethyl-4,4'-dihydroxy-1,1'-biphenyl.

  Bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1,1-bis- (4-hydroxy) Phenyl) ethane, 1,1-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxyphenyl) pentane, 2,2-bis- (4-hydroxyphenyl) -3-methylbutane, 2,2-bis -(4-hydroxyphenyl) hexane, 2,2-bis- (4-hydroxyphenyl) -4-methylpentane, 1,1-bis- (4-hydroxyphenyl) ) 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-bis- (4-hydroxy-3-methyl) Phenyl) ethane, 2,2-bis- (4-hydroxy-3-ethylphenyl) propane, 2,2-bis- (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis- (4-hydroxy) -3-sec-butylphenyl) propane, 1,1-bis- (4-hydroxy-3,5-dimethylphenyl) ethane, 2,2-bis- (4- Droxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxy-3,6-dimethylphenyl) ethane, bis- (4-hydroxy-2,3,5-trimethylphenyl) methane, , 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) dibenzylmethane, 4,4 ′-[1,4-phenylene Bis (1-methylethylidene)] bis- [phenol], 4,4 ′-[1,4-phenylenebismethylene] bis- [phenol], 4,4 ′-[1,4-phenylenebis (1-methyl) Ethylidene)] bis- [2,6-dimethylphenol], 4,4 ′-[1,4-phenylenebismethylene] bis- [2,6-dimethylphenol], 4,4 ′-[1,4-phenylene Bismethylene] 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′-tetramethyl-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone, 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) Tan, (2-hydroxy-5-methylphenyl) (4-hydroxy-3-methylphenyl) methane, 1,1- (2-hydroxyphenyl) (4-hydroxyphenyl) ethane, 2,2- (2-hydroxy) Bisphenol compounds such as phenyl) (4-hydroxyphenyl) propane and 1,1- (2-hydroxyphenyl) (4-hydroxyphenyl) propane.

Halogenated bisphenol compounds such as 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane.
Among these, preferable dihydroxy compounds include bis- (4-hydroxy-3,5-dimethylphenyl) methane, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, 1 , 1-bis- (4-hydroxyphenyl) ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis -(4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis- (4-hydroxyphenyl) cyclohexane, 1,1-bis- (4-hydroxy-3,3,5-trimethylphenyl) cyclohexane , Bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl Tan, 1,1-bis- (4-hydroxyphenyl) -1-phenylpropane, bis- (4-hydroxyphenyl) diphenylmethane, 2-hydroxyphenyl (4-hydroxyphenyl) methane, 2,2- (2-hydroxy Phenyl) (4-hydroxyphenyl) propane.

  Among these, in particular, bis- (4-hydroxyphenyl) methane, bis- (4-hydroxy-3-methylphenyl) methane, bis- (4-hydroxy-3,5-dimethylphenyl) methane, 2,2-bis -(4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxy-3-methylphenyl) propane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -Bis- (4-hydroxyphenyl) cyclohexane and 1,1-bis- (4-hydroxy-3,3,5-trimethylphenyl) cyclohexane are preferred.

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 may be used. As an example, a method for producing an aromatic polycarbonate resin (B) by a transesterification method will be described below.
The transesterification method is a production method in which a dihydroxy compound and a carbonic acid diester are added with a basic catalyst, and further an acidic substance that neutralizes the basic catalyst is added to perform melt transesterification polycondensation. Examples of the dihydroxy compound include the biphenyl compounds and bisphenol compounds exemplified above.

  Representative examples of carbonic acid diesters include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and the like. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.

  The viscosity average molecular weight of the aromatic polycarbonate resin (B) is usually in the range of 8,000 or more and 30,000 or less, preferably 10,000 or more and 25,000 or less, from the balance of mechanical properties and molding processability. . The reduced viscosity of the aromatic polycarbonate resin (B) was measured at a temperature of 20.0 ° C. ± 0.1 ° C., using methylene chloride as a solvent and adjusting the polycarbonate concentration to 0.60 g / dl. 0.23 dl / g or more and 0.72 dl / g or less, preferably 0.27 dl / g or more and 0.61 dl / g or less.

  In the present invention, the aromatic polycarbonate resin (B) may be used alone or in combination of two or more.

[Epoxy compound (C)]
The epoxy compound (C) used in the present invention is represented by the following formula (2).

（式中、ｎは０から３の整数を表す。）

(In the formula, n represents an integer of 0 to 3.)

  The first epoxy compound (C) can be obtained by reacting the dihydroxy compound having the formula (1) with epihalohydrin in the presence of an alkali by a conventional method. In particular, it is preferable to synthesize by the method described in JP 2014-189713 A.

  Content of the said epoxy compound (C) in a polycarbonate resin composition is 0.5 to 5 weight part with respect to a total of 100 weight part of polycarbonate resin (A) and aromatic polycarbonate resin (B). is there. When the amount is less than 0.5 part by weight, the transparency of the resin composition becomes insufficient. On the other hand, when the amount exceeds 5 parts by weight, the color becomes violent although it becomes transparent. Moreover, the molecular weight (melt viscosity) of the resin composition is lowered, and the impact resistance of the resin composition becomes insufficient. From the viewpoint of further improving transparency and impact resistance and further suppressing coloring, the content of the epoxy compound (C) is 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). On the other hand, it is preferably 1 part by weight to 3 parts by weight, and more preferably 1 part by weight to 2 parts by weight.

