JP2018165341A - Polycarbonate resin composition, method for producing the same, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition that has high levels of transparency, color tone, impact resistance, and heat resistance in a balanced manner, a method for producing the same, and a molding of a polycarbonate resin composition.SOLUTION: A polycarbonate resin composition contains a polycarbonate resin (A) having a constitutional unit derived from a compound represented by the following formula (1), an aromatic polycarbonate resin (B), an impact strength modifier (C), and an acidic compound (D).SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition having a balance of transparency, color tone, impact resistance, and heat resistance, a method for producing the same, and a molded article obtained 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 environmental viewpoint.

  As a technique for improving impact resistance, it is known that impact resistance is improved by adding a core-shell type elastomer to a polycarbonate resin (for example, Patent Document 8).

  Patent Document 9 discloses that a polycarbonate resin containing an ISB-derived structural unit and an aromatic polycarbonate resin are kneaded in the presence of a catalyst, so that transparency, heat resistance, moist heat resistance, and impact resistance are at a high level. A method of obtaining a polycarbonate resin composition having a good balance is disclosed.

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. 2012/008344 Pamphlet International Publication No. 2017/002886 Pamphlet

  The polycarbonate resin composition disclosed in Patent Document 8 has improved impact resistance. However, in terms of transparency, color tone, and heat resistance, further improvement in balance has been required for practical use.

  Further, the polycarbonate resin composition disclosed in Patent Document 9 has improved impact resistance by the high-speed surface impact test, but the impact resistance when the impact energy is concentrated on the notch portion as in the notched impact strength test is There is room for improvement. For example, when there is a defect in a molded product when used in an automotive application, strong impact energy may be concentrated on the defect and the molded product may be damaged.

  The present invention has been made in view of such a background, and is a polycarbonate resin composition having a high balance of transparency, color tone, impact resistance, and heat resistance, a method for producing the same, and a polycarbonate resin composition. An object is to provide a molded body.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a specific polycarbonate resin (A), an aromatic polycarbonate resin (B), an impact strength modifier (C), and an acidic compound (D). It has been found that a polycarbonate resin composition containing a combination of transparency, color tone, and impact resistance at a high level in a well-balanced manner, leading to the present invention. That is, the gist of the present invention resides in the following [1] to [14].

[1] A polycarbonate resin (A) having a structural unit derived from a compound represented by the following formula (1) with respect to 100 mol% of a structural unit derived from all diols;
An aromatic polycarbonate resin (B);
Impact strength modifier (C);
A polycarbonate resin composition containing an acidic compound (D).

[2] The polycarbonate resin composition further contains at least one compound (E) selected from a compound of a long-period periodic table group I metal and a long-period periodic table group II metal compound. The polycarbonate resin composition according to [1].

[3] The content of the compound (E) is 100 parts by weight with respect to the total amount of the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the impact strength modifier (C). The polycarbonate resin composition according to [1] or [2], wherein the amount of metal in the compound (E) is 0.8 ppm by weight or more and 1000 ppm by weight or less.

[4] The compound (E) is at least one selected from the group consisting of inorganic salts (including carbonates), carboxylates, phenolates, halogen compounds, and hydroxide compounds, [2] or [3 ] The polycarbonate resin composition of description.

[5] The polycarbonate resin according to any one of [2] to [4], wherein the compound (E) is at least one selected from the group consisting of a lithium compound, a sodium compound, a potassium compound, and a cesium compound. Composition.

[6] The polycarbonate resin composition according to [5], wherein the content of the acidic compound (D) is 0.5 to 5 times the mol of the metal in the compound (E). object.

[7] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [6].

[8] For a composition comprising a polycarbonate resin (A) containing a structural unit derived from a compound represented by the following formula (1) and an aromatic polycarbonate resin (B), a long-period periodic table group I A pre-step (i) of melt-kneading at least one compound (D) selected from a metal compound of the above, a compound of a metal of Group II of the long-period periodic table; and
The manufacturing method of a polycarbonate resin composition which has the post-process (ii) which melt-kneads the resin composition obtained by this process, an impact strength modifier (C), and an acidic compound (D) after this process.

[9] The method for producing a polycarbonate resin composition according to [8], wherein the step (i) is performed under reduced pressure.

[10] The step (i) is performed under the condition of a degree of vacuum of 30 kPa or less. [8] or [9]
The manufacturing method of the polycarbonate resin composition as described in any one of.

[11] The compound (E) is at least one selected from the group consisting of inorganic salts (including carbonates), carboxylates, phenolates, halogen compounds, and hydroxide compounds. [8] to [10] The manufacturing method of the polycarbonate resin composition as described in any one of these.

[12] The polycarbonate resin according to any one of [8] to [11], wherein the compound (E) is at least one selected from the group consisting of a lithium compound, a sodium compound, a potassium compound, and a cesium compound. A method for producing the composition.

[13] Any of [8] to [12], wherein the addition amount of the acidic compound (D) is 0.5 to 5 times the amount of the metal addition of the compound (E). The manufacturing method of the polycarbonate resin composition as described in any one.

  The polycarbonate resin composition and molded product thereof of the present invention have transparency, color tone, impact resistance, and heat resistance at a high level in a well-balanced manner. The polycarbonate resin composition of this invention is obtained by performing an addition process and a reaction process as mentioned above.

  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) is a polycarbonate resin having 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-pentanediol, 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 (2), dioxane glycol represented by the following structural formula (3), 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 40 mol% or more, and more preferably 45 mol% or more. Preferably, it is 50 mol% or more and 95 mol% or less, more preferably 55 mol% or more and 90 mol% or less, and most preferably 60 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. In addition, the content ratio of the structural unit (a) in the polycarbonate resin (A) may be 100 mol%, but from the viewpoint of further increasing the molecular weight and improving the impact resistance, the content other than the structural unit (a). The structural unit is preferably 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; 2,2-bis (4- (2-hydroxyethoxy) phenyl) propane, 2,2-bis (4- (2-hydroxypropoxy) phenyl) propane, 1,3-bis (2-hydroxyethoxy) benzene, 4,4′-bis Dihydroxy compounds having an ether group bonded to an aromatic group such as (2-hydroxyethoxy) biphenyl and bis (4- (2-hydroxyethoxy) phenyl) sulfone; 9,9-bis (4- (2-hydroxyethoxy) Phenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, , 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-hydroxyeth C) -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, tet Basic ammonium compounds such as raphenylammonium hydroxide, benzyltriphenylammonium hydroxide, methyltriphenylammonium hydroxide, and butyltriphenylammonium hydroxide; diethylamine, dibutylamine, triethylamine, morpholine, N-methylmorpholine, pyrrolidine, piperidine , 3-amino-1-propanol, ethylenediamine, N-
Methyldiethanolamine, diethylethanolamine, diethanolamine, triethanolamine, 4-aminopyridine, 2-aminopyridine, N, N-dimethyl-4-aminopyridine, 4-diethylaminopyridine, 2-hydroxypyridine, 2-methoxypyridine, 4 Amine compounds such as -methoxypyridine, 2-dimethylaminoimidazole, 2-methoxyimidazole, imidazole, 2-mercaptoimidazole, 2-methylimidazole and aminoquinoline, and di- (tert-butyl) amine and 2,2,6 Hindered amine compounds such as 1,6-tetramethylpiperidine;

  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 weight. 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 weight.

