Polycarbonate-based resin composition

Abstract

This polycarbonate-based resin composition has a specific viscosity average molecular weight (MvPC) and contains a polycarbonate-based resin (S) that contains: a polycarbonate-polyorganosiloxane copolymer (S-1) that includes a polycarbonate block (A-1) containing a repeating unit having a specific structure and a polyorganosiloxane block (A-2) having a specific average chain length and containing a repeating unit having a specific structure and a specific amount; and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1). The difference between the viscosity average molecular weight (MvPC) of the polycarbonate-based resin (S) and the viscosity average molecular weight (MvSi) of the polycarbonate-polyorganosiloxane copolymer (S-1) (MvSi-MvPC) is -3100-6000.

Description

Polycarbonate resin composition

[0001] The present invention relates to a polycarbonate resin composition and a molded article thereof.

[0002] Polycarbonate-polyorganosiloxane copolymers (hereinafter sometimes abbreviated as "PC-POS copolymers") have attracted attention due to their excellent properties, such as high impact resistance, chemical resistance, and flame retardancy. Therefore, they are expected to be widely used in various fields, including electrical and electronic equipment and the automotive industry. In particular, they are being used extensively in housings for mobile phones, mobile personal computers, digital cameras, video cameras, power tools, and other everyday items. A typical polycarbonate typically used is a homopolycarbonate made using 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A) as the dihydric phenol raw material. To improve the physical properties of this homopolycarbonate, such as flame retardancy and impact resistance, a polycarbonate-polyorganosiloxane copolymer using polyorganosiloxane as a copolymerization monomer is known (Patent Document 1). To improve the impact resistance of a polycarbonate-based resin composition, particularly at low temperatures, a method using a long-chain polyorganosiloxane is known, as disclosed in Patent Document 2. However, this method suffers from the problem of reduced transparency. Conversely, to further improve the transparency of a polycarbonate-based resin composition, a method using a relatively short-chain polyorganosiloxane is known (see Patent Documents 3 and 4). However, this method suffers from the problem of reduced impact resistance. Patent Document 5 attempts to improve transparency while maintaining excellent impact resistance by blending two types of polycarbonate-polyorganosiloxane copolymers with different light transmittances, but the resulting transparency was not sufficient.

[0003] Japanese Patent No. 2662310 JP 2012-246430 A JP 8-81620 A JP 2011-46911 A JP 2006-523243 A

[0004] It is difficult to achieve both excellent transparency and excellent impact resistance, particularly low-temperature impact resistance, in a polycarbonate-based resin composition. The present inventors have recognized that further improvements are necessary to achieve both excellent transparency and excellent impact resistance, particularly when the viscosity-average molecular weight of the PC-POS copolymer is relatively high. An object of the present invention is to provide a polycarbonate-based resin composition containing a PC-POS copolymer having a relatively high viscosity-average molecular weight, which has excellent transparency and impact resistance, and a molded article thereof.

[0005] The present inventors have found that the above-mentioned problems can be solved by a polycarbonate-based resin composition that combines a PC-POS copolymer having a specific viscosity-average molecular weight with an aromatic polycarbonate-based resin other than the PC-POS copolymer having a specific viscosity-average molecular weight. That is, the present invention relates to the following items [1] to

[12] . [1] A polycarbonate-based resin composition comprising a polycarbonate-based resin (S) that includes a polycarbonate-polyorganosiloxane copolymer (S-1) that includes a polycarbonate block (A-1) containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1), wherein the viscosity-average molecular weight Mv of the polycarbonate-based resin (S) is 0.05 or more. ＰＣ is 20,000 or more and 30,000 or less, the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5 mass% or more and 9 mass% or less, the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60, and the viscosity average molecular weight Mv of the polycarbonate resin (S) is ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ The polycarbonate resin composition has a modulus of -3,100 or more and 6,000 or less.