  Regarding the method for adding the epoxy compound (C), a solid material may be supplied as it is, or a material that is soluble in water or a solvent may 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 solution, it may be added from the raw material input port of the extruder, or may be added from the cylinder using a pump or the like.

[Polycarbonate resin composition]
The polycarbonate resin composition preferably has a total light transmittance of 80% or more in the thickness direction of a molded product having a thickness of 2 mm formed by molding the polycarbonate resin composition. In addition, from the viewpoint of good applicability to transparent use and good image clarity when deposited, the total light transmittance is more preferably 85% or more. Further, the haze of the molded body having a thickness of 2 mm is preferably 1% or less, more preferably 0.5% or less, and further preferably 0.3% or less. In addition, the measuring method of a total light transmittance is demonstrated in the below-mentioned Example. Haze can also be measured by the same method as the total light transmittance.

  The polycarbonate resin composition preferably has a single glass transition temperature peak measured by differential scanning calorimetry. Moreover, it is preferable that the glass transition temperature of the said polycarbonate resin composition measured by differential scanning calorimetry is 90 degreeC or more and 200 degrees C or less. In these cases, since the heat resistance can be further improved, the deformation of the molded product can be further prevented. Moreover, in this case, the thermal deterioration of the polycarbonate resin (A) during the production of the resin composition can be further suppressed, and the impact resistance can be further improved. Furthermore, the thermal deterioration of the resin composition during molding can be further suppressed. From the same viewpoint, the glass transition temperature of the polycarbonate resin composition is more preferably 110 ° C. or more and 180 ° C. or less, further preferably 115 ° C. or more and 150 ° C. or less, and further preferably 115 ° C. or more and 130 ° C. or less.

  The polycarbonate resin composition showing the predetermined total light transmittance and glass transition temperature includes a polycarbonate resin (A) containing a structural unit derived from the compound represented by the formula (1), and an aromatic polycarbonate resin (B). And the specific epoxy compound (C), and the content of the epoxy compound (C) can be adjusted to the predetermined range.

  The compounding ratio of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the polycarbonate resin composition can be arbitrarily selected according to desired physical properties. From the viewpoint of increasing the biogenic substance content, the weight ratio (A / B) of the polycarbonate resin (A) to the aromatic polycarbonate resin (B) is preferably 95/5 to 50/50, More preferably, it is 90 / 10-60 / 40. Thereby, heat resistance, impact resistance, and biogenic substance content can be improved in a more balanced manner.

[Other additives]
Various additives can be added to the polycarbonate resin composition. Examples of the additives include dyes and pigments, antioxidants, UV absorbers, light stabilizers, mold release agents, heat stabilizers, flame retardants, flame retardant aids, inorganic fillers, impact modifiers, hydrolysis inhibitors, There are a foaming agent, a nucleating agent, etc., and additives usually used for polycarbonate resins can be used.

"Dye and pigment"
Examples of the dye / pigment include organic pigments such as inorganic pigments, organic pigments, and organic dyes.
Specific examples of the inorganic pigment include carbon black; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, copper-iron black, and the like. And oxide-based pigments.
Specific examples of organic dyes such as organic pigments and organic dyes include phthalocyanine dyes and pigments; condensation of azo, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, quinophthalone, etc. Polycyclic dyes; anthraquinone, perinone, perylene, methine, quinoline, heterocyclic, methyl dyes, and the like.
These dyes may be used alone or in combination of two or more.

Among organic dyes such as the inorganic pigment, organic pigment and organic dye, inorganic pigments are preferable. By using an inorganic pigment as a colorant, it is possible to maintain a long period of time such as sharpness even if the molded product is used outdoors.
The amount of the dye / pigment is preferably 0.05 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). More preferred is 0.05 to 3 parts by weight, and even more preferred is 0.1 to 2 parts by weight. If the amount of the colorant is less than 0.05 parts by weight, it is difficult to obtain a molded article with sharpness. When the amount is more than 5 parts by weight, the surface roughness of the molded product increases, and it is difficult to obtain an original molded product with sharpness.

"Antioxidant"
As the antioxidant, general antioxidants used for resins can be used. From the viewpoint of oxidation stability and thermal stability, phosphite antioxidants, sulfur antioxidants, and phenol antioxidants are used. Agents are preferred. Here, the addition amount of the antioxidant is preferably 5 parts by weight or less with respect to 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). In this case, it is possible to more reliably prevent the mold from being contaminated during molding and obtain a molded product having a superior surface appearance. From the same viewpoint, the addition amount of the antioxidant is preferably 3 parts by weight or less, and more preferably 2 parts by weight or less, with respect to 100 parts by weight of the total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). Moreover, the addition amount of the antioxidant is preferably 0.001 part by weight or more with respect to 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). In this case, the effect of improving the molding stability can be sufficiently obtained. From the same viewpoint, the addition amount of the antioxidant is preferably 0.002 parts by weight or more, more preferably 0.005 parts by weight or more with respect to 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). Is more preferable.