  As the carbonic acid diester used as a raw material for the polycarbonate resin (A), a compound represented by the following general formula (4) can be usually employed. These carbonic acid diesters may be used alone or in combination of two or more.

In the general formula (4), A ¹ and A ² are each a substituted or unsubstituted aliphatic hydrocarbon group having 1 to 18 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group, and A ¹ and A ² may be the same 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 (4), for example, substituted diphenyl carbonate such as diphenyl carbonate (DPC) and ditolyl carbonate, dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like 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, at least one compound selected from the group consisting of a magnesium compound, a calcium compound and 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 included. Preferably, calcium compounds are most preferred.

  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, it is particularly selected from the group consisting of magnesium compounds, calcium compounds and barium compounds. When at least one compound is used, the amount of the polymerization catalyst used is preferably 0.1 μmol or more, more preferably 0.3 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. 0.5 μmol or more is particularly preferable. 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 ppm by weight 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 ppm by weight or less. In addition, these metals may mix not only from the catalyst to be used but 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 improve the color tone of the resulting polycarbonate resin (A) while maintaining the polymerization rate appropriately and suppressing monomer distillation, it is important to select the type and amount of the polymerization catalyst described above. is there.

  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. In addition, the pressure in the polymerization reactor (hereinafter, the pressure represents an absolute pressure) is usually 1
It is set in a range of ˜110 kPa, preferably 5 to 70 kPa, more preferably 7 to 30 kPa. The reaction time is usually set in the range of 0.1 to 10 hours, preferably 0.5 to 3 hours. The first stage reaction is 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 weight or less, more preferably 1500 ppm by weight or less, and even more preferably 1000 ppm by weight 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.

  It is preferable that the residual amount of the monohydroxy compound is small, but if it is attempted to reduce it to less than 100 ppm by weight, 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 weight or more, preferably 150 ppm by weight 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.

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.].

  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 (5) or the following structural formula (6). 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) at high temperature can be further suppressed by deactivating the polymerization catalyst.

  Specific phosphorus compounds containing the partial structure represented by the structural formula (5) or structural formula (6) 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 ppm by weight to 5 ppm by weight 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 as a main structural unit the structural unit derived from the aromatic dihydroxy compound represented, for example by following General formula (7).

R ^{1 to} R ⁸ in the general formula (7) each independently represent a hydrogen atom or a substituent. Y represents a single bond or a divalent group. Formula (2) The substituent of R ¹ to R ⁸ in the 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 (2), 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 (2) 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 the aromatic polycarbonate resin (B), the content ratio of the structural unit derived from the dihydroxy compound represented by the general formula (2) with respect to 100 mol% of all structural units derived from the entire dihydroxy compound 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-trimethyl) Phenyl) 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-phen Renbisu (1-methylethylidene)] bis - [phenol], 4,4 '- [1,4-phenylene-bis-methylene] bis - [phenol], 4,4' - [1,
4-phenylenebis (1-methylethylidene)] bis- [2,6-dimethylphenol],
4,4 '-[1,4-phenylene bismethylene] 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′-dihydroxy Diphenyl sulfone, 4,4′-dihydroxydiphenyl sulfide, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether, 3,3 ′, 5,5′-tetramethyl-4,4 ′ -Dihydroxydiphenyl sulfone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide phenolphthalein, 4,4'-[1,4-phenylenebis (1-methylvinylidene)] bisphenol 4,4 ′-[1,4-phenylenebis (1-methylvinylidene)] bis [2-methylphenol], (2-hydroxyphenyl) 4-hydroxyphenyl) methane,
(2-hydroxy-5-methylphenyl) (4-hydroxy-3-methylphenyl) methane, 1,1- (2-hydroxyphenyl) (4-hydroxyphenyl) ethane, 2,2- (2-hydroxyphenyl) Bisphenol compounds such as (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, and melt transesterification condensation polymerization is performed. 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 carnate, bis (biphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. Is mentioned. Of these, diphenyl carbonate is particularly preferably used.

  The viscosity average molecular weight of the aromatic polycarbonate resin (B) 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.

[Impact strength modifier (C)]
As the impact strength modifier (C) to be blended with the polycarbonate resin, it is possible to use a conventionally known impact strength improving agent, for example, a thermoplastic elastomer as described in detail below, Examples thereof include impact strength modifiers having a core / shell structure and soft styrene resins.

<Thermoplastic elastomer>
It is preferable to use an elastomer, and among them, it is preferable to use a thermoplastic elastomer. As the thermoplastic elastomer, various copolymer resins are used. The glass transition temperature is usually 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, and further preferably −30 ° C. or lower. Are preferred.
More specifically, examples of the impact strength modifier include SB (styrene-butadiene) copolymer, SBS (styrene-butadiene-styrene block) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-butadiene-styrene) copolymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer Polymer, AES (acrylonitrile-ethylene propylene rubber-styrene) copolymer, MA (methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic Le - butadiene rubber copolymer, methyl methacrylate - acrylic - butadiene rubber - styrene copolymer, methyl methacrylate - can be used - (acryl silicone IPN rubber) copolymer, and natural rubber.

Preferably, the impact strength modifier is a copolymer containing butadiene.
In this case, a particularly significant impact strength modification effect can be obtained in combination with the polycarbonate resin.

  Specific examples of the copolymer containing butadiene include SBS (styrene-butadiene-styrene block) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, and MBS (methyl methacrylate-butadiene-styrene) copolymer. There are polymers, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) copolymers, MB (methyl methacrylate-butadiene) copolymers, methyl methacrylate-acryl-butadiene rubber copolymers, and the like.

<Impact strength modifier with core / shell structure>
The impact strength modifier having a core / shell structure is as described in detail below. In this specification, the “impact strength modifier having a core / shell structure” is composed of an innermost layer (core layer) and one or more layers (shell layer) covering the inner layer (core layer). A core-shell type graft copolymer obtained by graft copolymerizing a polymerizable monomer component as a shell layer.

An impact strength modifier having a core / shell structure is usually a core / shell type graft in which a polymer component called a rubber component is used as a core layer and a monomer component copolymerizable therewith is used as a shell layer for graft copolymerization. A copolymer is preferred.
The core / shell type graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be one-stage graft or multi-stage graft. There may be. However, in the second aspect of the present invention, a commercially available core / shell type elastomer can be used as it is. Examples of commercially available core-shell type elastomers will be listed later.