[0006]

[0007] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a and b each independently represent an integer of 0 to 4.] [2] The viscosity average molecular weight Mv of the polycarbonate resin (S) ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ [3] The polycarbonate-based resin composition according to the above [1], wherein the viscosity average molecular weight Mv of the polycarbonate-based resin (S) is -1,500 or more and 6,000 or less. ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ [4] The polycarbonate-polyorganosiloxane copolymer (S-1) has a viscosity average molecular weight Mv of -500 or more and 6,000 or less. Ｓｉ[5] The polycarbonate-based resin composition according to any one of [1] to [4] above, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 8% by mass or less. [6] The polycarbonate-based resin composition according to any one of [1] to [5] above, wherein the polyorganosiloxane block (A-2) is a block unit represented by any one of the following general formulas (II-I), (II-II), and (II-III):

[0008]

[0009] [In the formula, R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different. Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 O-R 10 The R represents —O—, and a plurality of Ys may be the same or different. 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 represents a diarylene group. 10represents a linear, branched, or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. n is as defined above, and p is an integer of 1 or more and n-2 or less.] [7] The polycarbonate-based resin composition according to any one of [1] to [6] above, wherein a haze value of a 3 mm-thick molded article measured in accordance with ISO 14782:1999 is 0.1 or more and 1.0 or less. [8] The polycarbonate-based resin composition according to any one of [1] to [7] above, wherein the polycarbonate-polyorganosiloxane copolymer (S-1) is substantially free of block units (A-3) represented by the following general formula (IV):

[0010]

[0011] [In the formula, R ２１ ~R ２４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ２５ is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. ２ is a divalent aliphatic group having 1 to 10 carbon atoms. m represents an average chain length and is an integer of 10 or more.] [9] The polycarbonate-based resin composition according to any one of the above items [1] to [8], wherein the polycarbonate-polyorganosiloxane copolymer (S-1) consists solely of a polycarbonate block (A-1) and a polyorganosiloxane block (A-2).

[10] The polycarbonate-based resin composition according to any one of the above items [1] to [9], wherein the average chain length n of the polyorganosiloxane block (A-2) is greater than 30 and less than 60.

[11] The polycarbonate-based resin composition according to any one of the above items [1] to

[10] , wherein the viscosity-average molecular weight of the aromatic polycarbonate-based resin (S-2) is 11,000 or more and 30,000 or less.

[12] A molded article obtained by molding the polycarbonate resin composition according to any one of the above items [1] to

[11] .

[0012] According to the present invention, it is possible to provide a polycarbonate resin composition containing a PC-POS copolymer having excellent transparency and impact resistance and a relatively high viscosity average molecular weight, and a molded article thereof.

[0013] Fig. 1 is a cross-sectional view of a test piece used in the evaluation of chemical resistance. Fig. 2 is a cross-sectional view in the short direction of a jig used in the evaluation of chemical resistance. Fig. 3 is a schematic view of a test piece fixed to a jig used in the evaluation of chemical resistance.

[0014] The polycarbonate-based resin composition of the present invention is a polycarbonate-based resin composition comprising a polycarbonate-based resin (S) including a polycarbonate-polyorganosiloxane copolymer (S-1) containing a polycarbonate block (A-1) containing a specific repeating unit and a polyorganosiloxane block (A-2) containing a specific repeating unit, and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1), wherein the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.05 to 0.15. Ｓｉ is 20,000 or more and 30,000 or less, the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5 mass% or more and 9.0 mass% or less, the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60, and the viscosity average molecular weight Mv of the polycarbonate resin (S) is ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ is between -3,100 and 6,000.

[0015] The polycarbonate resin composition and molded article thereof of the present invention will be described in detail below. In this specification, the preferred definitions can be adopted arbitrarily, and a combination of preferred definitions can be considered more preferable. In this specification, the expression "XX to YY" means "XX or more and YY or less."

[0016] [Polycarbonate-Based Resin Composition] The polycarbonate-based resin composition of the present invention comprises a polycarbonate-based resin (S) including a polycarbonate-polyorganosiloxane copolymer (S-1) and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1).

[0017] <Polycarbonate Resin (S)> The polycarbonate resin (S) constituting the polycarbonate resin composition of the present invention comprises a polycarbonate-polyorganosiloxane copolymer (S-1) containing a polycarbonate block (A-1) containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), and an aromatic polycarbonate resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1), and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) is Ｓｉ is 20,000 or more and 30,000 or less, the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5 mass% or more and 9.0 mass% or less, the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60, and the viscosity average molecular weight Mv of the polycarbonate resin (S) is ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ is between -3,100 and 6,000.