(Phosphite antioxidant)
Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl Phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert- Butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol Diphosphite, bis (2,4-di -tert- butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and the like.
Among these, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is preferably used. These compounds can be used alone or in combination of two or more.

(Sulfur-based antioxidant)
Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, ditridecyl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, diester Stearyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), bis [2-methyl-4- (3 -Laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, 1,1′-thiobis (2-naphthol) and the like. . Of the above, pentaerythritol tetrakis (3-laurylthiopropionate) is preferred. These compounds can be used alone or in combination of two or more.

(Phenolic antioxidant)
Examples of the phenolic antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), glycerol-3-stearylthiopropionate, triethylene glycol-bis [ 3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1 , 3,5-trimethyl-2 4,6-tris (3,5-di-tert-bull-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4′-biphenylenediphosphinic acid tetrakis ( 2,4-di-tert-butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane, 2,6-di-tert-butyl-p-cresol, 2 Compounds such as 6-di -tert- butyl-4-ethyl phenol.
Among these compounds, an aromatic monohydroxy compound substituted with one or more alkyl groups having 5 or more carbon atoms is preferable. Specifically, octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate, pentaerythrityl-tetrakis {3- (3,5-di-t-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) benzene and the like, preferably pentaerythris Lithyl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is more preferred. These compounds can be used alone or in combination of two or more.

"UV absorber"
UV absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, benzoate compounds, hindered amine compounds, salicylic acid phenyl ester compounds, cyanoacrylate compounds, malonic acid ester compounds, oxalic acid anilide compounds, etc. Is mentioned. These may be used alone or in combination of two or more.

  More specific examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-methyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl- 5'-hexylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t -Octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-dodecylphenyl) benzotriazole, 2- (2'-hydroxy-3'-methyl-5'-t-dodecylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, methyl-3- (3- (2H-benzotriazol-2-yl ) -5-t-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of the triazine 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) -s-triazine, 2- (4,6-diphenyl-1,3, 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol (manufactured by BASF Japan, Tinuvin 1577FF) and the like.

Examples of hydroxybenzophenone compounds include 2,2′-dihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and the like.
Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2′-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
Examples of the malonic acid ester compounds include 2- (1-arylalkylidene) malonic acid esters. Of these, malonic acid [(4-methoxyphenyl) -methylene] -dimethyl ester (manufactured by Clariant, Hostavin PR-25) and dimethyl 2- (paramethoxybenzylidene) malonate are preferable.
Examples of the oxalic acid anilide compound include 2-ethyl-2′-ethoxy-oxalanilide (manufactured by Clariant, Sanduvor VSU).

  Among these, 2- (2′-hydroxy-3′-t-butyl-5′-hexylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- [ 4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,2 ′, 4,4′-tetrahydroxybenzophenone is preferred.

"Light stabilizer"
Examples of the light stabilizer include hindered amine light stabilizers, and the molecular weight is preferably 1000 or less. In this case, the weather resistance of the molded product can be further improved. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 900 or less. The molecular weight of the light stabilizer is preferably 300 or more. In this case, heat resistance can be further improved, and contamination of the mold during molding can be more reliably prevented. As a result, it is possible to obtain a molded product having a more excellent surface appearance. From the same viewpoint, the molecular weight of the light stabilizer is more preferably 400 or more. Furthermore, the light stabilizer is preferably a compound having a piperidine structure. The piperidine structure defined here may be a saturated 6-membered amine structure, and includes a structure in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent include an alkyl group having 4 or less carbon atoms, and a methyl group is particularly preferable. In particular, a compound having a plurality of piperidine structures is preferable, and a compound in which the plurality of piperidine structures are linked by an ester structure is preferable.

  Such light stabilizers include 4-piperidinol, 2,2,6,6-tetramethyl-4-benzoate, bis (2,2,6,6-tetramethyl-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethylpiperidine-4-carboxylic acid) 1,2,3,4-butanetetrayl, 2,2, A condensation product of 6,6-tetramethyl-pyridinol, tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidyl, and tridecyl alcohol Tridecyl-1,2,3,4-butanetetracarboxylate, bis (1,2,3,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) ) -4-Hydroxyphenyl] methyl] butyl malonate, decanedioic acid bis (2,2,26,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, 1,1-dimethylethyl hydroperoxide And octane reaction product, 1- [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-tert -Butyl-4--4-hydroxyphenyl) propionyloxy] ethyl] -2,2,6,6-tetramethylpiperidine, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2, 3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6 , 6-Teto Methyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], N, N′-bis (2,2,6,6-tetramethyl-4 -Piperidyl) -1,6-hexanediamine polymer and 2,4,6-trichloro-1,3,5-triazine, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Condensate of methyl-4-piperidinol with β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane-diethanol, N, N ′ -Bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3 , 5-Triazine condensate, dimethyl succinate-1- (2- Dorokishiechiru) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like.