  The polymer component forming the core layer has a glass transition temperature of usually 0 ° C. or lower, preferably −10 ° C. or lower, more preferably −20 ° C. or lower, and further preferably −30 ° C. or lower. Specific examples of the polymer component forming the core layer include polybutadiene, polyisoprene, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylates such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane. Silicone rubber such as rubber, butadiene-acrylic composite, IPN (Interpenetrating Polymer Network) composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene copolymer, ethylene-propylene copolymer and ethylene -Butene copolymer, ethylene-α olefin copolymer such as ethylene-octene copolymer, ethylene-acrylic copolymer, fluoro rubber, etc. That. These may be used alone or in admixture of two or more. Among these, from the viewpoint of mechanical properties and surface appearance, polybutadiene, polyalkyl acrylate, polyorganosiloxane, a composite composed of polyorganosiloxane and polyalkyl acrylate, and a butadiene-styrene copolymer are preferable.

Specific examples of the monomer component that can be graft-copolymerized with the polymer component of the core layer constituting the shell layer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic compounds. Acid group, epoxy group-containing (meth) acrylic acid ester compound such as glycidyl (meth) acrylate; maleimide compound such as maleimide, N-methylmaleimide, N-phenylmaleimide; α, β such as maleic acid, phthalic acid, itaconic acid -Unsaturated carboxylic acid compounds and their anhydrides (for example, maleic anhydride etc.) etc. are mentioned. These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. Of these, methyl (meth) acrylate and ethyl (meth) acrylate, which are relatively easily available, are preferred, and methyl (meth) acrylate is more preferred. Here, “(meth) acryl” is a general term for “acryl” and “methacryl”.

  The impact strength modifier comprising a core / shell structure is at least selected from polybutadiene-containing rubber, polybutylacrylate-containing rubber, polyorganosiloxane rubber, and IPN composite rubber comprising polyorganosiloxane rubber and polyalkylacrylate rubber. A core-shell type graft copolymer comprising a shell layer formed by graft copolymerizing (meth) acrylic acid ester around one polymer component as a core layer is particularly preferred.

  Preferred examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone composite) copolymers.

  Examples of such core-shell type graft copolymers include “Paraloid (registered trademark) EXL2602”, “Paraloid (registered trademark) EXL2603”, and “Paraloid (registered trademark)” manufactured by Rohm and Haas Japan. "EXL2655", "Paraloid (registered trademark) EXL2311", "Paraloid (registered trademark) EXL2313", "Paraloid (registered trademark) EXL2315", "Paraloid (registered trademark) KM330", "Paraloid (registered trademark) KM336P", "Paraloid" (Registered Trademark) KCZ201 "," Metablene (Registered Trademark) C-223A "," Metablene (Registered Trademark) E-901 "," Metablene (Registered Trademark) S-2001 "," Metablene (Registered Trademark) "manufactured by Mitsubishi Rayon Co., Ltd. ) W-450A "" Metabrene (registered trademark) S "K-200", "Kaneace (registered trademark) M-511", "Kaneace (registered trademark) M-600", "Kaneace (registered trademark) M-400", "Kaneace (registered trademark) M-" manufactured by Kaneka Corporation 580 "," Kane Ace (registered trademark) MR-01 ", and the like.

  These impact strength modifiers having a core-shell structure such as a core-shell type graft copolymer may be used alone or in combination of two or more.

<Soft styrene resin>
As the conjugated diene polymer block used in the soft styrene resin, homopolymers such as butadiene, isoprene and 1,3-pentadiene, copolymers thereof, or monomers copolymerizable with conjugated diene monomers are used. A copolymer or the like contained in the block can be used. Specific examples include styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer (SIS), and the like. Specific products include “Clayton D” series manufactured by Kraton Polymer Co., “AR-100” series manufactured by Aron Kasei Co., Ltd. and the like.

The block copolymer includes a pure block, a random block, a tapered block, and the like, and the form of copolymerization is not particularly limited. Further, the block unit may be overlapped by any number of repeating units. Specifically, in the case of a styrene / butadiene block copolymer, there are several block units such as a styrene / butadiene copolymer, a styrene / butadiene / styrene block copolymer, and a styrene / butadiene / styrene / butadiene block copolymer. It does not matter if it is repeated.

  Also, a hydrogenated styrene / butadiene / styrene block copolymer (SEBS) obtained by hydrogenating a part or all of the double bond of the conjugated diene polymer block of SBS or SIS, hydrogenated styrene / isoprene / styrene. A block copolymer (SEPS) can also be used. Specific products include “Tough Tech H” series manufactured by Asahi Kasei Chemicals, “Clayton G” series manufactured by Kraton Polymer, and the like.

In addition, it is possible to give a functional group having polarity to the soft styrene resin. Specific examples of polar functional groups include acid anhydride groups, carboxylic acid groups, carboxylic acid ester groups, carboxylic acid chloride groups, carboxylic acid amide groups, carboxylic acid groups, sulfonic acid groups, sulfonic acid ester groups, sulfones. Examples thereof include acid chloride groups, sulfonic acid amide groups, sulfonic acid groups, epoxy groups, amino groups, imide groups, and oxazoline groups.
Among these, it is preferable to give an acid anhydride group or an epoxy group, and as the acid anhydride group, a functional group derived from maleic anhydride is particularly preferable. By imparting such a functional group, the compatibility between the polycarbonate resin composition and the soft styrene resin is improved, and the soft styrene resin is finely dispersed in the polycarbonate resin composition. Impact properties can be improved.

  As the soft styrenic resin imparted with a functional group having polarity, SEBS and SEPS modified products are preferably used. Specific examples include maleic anhydride-modified SEBS, maleic anhydride-modified SEPS, epoxy-modified SEBS, and epoxy-modified SEPS. Specific products include “Tough Tech M” series manufactured by Asahi Kasei Chemicals, “Dynalon” series manufactured by JSR, “Epofriend” series manufactured by Daicel Chemical Industries, and the like.

  The melt flow rate (MFR) of the soft styrene resin at 230 ° C. and 2.16 kg load is preferably 1 g / 10 min or more and 10 g / 10 min or less. The lower limit of MFR is more preferably 2 g / 10 minutes, and further preferably 4 g / 10 minutes. Moreover, as an upper limit of MFR, More preferably, it is 8 g / 10min, More preferably, it is 6 g / 10min. If the MFR of the soft styrenic resin is within such a range, a resin composition having good dispersibility with the polycarbonate resin composition and excellent transparency and impact resistance can be provided.