[0018] [In the formula, R 1 and R 2each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. R 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a and b each independently represent an integer of 0 to 4.

[0019] (Polycarbonate-Polyorganosiloxane Copolymer (S-1)) The polycarbonate-polyorganosiloxane copolymer (S-1) comprises a polycarbonate block (A-1) containing a repeating unit represented by the above general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the above general formula (II), the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9.0% by mass or less, and the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60. Hereinafter, the polycarbonate-polyorganosiloxane copolymer (S-1) may be abbreviated as "PC-POS copolymer (S-1)."

[0020] Polycarbonate block (A-1) In the above general formula (I), R 1 and R 2 The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 and R 2 Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" includes linear and branched groups, and the same applies hereinafter in the specification), various pentyl groups, and various hexyl groups. 1 and R2 The alkoxy groups independently represented by the formula (I) include those having the above alkyl group as the alkyl group moiety.

[0021] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and an alkylene group having 5 to 10 carbon atoms is preferred. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group, and an alkylidene group having 5 to 10 carbon atoms is preferred, and an alkylidene group having 5 to 8 carbon atoms is more preferred. The aryl moiety of the aryl alkylene group represented by X includes aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and the alkylene group includes the alkylenes described above. The aryl moiety of the aryl alkylidene group represented by X includes aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and the alkylidene group includes the alkylidene groups described above.

[0022] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, a compound in which a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a compound in which a and b are 0 and X is an alkylidene group having 3 carbon atoms, particularly an isopropylidene group, is preferred.

[0023] The polycarbonate block (A-1) preferably consists essentially of repeating units represented by the above general formula (I).

[0024] Polyorganosiloxane Block (A-2) The polyorganosiloxane block (A-2) is a structural unit present between the two most adjacent polycarbonate bonds on the main chain of the PC-POS copolymer (S-1), and contains at least one repeating unit represented by the general formula (II) above. 3 or R 4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 3 or R 4 Examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. 3 or R 4 The alkoxy group represented by the formula (I) may be one in which the alkyl group moiety is the above-mentioned alkyl group. 3 or R 4 Examples of the aryl group represented by R include a phenyl group and a naphthyl group. 3 and R 4 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably a methyl group.

[0025] The average chain length n of the polyorganosiloxane block (A-2) contained in the PC-POS copolymer (S-1) is 20 or more and less than 60, preferably 20 or more and 55 or less, more preferably 25 or more and 50 or less, and even more preferably more than 30 and 43 or less. When the average chain length is within the above range, a polycarbonate resin composition having superior transparency and impact resistance, particularly impact resistance at low temperatures, can be obtained. In one preferred embodiment, the PC-POS copolymer (S-1) is substantially free of block units derived from polyorganosiloxanes having an average chain length of 60 or more as the polyorganosiloxane block (A-2). The average chain length of the polyorganosiloxane block (A-2) refers to the number of —SiR groups contained in the polyorganosiloxane block (A-2) present between the two most adjacent polycarbonate bonds on the main chain of the PC-POS copolymer (S-1). ３ R ４ The average number of repeating units represented by the general formula (II) contained in the polyorganosiloxane block (A-2) is n-1. The average chain length n of the polyorganosiloxane block (A-2) contained in the PC-POS copolymer (S-1) is calculated by nuclear magnetic resonance (NMR) measurement.