  It is preferable that content of a light stabilizer is 0.001 weight part or more and 5 weight part or less with respect to a total of 100 mass parts of polycarbonate resin (A) and aromatic polycarbonate resin (B). In this case, coloring of the polycarbonate resin composition can be further prevented. As a result, for example, when a colorant is added, a jet black with depth and clarity can be obtained. In this case, the light resistance of the polycarbonate resin composition can be further improved, and excellent light resistance can be exhibited even when the polycarbonate resin composition is applied to, for example, automotive interior and exterior products. The content of the light stabilizer is more preferably 0.005 parts by weight or more and 3 parts by weight or less with respect to 100 parts by weight of the total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). More preferably, it is at least 1 part by weight. The aromatic polycarbonate resin (B) tends to be easily decomposed by the hindered amine light stabilizer. Therefore, when the amount of the aromatic polycarbonate resin (B) increases in the ratio of the polycarbonate resin (A) to the aromatic polycarbonate resin (B), it is preferable to set the addition amount of the light stabilizer conservatively.

"Release agent"
The polycarbonate resin composition contains 0.0001 part by weight or more and 2 parts by weight or less of a fatty acid ester of a polyhydric alcohol with respect to 100 parts by weight of the polycarbonate resin as a release agent for imparting release properties at the time of molding. May be. By adjusting the amount of the fatty acid ester of the polyhydric alcohol within this range, the effect of addition can be sufficiently obtained, and more reliably prevent the molded product from cracking due to defective mold release at the time of mold release in the molding process. Can do. Furthermore, in this case, it is possible to further suppress the cloudiness of the resin composition and the increase in deposits attached to the mold during the molding process. The content of the fatty acid ester of the polyhydric alcohol is more preferably 0.01 parts by weight or more and 1.5 parts by weight or less, and further 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 total ester of a polyhydric alcohol having 1 to 20 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Such partial esters or total esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol distearate. Pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, isopropyl palmitate, sorbitan monostearate and the like. Of these, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used.
Further, from the viewpoints of heat resistance and moisture resistance, all esters are more preferable as fatty acid esters of polyhydric alcohols.

  As the fatty acid, a higher fatty acid is preferable, and a saturated fatty acid having 10 to 30 carbon atoms is more preferable. Such fatty acids include myristic acid, lauric acid, palmitic acid, stearic acid, behenic acid and the like.

  In the fatty acid ester of polyhydric alcohol, the polyhydric alcohol is preferably ethylene glycol. In this case, when added to the resin, the releasability can be improved without impairing the transparency of the resin.

  The fatty acid ester of the polyhydric alcohol is preferably a fatty acid diester of a dihydric alcohol. In this case, when added to the resin, a decrease in the molecular weight of the resin composition in a moist heat environment can be suppressed.

  In this Embodiment, the addition time of the mold release agent mix | blended with a polycarbonate resin composition and the addition method are not specifically limited. As the addition time, for example, when a polycarbonate resin is produced by the transesterification method, at the end of the polymerization reaction; regardless of the polymerization method, the polycarbonate resin composition during the kneading of the polycarbonate resin composition and other compounding agents, etc. In a melted state; using an extruder or the like, blending and kneading with a solid polycarbonate resin composition such as pellets or powder. As a method of addition, a method of directly mixing or kneading a release agent into a polycarbonate resin composition; adding as a high concentration master batch prepared by using a release agent with a small amount of a polycarbonate resin composition or other resin, etc. You can also.

"Other resins"
Further, the polycarbonate resin composition is within a range that does not impair the effects of the present invention, for example, synthetic resins such as aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, amorphous polyolefin, ABS, AS, polylactic acid, poly It can also be used as a polymer alloy by kneading with one or more biodegradable resins such as butylene succinate.

"Inorganic and organic fillers"
The polycarbonate resin composition includes glass fiber, glass milled fiber, glass flake, glass bead, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc as long as the design can be maintained. , Calcium silicate such as mica and wollastonite, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, silicon nitride, silicon nitride fiber, brass fiber, stainless steel fiber, potassium titanate fiber , Inorganic fillers such as whiskers, and powdery organic fillers such as wood powder, bamboo powder, coconut starch, cork powder, pulp powder; baluns such as crosslinked polyester, polystyrene, styrene / acrylic copolymer, urea resin -Like, spherical organic fillers; carbon fiber, synthetic fiber, natural fiber It may be added to the fibrous organic filler.

[Production Method of Polycarbonate Resin Composition]
The polycarbonate resin composition performs an addition step of adding the predetermined amount of the specific epoxy compound (C) to the specific polycarbonate resin (A) and the aromatic polycarbonate resin (B), and then the polycarbonate resin (A ) And the aromatic polycarbonate resin (B). In the reaction step, the presence of the epoxy compound (C) promotes compatibilization of the polycarbonate resin (A) and the aromatic polycarbonate resin (B), and a highly compatible resin composition is obtained. In addition, as a polycarbonate resin (A), an aromatic polycarbonate resin (B), and an epoxy compound (C), the same thing as the above-mentioned can be used.

  The polycarbonate resin composition can be produced by mixing the above components at a predetermined ratio simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, extruder or the like. it can. Especially, what can be mixed in the state of pressure reduction at the time of melt mixing is more preferable.