  Further, the difference between the average refractive index of the polycarbonate resin composition of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) and the average refractive index of the impact strength modifier (C) (“average refractive index of the polycarbonate resin composition”). Ratio ”—“ average refractive index of impact strength modifier (C) ”) is preferably −0.015 or more and +0.015 or less, and preferably −0.013 or more and +0.013 or less. More preferably, it is -0.010 or more and +0.010 or less. If the difference in average refractive index between the polycarbonate resin composition and the impact strength modifier (C) is within such a range, a resin composition having particularly excellent transparency can be provided. Among these, an impact strength modifier having a core / shell structure is preferable because of its good transparency when used as a resin composition.

In addition, the average refractive index of the said polycarbonate resin composition and the said impact strength modifier (C) was computed using the following method.
A sample molded to a thickness of 100 μm is measured with an Atbé Abbe refractometer using sodium D-line (589 nm) as a light source and measured at n = 5 at an ambient temperature of 23 ° C. based on JIS K7142 (2008). The average value of the refractive index was calculated as the average refractive index.

In the polycarbonate resin composition, the impact strength modifier (C) out of a total of 100% by weight of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). Is preferably 0% by weight or more, more preferably 1% by weight or more, still more preferably 3% by weight or more, particularly preferably 5% by weight or more, and most preferably 8% by weight or more. On the other hand, the content of the impact strength modifier (C) with respect to 100% by weight of the polycarbonate resin composition is preferably 25% by weight or less as an upper limit, more preferably 20% by weight or less, It is more preferable that the amount is not more than wt%, and 12 wt% is particularly preferable.
When the content of the impact strength modifier (C) is not less than the above lower limit value, a sufficient impact strength modification effect can be obtained. On the other hand, by being below the above-mentioned upper limit, not only the occurrence of burns during molding can be prevented and the moldability can be kept good, but also the transparency can be kept good.

In the measurement method detailed in the Examples, Charpy notched impact strength of the polycarbonate resin composition is preferably 30 kJ / m ² or more, more preferably 35 kJ / m ² or more, particularly preferably at least 40 wt%.

The notched Charpy impact strength can be controlled by adjusting the molecular weight, the molar ratio of the dihydroxy compound, the type or content of the impact strength modifier (C), etc. in the polycarbonate resin composition.
[Acid compound (D)]
The polycarbonate resin composition preferably further contains an acidic compound (D). The acidic compound (D) is added when the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the impact strength modifier (C) are blended, and the polycarbonate resin (A) and It is a concept that does not include the above-described catalyst deactivator used in the production of the aromatic polycarbonate resin (B). This is because these catalyst deactivators lose their effects themselves in the production stage of the polycarbonate resin (A) and the aromatic polycarbonate resin (B). In addition, as an acidic compound (D), the same substance as the above-mentioned catalyst deactivator can be used. By blending a mixture of the polycarbonate resin (A) and the polycarbonate resin (B) with the impact strength modifier (C) and the acidic compound (D), the notched Charpy impact strength of the resulting polycarbonate resin composition can be improved. A further improvement effect can be obtained. An impact strength modifier in a resin composition obtained by combining an impact strength modifier (C) and an acidic compound (D) in a mixture of the polycarbonate resin (A) and the polycarbonate resin (B). It is considered that the dispersibility of (C) is improved and the impact strength is further improved.

In the polycarbonate resin composition, the content of the acidic compound (D) with respect to a total of 100% by weight of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C), The lower limit is preferably 2.5 ppm by weight or more, more preferably 7.5 ppm by weight or more, and even more preferably 10 ppm by weight or more. On the other hand, it is preferable that content of the said acidic compound (D) with respect to a polycarbonate resin composition is less than 25 weight ppm as an upper limit, It is more preferable that it is 20 weight ppm or less, It is 13 weight ppm or less Is more preferable.
When content of the said acidic compound (D) is more than the above-mentioned lower limit, the further improvement effect of notched Charpy strength at the time of using together with an impact strength modifier (C) can be acquired. On the other hand, discoloration under high temperature and high humidity can be suppressed by being below the above-mentioned upper limit.

Moreover, when mix | blending the below-mentioned compound (E) with a polycarbonate resin composition, the addition amount of an acidic compound (D) is 0.5 with respect to 1 mol of compounds (E) contained in a polycarbonate resin composition. It is preferable that it is more than double mole and less than 5 moles. In this case, the heat and humidity resistance can be further improved, and the thermal stability during molding and the like can be further improved. From the same viewpoint, the addition amount of the acidic compound (D) is more preferably from 0.6 to 2 mol, and from 0.7 to 1 mol per mol of the compound (E). More preferably, it is 8 times mol or less.

[Compound (E)]
The said compound (E) mix | blended with respect to a polycarbonate resin composition can accelerate | stimulate the transesterification reaction of a polycarbonate resin (A) and an aromatic polycarbonate resin (B). The transesterification reaction occurs, for example, by heating during kneading of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) when the resin composition is produced, and is accelerated by the compound (E). As a result, since the compatibility of the polycarbonate resin (A) and the aromatic polycarbonate resin (B) in the resin composition is improved, the transparency of the resin composition can be increased. In addition, it is possible to realize a resin composition excellent in characteristics such as heat resistance, moist heat resistance, and impact resistance without reducing the biogenic substance content rate while having high transparency. The compound (E) may be a compound containing at least one selected from the group consisting of Group 1 metals and Group 2 metals.

  Examples of the metal in the compound (E) include lithium, sodium, potassium, rubibidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like.

  The metal in the compound (E) preferably has an electronegativity of 0.7 to 1.1, more preferably 0.75 to 1.0 among Group 1 and Group 2 metals. Even more preferred is 75-0.98. Specifically, cesium (0.79), potassium (0.82), sodium (0.93), lithium (0.98), barium (0.89), strontium (0.95), calcium (1 .0). The numbers in parentheses are electronegativity. By adopting a metal having an electronegativity in the above range, the transparency of the polycarbonate resin composition can be further improved, and the impact resistance can be further improved.

  Examples of the compound (E) include metal salts composed of the metal and organic acids such as carboxylic acid, carbonic acid, and phenol, nitric acid, phosphoric acid, boric acid, and the like. Examples of the metal salt also include the metal halides and hydroxides.

  The acid dissociation constant (pKa) of the counter ion of the metal ion in the compound (E) is preferably 2-16. In this case, the transparency of the polycarbonate resin composition can be increased without increasing the amount of catalyst in terms of metal, and the hue can be further prevented from deteriorating. From the same viewpoint, the acid dissociation constant (pKa) of the counter ion of the metal ion in the compound (E) is more preferably 3 to 11, and particularly preferably 5 to 10.

As the group 1 metal compound used as the compound (E), 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. Among these, at least one selected from the group consisting of sodium compounds, potassium compounds, and cesium compounds is preferable, and potassium compounds and / or cesium compounds are more preferable from the viewpoint of further improving transparency, color tone, and heat and humidity resistance. . Particularly preferred are potassium bicarbonate, cesium bicarbonate, potassium carbonate, cesium carbonate, potassium acetate, cesium acetate, potassium stearate, and cesium stearate.