[0026] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) (also referred to as the polyorganosiloxane amount) is 0.5% by mass or more and 9% by mass or less. When the polyorganosiloxane amount in the PC-POS copolymer (S-1) is within the above range, a polycarbonate resin composition having excellent transparency and impact resistance can be obtained. The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) is preferably 0.5% by mass or more and 8% by mass or less, more preferably 0.5% by mass or more and less than 8% by mass, even more preferably 2% by mass or more and 7.5% by mass or less, still more preferably 4% by mass or more and 7% by mass or less, and particularly preferably 5% by mass or more and 7% by mass or less. In this specification, the "content of polyorganosiloxane block (A-2) in PC-POS copolymer (S-1)" refers to the percentage of the mass of the general formula (II) relative to the total mass of the polycarbonate block (A-1), the general formula (II), and, if necessary, the terminal structure derived from the terminal terminator contained in the PC-POS copolymer (S-1), as described below. The same applies to the "content of polyorganosiloxane block (A-2) in polycarbonate resin (S)" and the "content of polyorganosiloxane block (A-2) in a polycarbonate resin composition," which will be described later. The content of polyorganosiloxane block (A-2) in PC-POS copolymer (S-1) is calculated by nuclear magnetic resonance (NMR) measurement. Specifically, 1 H-NMR measurement is carried out, and the value is calculated from the integrated values ​​of the peak derived from formula (I), the peak derived from formula (II), and the peak derived from the terminal group.

[0027] A preferred embodiment of the polyorganosiloxane block (A-2) containing the repeating unit represented by the above general formula (II) is a block unit represented by any one of the following general formulas (II-I) to (II-III).

[0028]

[0029] [In the formula, R 3 ~R 6each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R 3 ~R 6 may be the same or different. Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 O-R 10 The R represents —O—, and the plurality of Ys may be the same or different. 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 represents a diarylene group. 10 represents a linear, branched, or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. n is as defined above. p is an integer of 1 or more and n-2 or less.]

[0030] R 3 ~R 6 The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 3 ~R 6 Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 3 ~R 6 The alkoxy groups each independently represent include those in which the alkyl group moiety is the above-mentioned alkyl group. 3 ~R 6 Examples of the aryl group that each R represents independently include a phenyl group and a naphthyl group. 3 ~R6 is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. 3 ~R 6 are preferably all methyl groups.

[0031] Y indicates -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R 9 -O- or -R 7 O-R 10 In —O—, R 7 is bonded to the Si atom. In -COO- represented by Y, the C atom is bonded to the Si atom. In -R represented by Y, 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R 9 -O- or -R 7 O-R 10 R in -O- 7 The linear or branched alkylene group represented by R is an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. 7 The cyclic alkylene group represented by the formula (I) includes a cycloalkylene group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

[0032] R 7 The aryl-substituted alkylene group represented by may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring, and its specific structure can be, for example, the structure of the following general formula (i) or (ii). 7 represents an aryl-substituted alkylene group, the alkylene group is bonded to the Si atom. 7 O-, -R 7 COO-, -R 7 NH-, -R7 NR 8 -, -R 7 COO-R 9 -O- or -R 7 O-R 10 In —O—, the arylene group is R 7 is bonded to an oxygen atom, carbon atom, or nitrogen atom adjacent to the

[0033]

[0034] [In the formula, c represents a positive integer, and is usually an integer of 1 to 6.]

[0035] R 7 , R 9 and R 10 The diarylylene group represented by the formula (I) is a group in which two arylene groups are linked directly or via a divalent organic group, and specifically, -Ar 1 -W-Ar 2 -, where Ar 1 and Ar 2 represents an arylene group, and W represents a single bond or a divalent organic group. The divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group, or a trimethylene group. R 7 , Ar 1 and Ar 2 Examples of the arylene group represented by the formula (I) include arylene groups having 6 to 14 ring carbon atoms, such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may have any substituent, such as an alkoxy group or an alkyl group.

[0036] R 8 The alkyl group represented by R is a straight or branched chain alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. 8 The alkenyl group represented by R is a straight-chain or branched-chain alkenyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. 8 Examples of the aryl group represented by R include a phenyl group and a naphthyl group. 8 Examples of the aralkyl group represented by R include a phenylmethyl group and a phenylethyl group. 10 The linear, branched or cyclic alkylene group represented by R 7is the same as:

[0037] Y is preferably —R 7 O- and R 7 is an aryl-substituted alkylene group. 7 is more preferably a residue of a phenolic compound having an alkyl group, and even more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol. Note that with respect to p in formula (II-II), it is preferable that p=n-p-2.

[0038] β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples thereof include divalent groups represented by the following general formulas (iii) to (vii).

[0039]

[0040] For example, examples of the block unit represented by the following general formula (II-I) include block units represented by the following general formulae (II-I-1) to (II-I-11).