  By performing the reaction step under reduced pressure and controlling the reduced pressure condition to the specific range, it may occur during the transesterification reaction between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the reaction step. By-products are easily removed. As a result, the transesterification reaction easily proceeds, and a resin composition having higher compatibility between the polycarbonate resin (A) and the aromatic polycarbonate resin (B) can be produced.

[Molded body]
The polycarbonate resin composition can be molded by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. The molded body obtained by molding is excellent in transparency and has a high balance of biogenic material content, heat resistance, and impact resistance at a high level. Further, in the molded product, it is possible to improve color tone, weather resistance, optical properties, mechanical strength, etc., and to reduce residual low molecular components and foreign matters. Therefore, the molded body is suitable for interior parts for vehicles.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded.

[Evaluation method]
In the following, the physical properties or characteristics of the polycarbonate resin (A), aromatic polycarbonate resin (B), and polycarbonate resin composition were evaluated by the following methods.

(1) Measurement of reduced viscosity A sample of polycarbonate resin (A) or aromatic polycarbonate resin (B) was dissolved in methylene chloride to prepare a polycarbonate resin solution having a concentration of 0.6 g / dL. Using a Ubbelohde type viscosity tube manufactured by Moriyu Rika Kogyo Co., Ltd., the solvent passage time t ₀ and the solution passage time t were measured under the conditions of a temperature of 20.0 ° C. ± 0.1 ° C., and based on the following formula (i) Relative viscosity η _rel was calculated. Next, the specific viscosity η _sp was determined from the relative viscosity η _rel based on the following formula (ii).
η _rel = t / t ₀ (i)
η _sp = η _rel −1 (ii)
The reduced viscosity (η _sp / c) was determined by dividing the obtained specific viscosity η _sp by the concentration c (g / dL) of the solution. The higher the reduced viscosity value, the higher the molecular weight.

(2) Measurement of melt viscosity The melt viscosity of the aromatic polycarbonate resin (B)) was measured using a capillary rheometer “Capillograph 1B” manufactured by Toyo Seiki Seisakusho Co., Ltd., with a die diameter of 1 mm, a length of 10 mm, an inflow angle of 90 ° C. It is a viscosity measured at a shear rate of 12.16 to 6080 sec ⁻¹ at a measurement temperature of 240 ° C. for 2 minutes and a shear rate (SR) of 91.2 sec ⁻¹ . In the measurement of melt viscosity, the aromatic polycarbonate resin used for the measurement is previously dried at 90 ° C. for 4 hours or more.

(3) Measurement of glass transition temperature (Tg) The Tg of the polycarbonate resin composition is a differential scanning calorimeter “DSC7” manufactured by Perkin Elmer, Inc., and heated at a heating rate of 20 ° C./25° C. to 25 ° C. under a nitrogen gas atmosphere The temperature was raised at 200 ° C. for 3 minutes, lowered to 25 ° C. at a cooling rate of 20 ° C./minute, held at 25 ° C. for 3 minutes, and then again raised to 200 ° C. at a heating rate of 5 ° C./minute. It is the value of T _mg determined based on the method of JIS-K7121 (1987) from the obtained DSC curve when warmed. Moreover, the singleness of the glass transition temperature was evaluated. Specifically, when the DSC curve has a single peak, the unity is evaluated as “◯”, and when the DSC curve has a plurality of peaks, the unity is evaluated as “x”. In addition, the number of peaks was examined.

(4) Measurement of total light transmittance The pellets of the polycarbonate resin composition were dried at 90 ° C for 4 hours or more using a hot air dryer. Next, the dried pellets are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate (Width 100 mm × length 100 mm × thickness 2 mm) was obtained. Based on JIS K7136 (2000), the total light transmittance of the injection-molded plate was measured with a D65 light source using a Nippon Denshoku Industries Co., Ltd. haze meter “NDH2000”. In addition, when the total light transmittance is 80% or more and it is clear that the injection-molded plate is opaque, the evaluation result is “opaque” instead of showing the measured value of the total light transmittance. It was.
(5) Heat resistance test The pellets of the polycarbonate resin composition were dried at 90 ° C for 4 hours or more using a hot air dryer. Next, the dried pellets are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.), and molding is performed under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds. (2009) The multipurpose test piece A type described was obtained. A test piece having a length of 80 mm, a width of 10 mm, and a thickness of 4 mm is cut from the obtained multipurpose test piece, and in accordance with JIS-K7191-2 (2007), method A (bending stress applied to the test piece is 1.80 MPa) The deflection temperature under load was measured. In addition, in this test, although 90 degreeC or more is set as a pass, More preferably, 95 degreeC or more is good, More preferably, 100 degreeC or more is good.

(6) High-rate test The pellet of the polycarbonate resin composition was dried at 90 ° C. for 4 hours or more using a hot air dryer. Next, the dried pellets are supplied to an injection molding machine (J75EII type manufactured by Nippon Steel Co., Ltd.) and molded under the conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds, whereby an injection molded plate (Width 100 mm × length 100 mm × thickness 2 mm) was obtained. The obtained injection-molded plate is “Shimadzu Hydroshot HITS-P10” manufactured by Shimadzu Corporation, and has a temperature of 23 ° C. or −20 ° C., striker diameter of 5/8 inch, support base diameter of 40 mm, test speed. A high rate test was conducted under the condition of 4 m / s. The ductile fracture rate was determined by dividing the number of ductile fractures by the evaluation score and multiplying by 100 among the samples evaluated at 5 points. In this test, those showing a numerical value of 50% or more were accepted.