  As the group 2 metal compound used as the compound (E), 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. Among these, a calcium compound is preferable from the viewpoint of further improving transparency and color tone. Particularly preferred are calcium hydroxide, calcium bicarbonate and calcium acetate.

The amount of metal derived from the compound (E) contained in the polycarbonate resin composition is 100 weights in total with the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). It is preferable that it is 0.8 weight ppm or more and 1000 weight ppm or less with respect to a part. Although it depends on the metal species, if it exceeds 1000 ppm by weight, the color tone of the resin composition deteriorates and the heat and humidity resistance decreases. If it is less than 0.8 ppm by weight, the transparency of the resin composition becomes insufficient. From the viewpoint of further improving color tone, heat resistance, and transparency, the amount of metal derived from the compound (E) is more preferably 0.9 ppm by weight or more and 100 ppm by weight or less, more preferably 1 ppm by weight or more, And it is especially preferable that it is 10 weight ppm or less. The compound (E) introduced into the polycarbonate resin composition from the polycarbonate resin (A) polymerization catalyst or aromatic polycarbonate resin (B) polymerization catalyst as a raw material is generally, for example, p after the polymerization step. -Since it is often inactivated by an acidic compound such as butyl toluenesulfonate, it is preferable to add the compound (E) separately as described later. The compound (E) contained in the polycarbonate resin composition is used in the production of the polycarbonate resin (A) and the aromatic polycarbonate resin (B), and is brought into the resin composition from each resin (A) and resin (B). This is a concept that includes both a polymerization catalyst corresponding to the compound (E) and a compound (E) that is added separately during the production of the resin composition.

  The amount of the compound (E) added during the production of the resin composition depends on the metal species, but the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the impact strength modifier (C) The total amount is 100 parts by weight of 0.5 to 1000 ppm by weight in terms of metal, preferably 1 to 100 ppm by weight, particularly preferably 1 to 10 ppm by weight. If it is less than 0.5 ppm by weight, the transparency of the resin composition becomes insufficient. On the other hand, when the content is more than 1000 ppm by weight, the resin composition becomes transparent, but the coloring is intense, the molecular weight (melt viscosity) of the resin composition is lowered, and a resin composition excellent in impact resistance cannot be obtained.

  Regarding the method for adding the compound (E), a solid compound may be supplied as it is, or a compound that can be dissolved 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]
(Total light transmittance, color tone)
The polycarbonate resin composition preferably has a total light transmittance of 70% or more in the thickness direction of a molded product having a thickness of 2 mm formed by molding the polycarbonate resin composition. Moreover, from the viewpoint that the applicability to transparent applications and the sharpness at the time of original deposition are improved, the total light transmittance is more preferably 75% or more, and further preferably 80% or more. Further, the YI value of the molded body having a thickness of 2 mm is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less. In addition, the measuring method of a total light transmittance and YI value is demonstrated in the below-mentioned Example.

  Moreover, the deflection temperature under load (HDT) of the polycarbonate resin composition refers to the deflection temperature under load measured in the examples described later. The load deflection temperature of the polycarbonate resin composition is preferably 100 ° C. or more as the lower limit. In this case, since the heat resistance can be further improved, deformation of the molded product can be further prevented. Further, the deflection temperature under load of the polycarbonate resin composition is preferably 125 ° C. or lower as an upper limit. In this case, the fluidity of the polycarbonate resin (A) during the production of the resin composition can be appropriately maintained, thermal deterioration can be further suppressed, and impact resistance can be further improved. Furthermore, the thermal deterioration of the resin composition during molding can be further suppressed.

  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 compound (E), and the content of the compound (E) 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 30/70, 80/20 to 40/60 is more preferable, 75/25 to 50/50 is more preferable, and 70/30 to 60/40 is particularly preferable. 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, hydrolysis inhibitors, foaming agents, and cores. The additive etc. which are normally used for polycarbonate resin 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 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), the aromatic polycarbonate resin (B) and the impact strength modifier (C). It is preferable that 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), the aromatic polycarbonate resin (B), and the impact strength modifier (C). . 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). Further, the addition amount of the antioxidant is 0.001 part by weight or more with respect to a total of 100 parts by weight of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). preferable. In this case, the effect of improving the molding stability can be sufficiently obtained. From the same point of view, the antioxidant is added in an amount of 0.002 weight per 100 weight parts of the total of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). Part or more is more preferable, and 0.005 part by weight or more is still 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"
Examples of ultraviolet 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- And hydroxyphenyl) propionate.

  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, 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 and 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, bis (2,2,26,6-tetramethyl-1- (octyloxy) -4-piperidinyl) decanedioate) Ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, 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-tetramethyl-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-butane Tetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β, β-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5 Condensate with 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, Haq dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like.

  The content of the light stabilizer is 0.001 part by weight or more and 5 parts by weight with respect to 100 parts by weight in total of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). Part or less. 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 0.005 to 3 parts by weight with respect to a total of 100 parts by weight of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). More preferably, it is 0.01 parts by weight or more and 1 part by weight or less. 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 is a total of the polycarbonate resin (A), the aromatic polycarbonate resin (B), and the impact strength modifier (C) as a release agent for imparting release properties at the time of molding. You may contain 0.0001 weight part or more and 2 weight part or less of the fatty acid ester of a polyhydric alcohol with respect to 100 weight%. 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. And 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"
In addition, the polycarbonate resin composition does not impair the effects of the present invention, for example, synthetic resins such as aromatic polyester, aliphatic polyester, polyamide, polystyrene, polyolefin, acrylic, and amorphous polyolefin, polylactic acid, and polybutylene succinate. It can also be used as a polymer alloy by kneading with one or more of biodegradable resins such as.

"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 said polycarbonate resin composition performs the process of kneading | mixing the said specific polycarbonate resin (A) and aromatic polycarbonate resin (B) first, Then, it knead | mixes the polycarbonate resin (A) and aromatic polycarbonate resin (B). It can manufacture by performing the process of mix | blending an impact strength modifier (C) and an acidic compound (D). In the reaction step, by further adding compound (E), the presence of compound (E) promotes the transesterification reaction between polycarbonate resin (A) and aromatic polycarbonate resin (B), and is highly compatible. A resin composition is obtained. In addition, as a polycarbonate resin (A), an aromatic polycarbonate resin (B), and a compound (E), the thing similar to the above can be used. When adding the compound (E), the specific compound (E) is added to the specific polycarbonate resin (A) and the aromatic polycarbonate resin (B) in an amount of 0.5 ppm to 1000 ppm by weight in terms of metal amount. It is preferable to do this.

  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.