[0041]

[0042] In the above general formulae (II-I-1) to (II-I-11), R 3 ~R 6 , n-1 and R 8 is the same as above, and the preferred ones are also the same. c represents a positive integer, usually an integer of 1 to 6. Among these, from the viewpoint of ease of polymerization of polyorganosiloxane, the block unit represented by the above general formula (II-I-1) is preferred. Furthermore, from the viewpoint of ease of availability, the block unit represented by the above general formula (II-I-2) and the block unit represented by the above general formula (II-I-3) are preferred.

[0043] Another preferred embodiment of the polyorganosiloxane block (A-2) is a block unit represented by the following general formula (II-IV).

[0044]

[0045] [wherein R3 and R 4 is the same as above. r×m is equal to n above.] The average chain length of the polyorganosiloxane block represented by general formula (II-IV) is (r×m), and the range of (r×m) is the same as n above.

[0046] From the viewpoints of transparency and impact resistance at low temperatures, in one preferred embodiment, the PC-POS copolymer (S-1) is substantially free of block units (A-3) represented by the following general formula (IV) as the polyorganosiloxane blocks (A-2):

[0047]

[0048] [In the formula, R ２１ ~R ２４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ２５ is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. ２ is a divalent aliphatic group having 1 to 10 carbon atoms, and m represents the average chain length and is an integer of 10 or more.

[0049] R ２１ ~R ２４ The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ２１ ~R ２４ Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. ２１ ~R ２４ The alkoxy groups each independently represent include those in which the alkyl group moiety is the above-mentioned alkyl group. ２１ ~R ２４ Examples of the aryl group that each independently represents include a phenyl group and a naphthyl group.

[0050] R ２５Examples of the alkyl group having 1 to 6 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. ２５ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ２５ The alkoxy group having 1 to 6 carbon atoms represented by R is a group in which the alkyl group moiety is the above-mentioned alkyl group. ２５ Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a toluyl group, a dimethylphenyl group, and a naphthyl group.

[0051] Q 2 The divalent aliphatic group having 1 to 10 carbon atoms represented by is preferably a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms. The number of carbon atoms in the saturated aliphatic group is preferably 1 to 8, more preferably 2 to 6, even more preferably 3 to 6, and still more preferably 4 to 6. m is the average chain length and is an integer of 10 or more.

[0052] A specific embodiment of the repeating unit (A-3) is a structure represented by the following formula (IV-I).

[0053]

[0054] [In the formula, m is as defined above.]

[0055] In a preferred embodiment of the PC-POS copolymer (S-1), the main chain of the PC-POS copolymer (S-1) consists solely of the polycarbonate block (A-1), the polyorganosiloxane block (A-2), and, if necessary, a terminal structure derived from a terminal terminator described below.

[0056] Physical Properties of Polycarbonate-Polyorganosiloxane Copolymer (S-1) The viscosity average molecular weight of the PC-POS copolymer (S-1) is preferably 18,500 or more and 25,000 or less, more preferably 20,000 or more and 25,000 or less, even more preferably 20,000 or more and 24,000 or less, and particularly preferably 21,000 or more and 23,500 or less. Viscosity average molecular weight Mv ＳｉWithin the above range, a polycarbonate resin composition having superior transparency and impact resistance, particularly low-temperature impact resistance, can be obtained. The viscosity-average molecular weight (Mv) of the PC-POS copolymer (S-1) can be appropriately adjusted to a desired molecular weight by using a molecular weight modifier (terminal capping agent) or the like depending on the intended use or product.

[0057] The viscosity average molecular weight (Mv) is a value calculated from the intrinsic viscosity [η] of a methylene chloride solution at 20° C. using the following Schnell formula:

[0058]

[0059] - Method for Producing Polycarbonate-Polyorganosiloxane Copolymer (S-1) The PC-POS copolymer (S-1) can be produced by known production methods such as interfacial polymerization (phosgene method), pyridine method, and transesterification method. In particular, when interfacial polymerization is employed, the process of separating the organic phase containing the PC-POS copolymer from the aqueous phase containing unreacted materials, catalyst residues, and the like is easy, and the organic phase containing the PC-POS copolymer and the aqueous phase are easily separated in each washing step, such as alkali washing, acid washing, and pure water washing. Therefore, the PC-POS copolymer can be obtained efficiently. For example, the method described in JP 2014-80462 A can be used as a method for producing the PC-POS copolymer.