(7) Measurement of biogenic substance content Radiation carbon 14 (C ¹⁴ ) is generated at a constant rate by cosmic rays in the atmosphere and lost at a constant rate (half-life: 5370 years). There is a certain amount. Although plants absorb carbon dioxide in the atmosphere for a certain amount containing the C ^14, so will disappear carbon dioxide assimilation and does not occur at a constant speed by a felling like, radiocarbon Using this property A dating method has been created. Since fossil fuel has not been affected by cosmic rays for a long time, all C ¹⁴ has disappeared. On the other hand, since bio-derived chemicals have only a short time since the supply of C ¹⁴ ceased, it can be said that the content of C ¹⁴ is a substantially constant value.

The calculation method of biogenic substance content is demonstrated concretely using the said method. First, the ISB-PC ISB carbonate constituent unit is composed of 6 bio-derived ISB carbons and 1 carbon derived from fossil fuel DPC. Of carbon: 6 / total number of carbons: 7 = 85.7%. Here, the influence of the terminal was ignored because the polymer chain was sufficiently long. Further, in the case of a copolymerized polycarbonate resin as in Production Example 1 described later, since CHDM is a fossil fuel-derived raw material, the content of biologically derived substances in CHDM-PC is the number of bio-derived carbon atoms: 0 / total Carbon number: 9 = 0%. In the case of ISB / CHDM = 70/30 mol% in Production Example 1, since only the ISB-PC component is bio-derived, the biogenic substance content is 85.7% × 70 mol% = 60%.
Next, as in the example, the content of the biogenic substance in the case of the blend of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) is that the aromatic polycarbonate resin (B) is manufactured from a fossil fuel-derived raw material. Since it is a polymer, its biogenic content is 0%. Since the examples are blended in a weight ratio, the molar mass (unit: g / mol) of each polycarbonate resin is calculated, the weight is divided by the molar mass, and the molar fraction is converted accordingly. From this, the biogenic substance content of the blend is calculated from the product of the above-mentioned polycarbonate resin (A) biogenic substance content and its mole fraction. In addition, regarding calculation of a biological origin origin substance, it calculates only with a resin component and does not consider about components, such as an epoxy compound (C), a heat stabilizer, and a mold release agent. In this test, those that showed a numerical value of 20% or more were accepted.
(8) Measurement of epoxy equivalent The epoxy equivalent of the epoxy compound (C) was determined according to the method of JIS-K7236 (2001) using a potentiometric automatic titrator AT-610 manufactured by Kyoto Electronics Industry Co., Ltd.

[Raw materials]
The abbreviations and manufacturers of the compounds used in the following Examples and Comparative Examples are as follows.

<Dihydroxy compound>
・ ISB: Isosorbide (Rocket Fleure)
CHDM: 1,4-cyclohexanedimethanol [manufactured by SK Chemical]
<Carbonated diester>
・ DPC: Diphenyl carbonate [Mitsubishi Chemical Corporation]

<Thermal stabilizer (antioxidant)>
Irganox 1010: pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] [manufactured by BASF]
AS2112: Tris (2,4-di-tert-butylphenyl) phosphite [manufactured by ADEKA Corporation] (molecular weight 646.9)
<Release agent>
E-275: ethylene glycol distearate [manufactured by NOF Corporation]

[Production Example 1: Polycarbonate resin (A)]
Polycarbonate resin was polymerized using a continuous polymerization facility comprising three vertical stirring reactors, one horizontal stirring reactor, and a twin screw extruder. Specifically, first, ISB, CHDM, and DPC were respectively melted in the tank of the reactor, and ISB was 35.2 kg / hr, CHDM was 14.9 kg / hr, and DPC was 74.5 kg / hr (molar ratio). At a flow rate of ISB / CHDM / DPC = 0.700 / 0.300 / 1.010) was continuously fed 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 with respect to 1 mol of all dihydroxy compounds. The reaction temperature, internal pressure and residence time of each reactor are as follows: first vertical stirring reactor: 190 ° C., 25 kPa, 90 minutes, second vertical stirring reactor: 195 ° C., 10 kPa, 45 minutes, third vertical type Stirring reactor: 210 ° C., 3 kPa, 45 minutes, fourth horizontal stirring reactor: 225 ° C., 0.5 kPa, 90 minutes. The operation was performed while finely adjusting the internal pressure of the fourth horizontal stirring reactor so that the reduced viscosity of the obtained polycarbonate resin was 0.41 dL / g to 0.43 dL / g.