The melt kneader is not limited to the type of twin screw extruder or single screw extruder as long as it can achieve mixing in a reduced pressure state, but the specific polycarbonate resin (A) to be used is not limited. And a twin screw extruder is more preferable for the purpose of achieving reaction mixing according to the characteristics of the aromatic polycarbonate resin (B).
The mixing temperature of the polycarbonate resin composition is preferably 200 ° C to 300 ° C. In this case, the time required for the reaction kneading can be shortened, and the amount of the compound (E) required for the reaction can be suppressed. As a result, it is possible to more reliably prevent deterioration of the color tone due to the deterioration of the resin, and to further improve practical physical properties such as impact resistance and heat-and-moisture resistance. From the same viewpoint, the mixing temperature is more preferably 220 ° C to 280 ° C.
Further, regarding the mixing time, unnecessary lengthening should be avoided from the viewpoint of more surely avoiding the same resin deterioration as described above, which is a balance between the amount of the compound (E) and the mixing temperature. It is preferably 150 seconds or longer and more preferably 10 seconds or longer and 25 seconds or shorter, and it is necessary to set conditions for the amount of the compound (E) and the mixing temperature so as to satisfy this.

  It is preferable to carry out the melting reaction in the reaction step under the condition that the degree of vacuum is 30 kPa or less. More preferably, the degree of vacuum is 25 kPa or less, and further preferably the degree of vacuum is 15 kPa or less. Here, the degree of vacuum represents an absolute pressure, which is obtained by reading a vacuum pressure gauge and calculating by a conversion formula (101 kPa- (vacuum pressure count value)).

  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, moist heat resistance, and impact resistance at a high level. In addition, in a molded product formed by molding a polycarbonate resin composition, it is possible to improve color tone, weather resistance, mechanical strength, etc., and to reduce residual low molecular components and foreign substances. Therefore, the molded body is suitable for interior parts for vehicles.

  The polycarbonate resin composition is excellent in hue, transparency, heat resistance, weather resistance, mechanical strength, and the like, and also excellent in stability of hue and optical properties under wet heat. Injection molding field such as glass substitute application; Extrusion field such as film, sheet field, bottle and container field; Lens application such as camera lens, finder lens, CCD and CMOS lens; Used for liquid crystal and organic EL display Optical films such as retardation films, diffusion sheets, light guide plates, polarizing films, optical sheets; optical discs, optical materials, optical components; binder applications for fixing dyes, charge transfer agents, etc. are applicable. .

  The polycarbonate resin composition is excellent in transparency, heat resistance, weather resistance, mechanical strength, etc., and is excellent in sharpness even when colored with a colorant or the like. Applicable to body use. Examples of automotive exterior parts include fenders, bumpers, fascias, door panels, side garnishes, pillars, radiator grills, side protectors, side moldings, rear protectors, rear moldings, various spoilers, bonnets, roof panels, trunk lids, detachable tops, wind reflectors. , Mirror housing, outer door handle, etc. Examples of automobile interior parts include instrument panels, center console panels, meter parts, various switches, car navigation parts, car audio visual parts, and auto mobile computer parts. Electrical / electronic parts and casings include, for example, exterior parts of personal computers such as desktop personal computers and notebook personal computers, exterior parts of office automation equipment such as printers, copiers, scanners and fax machines (including these multifunction machines), display devices Exterior parts (such as CRT, liquid crystal, plasma, projector, and organic EL), exterior parts such as a mouse, switch mechanism parts such as keyboard keys and various switches, game machines (home game machines, arcade game machines, and Pachinko and slot machines). Further, a portable information terminal (so-called PDA), a mobile phone, a portable book (dictionaries, etc.), a portable TV, a drive for a recording medium (CD, MD, DVD, next-generation high-density disk, hard disk, etc.), a recording medium (IC card) , Smart media, memory stick, etc.) readers, optical cameras, digital cameras, parabolic antennas, electric tools, VTRs, irons, hair dryers, rice cookers, microwave ovens, hot plates, audio equipment, lighting equipment, refrigerators, air conditioners, air Examples include cleaners, negative ion generators, and electric / OA devices such as watches, and household appliances.

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

(1) Measurement of amount of metal in polycarbonate resin composition The amount of metal in the polycarbonate resin composition was measured using ICP-MS (inductively coupled plasma mass spectrometer). Specifically, about 0.5 g of a polycarbonate resin composition sample was accurately weighed and subjected to pressure sealed decomposition with sulfuric acid and nitric acid. For pressure sealed decomposition, a MULTITIWAV manufactured by Perkin Elmer, a microwave decomposition apparatus, was used. The decomposition solution was appropriately diluted with pure water, and measured with ICP-MS (ELEMENT by Thermoquest). The measured alkali and alkaline earth metals are Li, Na, K, Cs, Mg, Ca and Ba. In addition, the metal amount in the below-mentioned Examples 1-20 is not only the metal derived from the compound (C) but also the metal derived from the polycarbonate resin (A) (for example, Ca) or the aromatic polycarbonate resin (B) (for example, Cs).

(2) Melt flow rate (MFR)
The MFR of the polycarbonate resin composition was measured at a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K7210 (1999).

(3) Measurement of total light transmittance and YI 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 (EC-75SX manufactured by Toshiba Machine Co., Ltd.), and molding is performed under conditions of a resin temperature of 240 ° C., a mold temperature of 60 ° C., and a molding cycle of 50 seconds. A plate (width 100 mm × length 100 mm × thickness 2 mm) was obtained. Based on JIS K7136 (2000), the total light transmittance and Haze of the injection-molded plate were measured with a D65 light source using a Nippon Denshoku Industries Co., Ltd. haze meter “NDH2000”. If the total light transmittance is 70% or more and it is clear that the injection molded plate is opaque, the evaluation result is “opaque” instead of the measured value of the total light transmittance. It was. The YI value was measured in accordance with JIS K7373 (2006), using a spectrocolorimeter “CM-5” manufactured by Konica Minolta, Inc., and the YI of the injection-molded plate was measured with a C light source.
In this example, evaluation was performed as follows.
<Total light transmittance>
In the case of 75% or more: Judged to be particularly excellent in transparency, and determined as “◎”.
In the case of 70% or more: Judged to be excellent in transparency, and set as “◯”.
When it is less than 70%: It was judged that the transparency was not excellent, and “x” was assigned.
<YI value>
In the case of 5 or less: It was judged that the color tone was particularly excellent, and “◎” was given.
In the case of 10 or less: It was judged that the color tone was excellent, and “◯” was given.
When exceeding 10, it was judged that the color tone was not excellent, and it was set as “x”.