[0060] In the interfacial polymerization method (phosgene method), for example, a polycarbonate oligomer is prepared in advance by polymerizing a dihydric phenol compound with a carbonate precursor such as phosgene, and then the polycarbonate oligomer, polyorganosiloxane, and optionally a dihydric phenol compound are polymerized to produce the PC-POS copolymer (S-1). Specifically, the polycarbonate oligomer and polyorganosiloxane prepared in advance, which will be described later, are dissolved in a water-insoluble organic solvent (e.g., methylene chloride), and an alkaline compound aqueous solution (e.g., sodium hydroxide aqueous solution) of a dihydric phenol compound (e.g., bisphenol A) is added. The copolymer can be produced by an interfacial polycondensation reaction using a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzylammonium chloride) as a polymerization catalyst in the presence of a terminal terminator (a monohydric phenol such as p-tert-butylphenol). The PC-POS copolymer (S-1) can also be produced by copolymerizing, for example, a polyorganosiloxane, a dihydric phenol compound, and phosgene, a carbonate ester, or a chloroformate.

[0061] As the polyorganosiloxane used as the raw material, those represented by the following general formula (1), (2) and / or (3) can be used.

[0062]

[0063] [In the formula, R 3 ~R 6 , Y, β, n and p are as defined above.] R 3 ~R 6 Specific examples and preferred values ​​of Y, β, n, and p are as described above. Z represents a hydrogen atom or a halogen atom, and multiple Zs may be the same or different. For example, polyorganosiloxanes represented by general formula (1) include compounds of the following general formulas (1-1) to (1-11).

[0064]

[0065] In the above general formulas (1-1) to (1-11), R 3 ~R 6 , n-1 and R 8is the same as above, and the preferred ones are also the same. c represents a positive integer, usually an integer of 1 to 6. Among these, from the viewpoint of ease of polymerization of polyorganosiloxane, phenol-modified polyorganosiloxane represented by the above general formula (1-1) is preferred. Furthermore, from the viewpoint of ease of availability, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above general formula (1-2), and α,ω-bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above general formula (1-3), are preferred.

[0066] Alternatively, the polyorganosiloxane raw material may be one having the following general formula (4):

[0067]

[0068] [In the formula, R 3 , R 4 , r and m are the same as above.]

[0069] It is preferable not to use polyorganosiloxanes represented by the following general formula (5) or (6) as the raw material polyorganosiloxane.

[0070]

[0071] [In the formula, R ２１ ~R ２５ , Q ２ and m are the same as above.]

[0072]

[0073] [In the formula, m is the same as defined above.]

[0074] The method for producing the polyorganosiloxane is not particularly limited. For example, according to the method described in JP-A-11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize an α,ω-dihydrogenorganopentasiloxane, and then a phenolic compound (e.g., 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) is added to the α,ω-dihydrogenorganopentasiloxane in the presence of a hydrosilylation catalyst to produce a crude polyorganosiloxane. According to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (an acidic catalyst), and the resulting α,ω-dihydrogenorganopolysiloxane is subjected to an addition reaction with a phenolic compound or the like in the presence of a hydrosilylation catalyst, as described above, to obtain a crude polyorganosiloxane. The α,ω-dihydrogenorganopolysiloxane can be used by adjusting the chain length n appropriately depending on the polymerization conditions, or a commercially available α,ω-dihydrogenorganopolysiloxane can be used. Specifically, the α,ω-dihydrogenorganopolysiloxane described in Japanese Patent Laid-Open No. 2016-098292 can be used.

[0075] Polycarbonate oligomers can be produced by reacting a dihydric phenol compound with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, or chloroform. When producing a polycarbonate oligomer using a transesterification method, it can also be produced by reacting a dihydric phenol compound with a carbonate precursor such as diphenyl carbonate. As the dihydric phenol compound, it is preferable to use a dihydric phenol compound represented by the following general formula (viii):

[0076]

[0077] In the formula, R 1 , R 2 , a, b and X are as defined above.