  The polycarbonate resin was withdrawn from the fourth horizontal stirring reactor at an amount of 60 kg / hr, and then the bent twin-screw extruder [TEX30α manufactured by Nippon Steel Works, L / D: 42.0, while the resin was in a molten state] L (mm): screw length, D (mm): screw diameter]. The polycarbonate resin that passed through the extruder was passed through a candle type filter (manufactured by SUS316) having an aperture of 10 μm while being in a molten state, and foreign matters were filtered. Thereafter, the polycarbonate resin was discharged from the die in a strand shape, water-cooled and solidified, and then pelletized with a rotary cutter to obtain pellets of a copolymer polycarbonate resin having an ISB / CHDM molar ratio of 70/30 mol%.

  The extruder has three vacuum vents, where residual low molecular components in the resin were removed by devolatilization. Before the 2nd vent, 2000 mass ppm water was added with respect to resin, and water injection devolatilization was performed. Prior to the third vent, 0.1 part by mass, 0.05 part by mass, and 0.3 part by mass of Irganox 1010, AS2112, and E-275 were added to 100 parts by mass of the polycarbonate resin, respectively. Thus, an ISB / CHDM copolymer polycarbonate resin was obtained. The polycarbonate resin (A) obtained in Production Example 1 is referred to as “PC-A1”.

[Production Example 2: Polycarbonate resin (A)]
In a polymerization reactor equipped with a reflux condenser controlled at a temperature of 100 ° C. and a stirring blade, ISB, CHDM, and DPC purified by distillation to a chloride ion concentration of 10 ppb or less in a molar ratio of ISB / CHDM / DPC = 0.27 / 0.73 / 1.00 was charged, and further calcium acetate monohydrate was added so that the addition amount of calcium acetate monohydrate as a catalyst with respect to 1 mol of all dihydroxy compounds was 1.5 μmol. After the aqueous solution of the Japanese product was charged, nitrogen substitution was sufficiently performed. Subsequently, heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C., and the contents were melted and made uniform while controlling the internal temperature to be 100 ° C. Thereafter, the temperature increase was started, the internal temperature was adjusted to 210 ° C. over 40 minutes, and when the internal temperature reached 210 ° C., control was performed so as to maintain this temperature, and at the same time, the pressure reduction was started to 210 ° C. The internal pressure was adjusted to 13.3 kPa (absolute pressure, the same applies hereinafter) over 90 minutes after the arrival, and the pressure was maintained for another 30 minutes. The phenol vapor produced as a by-product with the polymerization reaction is led to the reflux condenser using the steam whose inlet temperature to the reflux condenser is controlled at 100 ° C. as a refrigerant, and the monomer component contained in the phenol vapor in a slight amount is introduced into the polymerization reactor. Then, the phenol vapor that did not condense was recovered by guiding it to a condenser using 45 ° C. warm water as a refrigerant. The contents thus oligomerized are once restored to atmospheric pressure and then transferred to another polymerization reaction apparatus equipped with a stirring blade and a reflux condenser controlled in the same manner as described above. The internal temperature was adjusted to 210 ° C. and the pressure to 200 Pa over 60 minutes. Thereafter, the internal temperature is adjusted to 220 ° C. and the pressure to 133 Pa or less over 20 minutes, the pressure is restored when the predetermined stirring power is reached, and the molten polycarbonate resin extruded from the outlet of the polymerization reactor is pelletized by a pelletizer. As a result, a pellet was obtained. The reduced viscosity was 0.63 dl / g.
Thus, a polycarbonate resin having an ISB / CHDM molar ratio of 27/73 mol% was obtained. The polycarbonate resin (A) obtained in Production Example 2 is referred to as “PC-A2”.

[Aromatic polycarbonate resin (B)]
Novalex 7022J manufactured by Mitsubishi Engineering Plastics (aromatic polycarbonate resin with 100 mol% bisphenol A constituent unit, melt viscosity (240 ° C., shear rate 91.2 sec ⁻¹ ) 3260 Pa · s)

[Production Example 3: Epoxy compound (C)]
In a 1 L volume flask equipped with a thermometer, a dropping funnel, and a separator, 100 parts by weight of ISB and 1 part by weight of benzyltriethylammonium chloride as a glycidylation catalyst were dissolved in 380 parts by weight of epichlorohydrin. Note that 380 parts by weight of epichlorohydrin per 100 parts by weight of ISB corresponds to 3 equivalents of epichlorohydrin per hydroxyl group of ISB. Subsequently, the pressure in the reaction system was reduced to 20 kPa and heated until epichlorohydrin was refluxed. Thereafter, while maintaining reflux of epichlorohydrin, 137 parts by weight of a 48% by weight aqueous sodium hydroxide solution was added dropwise to 100 parts by weight of ISB. In addition, 137 parts by weight of sodium hydroxide aqueous solution (concentration: 48% by weight) with respect to 100 parts by weight of ISB corresponds to 1.2 equivalents of sodium hydroxide per one hydroxyl group of ISB. The epoxy compound (C) is generated by dropping the aqueous sodium hydroxide solution. During the reaction, only epichlorohydrin was returned from the separator into the flask, taking care not to allow water to enter the flask. And after completion | finish of reaction, the inside of a flask was cooled to room temperature, methyl ethyl ketone 125 weight part and water 250 weight part were added, and it stirred for 1 hour. Then, the flask was left still and the aqueous phase was removed. Subsequently, the organic phase was heated under reduced pressure to remove unreacted epichlorohydrin and methyl ethyl ketone, followed by filtration. This obtained 139 weight part of epoxy compounds (C). The epoxy equivalent of this epoxy compound (C) was 154.