(4) Notched Charpy impact test A notched Charpy impact test was performed on the ISO physical specimens for mechanical properties obtained below in accordance with ISO 179 (2000). Regarding the notch, the tip radius R was measured for 0.25 mm. In addition, notch Charpy impact strength is superior in impact resistance strength as the value is larger,
In this example, evaluation was performed as follows.
In the case of 35 kJ / m ² or more: It was judged that the impact resistance was particularly excellent, and “◎” was given.
In the case of 30 kJ / m ² or more: It was judged that the impact resistance was excellent, and “◯” was given.
When it is less than 30 kJ / m ² : It was determined that the impact resistance was not excellent, and “x” was assigned.

(5) Heat resistance (deflection temperature under load)
The heat resistance of the polycarbonate resin composition was evaluated as follows.
The pellets of the polycarbonate resin composition were dried at 90 ° C. for 4 hours or more using a hot air dryer. Next, a dumbbell-shaped test piece for a tensile test was molded from the dried pellet by an injection molding machine (EC-75SX manufactured by Toshiba Machine Co., Ltd.). This dumbbell-shaped test piece was cut to prepare a test piece for measuring a deflection temperature under load. Using this test specimen for measuring the deflection temperature under load, the deflection temperature under load was measured according to ISO 75 (2004). The test was performed flat-wise, and the temperature at which the deflection of the test piece reached the specified deflection was defined as the deflection temperature under load. The load was measured at 1.80 MPa. It shows that heat resistance is so high that this value is high.
In this example, evaluation was performed as follows.
In the case of 100 ° C. or higher: judged to be excellent in heat resistance, and set as “◯”.
When the temperature is less than 100 ° C .: It is judged that the heat resistance is not excellent, and “x” is given.

(6) Comprehensive evaluation Based on the evaluations of (1) to (5) above, when there was at least one “×”, the evaluation was rejected, and the others were determined to be acceptable. In addition, the greater the number of “◎” in the pass, the better.

[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]

<Aromatic polycarbonate (B)>
PC-B1: Novalex 7022J manufactured by Mitsubishi Engineering Plastics (aromatic polycarbonate resin having a bisphenol A constituent unit of 100 mol%, melt viscosity (240 ° C., shear rate 91.2 sec ⁻¹ ) 3260 Pa · s)
<Impact strength modifier (C)>
-Paraloid EXL-2678 (Butadiene rubbery polymer manufactured by Dow Chemical Company: methacrylate, butadiene, styrene resin, refractive index 1.532-1.53)
-Methbrene C-223A (Mitsubishi Rayon Co., Ltd. butadiene rubbery polymer: methacrylate, butadiene, styrene resin, refractive index 1.52)
Methabrene E-807A (Mitsubishi Rayon Co., Ltd. butadiene rubber polymer: methacrylate, butadiene, styrene resin, refractive index 1.52)
B-513 (Baneca Rubber Polymer: Methacrylate / Butadiene / Styrene Resin, Refractive Index 1.53)
-Methbrene C-201A (Mitsubishi Rayon Co., Ltd. butadiene rubber polymer: methacrylate, butadiene, styrene resin, refractive index 1.53)
<Catalyst deactivator (acidic compound (D))>
・ Phosphonic acid [Reagent special grade phosphonic acid (phosphorous acid) manufactured by Wako Pure Chemical Industries] (molecular weight 82.0)
<Compound (E)>
Hyperform HPN-68L (Milken Japan (same): Bicyclo [2.2.1] Heptane-2,3-Dicarboxylic Acid, Disodium Salt. Contains 80%, other components include water, silica, etc.)

<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 of 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 are melted in tanks, ISB 35.2 kg / hr, CHDM 14.9 kg / hr, DPC 74.5 kg / hr (in terms of molar ratio 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 was supplied to the first vertical stirring reactor so that the addition amount of calcium acetate monohydrate as a catalyst was 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 second vent, 2000 ppm by weight of water was added to the resin to perform water injection and devolatilization. Prior to the third vent, 0.1 part by weight, 0.05 part by weight, and 0.3 part by weight of Irganox 1010, AS2112, and E-275 were added to 100 parts by weight of the polycarbonate resin, respectively. Thus, an ISB / CHDM copolymer polycarbonate resin was obtained. 0.65 weight ppm phosphorous acid (0.24 weight ppm as the amount of phosphorus atoms) was added to the polycarbonate resin as a catalyst deactivator. Phosphorous acid was added as follows. A master batch was prepared by mixing the polycarbonate resin pellets obtained in Production Example 1 with a solution of phosphorous acid in an ethanol solution. From the front of the first vent port of the extruder (from the resin supply port side of the extruder), The master batch was supplied at 1 part by weight with respect to 100 parts by weight of the polycarbonate resin in the extruder.
The polycarbonate resin (A) obtained in Production Example 1 is referred to as “PC-A1”. The melt viscosity of PC-A1 (240 ° C., shear rate 91.2 sec ⁻¹ ) is 720 Pa · s.

[Example 1]
In this example, as the kneading in the first stage, 70 parts by weight of PC-A1 is used as the polycarbonate resin (A), 30 parts by weight of PC-B1 is used as the aromatic polycarbonate resin (B), and the compound (D) is used. , Powdery hyperform HPN-68L containing Na (made by Milliken Japan Co., Ltd.) 2 ppm by mass, and 15-crown 5-ether with a molar ratio of 1 to the metal in compound (D) ( Using a metal equivalent (Na equivalent), a biaxial kneader (manufactured by Nippon Steel Works, TEX-30α (L / D = 52.5, L (mm): screw length, D (mm)) ): Screw diameter)), and the polycarbonate resin (A) and the aromatic polycarbonate resin (B) were melted. The kneading conditions are: flow rate: 60 kg / h, screw rotation speed: 430 rpm, cylinder temperature: 230 ° C. The extruder has two vacuum vent ports, and the vent vacuum was 113 kPa. After the melt reaction by kneading, the kneaded product was extruded into a strand shape, cut into a pellet shape through a water cooling step, and a kneaded product pellet was obtained. As the second stage kneading, 95% by weight of the obtained kneaded pellets, paraloid EXL-2678 as impact strength modifier (C), and phosphonic acid (Wako Pure Chemical Industries, Ltd.) as acidic compound (D) The reagent special grade) is 7.5 ppm by weight with respect to 100 parts by weight of the total amount of the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). Melting and kneading was again carried out using the above biaxial kneader to obtain pellets of a polycarbonate resin composition. The kneading conditions are: flow rate: 30 kg / h, screw rotation speed: 200 rpm, cylinder temperature: 230 ° C.

  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-75SX 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 for the changes shown in the following (1) and (2), a polycarbonate resin composition was prepared in the same manner as in Example 1, and a molded body (test piece) was prepared using this. The evaluation results of this example are shown in Table 1.
(1) Paraloid EXL-2678 used as the impact strength modifier (C) was changed to methabrene C-223A.
(2) The addition amount of the acidic compound (D) was changed from 7.5 ppm by weight to 10.8 ppm by weight.
(3) The biaxial kneader used in the first stage kneading was changed as follows.
Kneading machine: TEX54αII (L / D = 45.5), flow rate: 265 kg / h, screw rotation speed: 215 rpm, cylinder temperature: 230 ° C.)
The twin-screw kneader used in the second stage kneading is not changed from the first embodiment.