[Example 1]
In this example, the above-mentioned PC-A1 is used as the polycarbonate resin (A), Novarex 7022J is used as the aromatic polycarbonate resin (B), and the epoxy compound (C) obtained in Production Example 3 is used as the polycarbonate resin composition. A product was made. Specifically, 70 parts by weight of a polycarbonate resin, 30 parts by weight of an aromatic polycarbonate resin and 1 part by weight of an epoxy compound (C) are mixed into a biaxial kneader (manufactured by Nippon Steel Works, TEX-30α (L /D=52.5, L (mm): screw length, D (mm): screw diameter)) to melt the polycarbonate resin (A) and the aromatic polycarbonate resin (B). Reaction was performed. The ratio of the total length L _t of the kneading zone to the diameter D (mm) of the kneading machine screw is 6 (L _t / D = 6), and the kneading conditions are: flow rate: 20 kg / h, screw rotation speed: 200 rpm, Cylinder temperature: 230 ° C. The extruder has two vacuum vent ports, and the vent vacuum degree was 11 kPa. After the melt reaction by kneading, the resin composition was extruded into a strand shape, cut into a pellet shape through a water cooling process, and a pellet of a polycarbonate resin composition was obtained.

  Next, the obtained pellets were dried with a hot air drier at a temperature of 100 ° C. for 5 hours, and then the pellets were injection molded using a 75-ton injection molding machine (EC-75 manufactured by Toshiba Machine Co., Ltd.). Molding conditions are a mold temperature: 60 ° C. and a cylinder temperature: 240 ° C. Thus, the test piece which consists of a plate-shaped molded object of width 100mm x length 100mm x thickness 2mm was obtained. Moreover, the ISO tensile test piece was obtained by shape | molding similarly. The above evaluation was performed using these test pieces, and the results are shown in Table 1.

[Example 2]
Except having changed the addition amount of the epoxy compound (C) into 2.5 weight part, it carried out similarly to Example 1, and produced the polycarbonate resin composition, and produced the molded object (test piece) using this. The evaluation results of this example are shown in Table 1.

[Comparative Example 1]
A polycarbonate resin composition was prepared in the same manner as in Example 1 except that the addition amount of the epoxy compound (C) was changed to 0 part by weight, and a molded body (test piece) was prepared using the polycarbonate resin composition. The evaluation results of this example are shown in Table 1.

[Comparative Example 2]
A polycarbonate resin composition was prepared in the same manner as in Example 1 except that the addition amount of the epoxy compound (C) was changed to 0.3 parts by weight, and a molded body (test piece) was prepared using the polycarbonate resin composition. The evaluation results of this example are shown in Table 1.

[Comparative Example 3]
A polycarbonate resin composition was prepared in the same manner as in Example 1 except that the addition amount of the epoxy compound (C) was changed to 7 parts by weight, and a molded body (test piece) was prepared using this. The evaluation results of this example are shown in Table 1.

[Comparative Example 4]
Polycarbonate was obtained in the same manner as in Example 1 except that PC-A1 (see Production Example 1) was changed to PC-A2 (see Production Example 2) and the addition amount of the epoxy compound (C) was changed to 0 parts by weight. A resin composition was prepared, and a molded body (test piece) was prepared using the resin composition. The evaluation results of this example are shown in Table 1.

  As is known from Table 1, the polycarbonate resin composition of the examples includes a polycarbonate resin (A) containing a structural unit derived from the compound represented by the above formula (1), an aromatic polycarbonate resin (B), and The epoxy compound (C) having the specific structure described above, and the content of the epoxy compound (C) is 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B), 0.5 parts by weight or more and 5 parts by weight or less are included. Such a polycarbonate resin composition had a total light transmittance of 80% or more of a molded product having a thickness of 2 mm, and had a single glass transition temperature measured by differential scanning calorimetry. Such a polycarbonate resin composition and a molded product obtained using the resin composition are excellent in transparency and have a high balance of biogenic material content, heat resistance and impact resistance. It was.

Claims (5)

A polycarbonate resin (A) containing a structural unit derived from a compound represented by the following formula (1);
An aromatic polycarbonate resin (B);
An epoxy compound (C) represented by the following formula (2),
The content of the epoxy compound (C) is 0.5 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight in total of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). A polycarbonate resin composition.

(In formula (2), n represents an integer of 0 to 3)   The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition has a single glass transition temperature measured by differential scanning calorimetry.   3. The polycarbonate resin composition according to claim 1, wherein the molded product having a thickness of 2 mm formed by molding the polycarbonate resin composition has a total light transmittance of 80% or more.   The polycarbonate resin composition according to any one of claims 1 to 3, wherein a glass transition temperature of the polycarbonate resin composition measured by differential scanning calorimetry is 90 ° C or higher and 200 ° C or lower.   The molded object obtained by shape | molding the polycarbonate resin composition of any one of Claims 1-4.