[Example 3]
Except for the changes shown in the following (1) to (3), a polycarbonate resin composition was produced in the same manner as in Example 1, and a molded article (test piece) was produced using this. The evaluation results of this example are shown in Table 1.
(1) Paraloid EXL-2678 used as the impact strength modifier (C) was changed to Methbrene E-807A.
(2) The addition amount of the acidic compound (D) was changed from 7.5 ppm by weight to 10.8 ppm by weight.
(3) The conditions of the biaxial kneader used in the first stage kneading were changed to the change (3) in Example 2.

[Example 4]
Except for the changes shown in the following (1) to (3), a polycarbonate resin composition was produced in the same manner as in Example 1, and a molded article (test piece) was produced using this. The evaluation results of this example are shown in Table 1.
(1) Paraloid EXL-2678 used as the impact strength modifier (C) was changed to methabrene C-223A, and the amount added was changed from 5% by weight to 10% by weight.
(2) The addition amount of the acidic compound (D) was changed from 7.5 ppm by weight to 10.8 ppm by weight.
(3) The conditions of the biaxial kneader used in the first stage kneading were changed to the change (3) in Example 2.

[Example 5]
Except for the changes shown in the following (1) to (3), a polycarbonate resin composition was produced in the same manner as in Example 1, and a molded article (test piece) was produced using this. The evaluation results of this example are shown in Table 1.
(1) Paraloid EXL-2678 used as the impact strength modifier (C) was changed to Methbrene E-807A, and the amount added was changed from 5 wt% to 10 wt%.
(2) The addition amount of the acidic compound (D) was changed from 7.5 ppm by weight to 10.8 ppm by weight.
(3) The conditions of the biaxial kneader used in the first stage kneading were changed to the change (3) in Example 2.

[Comparative Example 1]
Except for the changes shown in the following (1) and (2), a polycarbonate resin composition was prepared in the same manner as in Example 1, and a molded body (test piece) was prepared using this. The evaluation results of this example are shown in Table 1.
(1) The amount of impact strength modifier (C) added was changed to zero.
(2) The addition amount of acidic compound (D) was changed to zero.

[Comparative Example 2]
Except for the changes shown in the following (1) to (2), a polycarbonate resin composition was produced in the same manner as in Example 1, and a molded article (test piece) was produced using this. The evaluation results of this example are shown in Table 1.
(1) The amount of impact strength modifier (C) added was changed to zero.
(2) In the first stage kneading, the screw rotation speed of the biaxial kneader was changed from 430 rpm to 325 rpm.

[Comparative Example 3]
Except for the changes shown in the following (1), a polycarbonate resin composition was prepared in the same manner as in Example 1, and a molded body (test piece) was prepared using the polycarbonate resin composition. The evaluation results of this example are shown in Table 1.
(1) The addition amount of acidic compound (D) was changed to 0.

[Comparative Example 4]
Except for the changes shown in the following (1) to (3), a polycarbonate resin composition was produced in the same manner as in Example 1, and a molded article (test piece) was produced using this. The evaluation results of this example are shown in Table 1.
(1) The addition amount of polycarbonate resin (B) was changed to 0.
(2) The addition amount of acidic compound (D) was changed to zero.
(3) The amount of compound (E) added was changed to zero.

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 impact strength modifier (C) and the acidic compound (D) are contained. Such a polycarbonate resin composition has a notch Charpy impact strength measured with a molded product having a thickness of 2 mm having a total light transmittance of 70% or more, a YI value of 10 or less, and a notch tip radius R of 0.25 mm. It was 30 kJ / m ² or more, heat resistance was 100 ° C. or more, and had transparency, color tone, impact resistance, and heat resistance at a high level in a well-balanced manner.

Claims (13)

A polycarbonate resin (A) having a structural unit derived from a compound represented by the following formula (1) with respect to 100 mol% of a structural unit derived from all diols;
An aromatic polycarbonate resin (B);
Impact strength modifier (C);
A polycarbonate resin composition containing an acidic compound (D).

  The polycarbonate resin composition further contains at least one compound (E) selected from a compound of a long-period periodic table group I metal and a long-period periodic table group II metal compound. Item 5. The polycarbonate resin composition according to Item 1.   The content of the compound (E) is 100 parts by weight of the total amount of the compound (E) with the polycarbonate resin (A), the aromatic polycarbonate resin (B) and the impact strength modifier (C). The polycarbonate resin composition according to claim 1 or 2, which is 0.8 ppm by weight or more and 1000 ppm by weight or less in terms of the amount of metal in ().   The polycarbonate according to claim 2 or 3, wherein the compound (E) is at least one selected from the group consisting of inorganic salts (including carbonates), carboxylates, phenolates, halogen compounds, and hydroxide compounds. Resin composition.   The polycarbonate resin composition according to any one of claims 2 to 4, wherein the compound (E) is at least one selected from the group consisting of a lithium compound, a sodium compound, a potassium compound, and a cesium compound.   The polycarbonate resin composition according to claim 5, wherein the content of the acidic compound (D) is 0.5 to 5 times the mol of the metal in the compound (E).   The molded object obtained by shape | molding the polycarbonate resin composition of any one of Claims 1-6. For a composition comprising a polycarbonate resin (A) containing a structural unit derived from a compound represented by the following formula (1) and an aromatic polycarbonate resin (B), A previous step (i) of melt-kneading the compound, at least one compound (D) selected from a compound of a long-period periodic table Group II metal; and
The manufacturing method of a polycarbonate resin composition which has the post-process (ii) which melt-kneads the resin composition obtained by this process, an impact strength modifier (C), and an acidic compound (D) after this process.

The method for producing a polycarbonate resin composition according to claim 8, wherein the step (i) is performed under reduced pressure. The manufacturing method of the polycarbonate resin composition of Claim 8 or 9 which performs the said process (i) on the conditions that a vacuum degree is 30 kPa or less.   The compound (E) is at least one selected from the group consisting of inorganic salts (including carbonates), carboxylates, phenolates, halogen compounds, and hydroxide compounds. The manufacturing method of the polycarbonate resin composition as described in any one of.   The method for producing a polycarbonate resin composition according to any one of claims 8 to 11, wherein the compound (E) is at least one selected from the group consisting of a lithium compound, a sodium compound, a potassium compound, and a cesium compound. .   The addition amount of the said acidic compound (D) is 0.5 times mole or more and 5 times mole or less with respect to the metal addition amount of the said compound (E), It is any one of Claims 8-12. A process for producing a polycarbonate resin composition.