[0078] Examples of dihydric phenol compounds represented by the general formula (viii) include bis(hydroxyphenyl)alkane compounds such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)cycloalkane; bis(4-hydroxyphenyl)oxide; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl)sulfoxide; and bis(4-hydroxyphenyl)ketone. These dihydric phenol compounds may be used alone or in combination of two or more. Among these, bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred. When bisphenol A is used as the dihydric phenol compound, the resulting PC-POS copolymer has the general formula (i) in which X is an isopropylidene group and a=b=0.

[0079] Examples of dihydric phenol compounds other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, etc. These dihydric phenol compounds may be used alone or in combination of two or more.

[0080] Examples of bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane.

[0081] Examples of bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 1,1-bis(4-hydroxyphenyl)cyclododecane, etc. Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, etc.

[0082] Examples of dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, etc. Examples of dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, etc. Examples of dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc.

[0083] Examples of dihydroxydiphenyls include 4,4'-dihydroxydiphenyl, etc. Examples of dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc. Examples of dihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

[0084] Other dihydric phenol compounds include, for example, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.

[0085] A terminal terminator (molecular weight regulator) can be used to adjust the molecular weight of the resulting PC-POS copolymer. Examples of terminal terminators include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0086] After the interfacial polycondensation reaction, the mixture is left to stand for an appropriate period to separate into an aqueous phase and an organic solvent phase [separation step], the organic solvent phase is washed (preferably with a basic aqueous solution, an acidic aqueous solution, and water in that order) [washing step], and the resulting organic phase is concentrated [concentration step] and dried [drying step], thereby obtaining a PC-POS copolymer (S-1).

[0087] (Aromatic Polycarbonate Resin (S-2)) The polycarbonate resin (S) further includes an aromatic polycarbonate resin (S-2) other than the PC-POS copolymer (S-1). The aromatic polycarbonate resin (S-2) has a main chain comprising repeating units represented by the following general formula (III). The polycarbonate resin is not particularly limited, and various known polycarbonate resins can be used. One type of aromatic polycarbonate resin may be used alone, or two or more types may be used in combination. Unlike the PC-POS copolymer (S-1), the aromatic polycarbonate resin (S-2) has a structure that does not include a polyorganosiloxane block as represented by formula (II). For example, the aromatic polycarbonate resin (S-2) is preferably a homopolycarbonate resin, more preferably a homopolycarbonate resin whose main chain comprises substantially only repeating units represented by the following general formula (III).

[0088]

[0089] [In the formula, R 9 and R 10 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X' represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. d and e each independently represent an integer of 0 to 4.

[0090] R 9 and R 10 Specific examples of R １ and R ２ The same as those listed above and the same preferred examples are also listed above. 9 and R 10 is more preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Specific examples of X' include the same as those of X, and the preferred examples are also the same. d and e each independently represent preferably 0 to 2, more preferably 0 or 1.

[0091] Physical Properties of Aromatic Polycarbonate Resin (S-2) The viscosity average molecular weight of the aromatic polycarbonate resin (S-2) is preferably from 11,000 to 30,000, more preferably from 13,500 to 26,000, and even more preferably from 16,000 to 24,000. When the viscosity average molecular weight is within the above range, a polycarbonate resin composition having superior transparency and impact resistance, particularly low-temperature impact resistance, can be obtained.

[0092] -Method for producing aromatic polycarbonate resin (S-2) Aromatic polycarbonate resin (S-2) can be obtained by conventional polycarbonate production methods, such as an interfacial polymerization method in which a dihydric phenol compound and phosgene are reacted in the presence of an inert organic solvent or an alkaline aqueous solution, followed by polymerization by adding a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt; a melt polymerization method (transesterification method) in which a dihydric alcohol and a carbonate diester are subjected to a transesterification reaction in a molten state without using a solvent and a basic catalyst is added; or a pyridine method in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced to produce the polycarbonate directly. During the above reaction, a molecular weight modifier (end-capping agent), a branching agent, etc. may be used as necessary. The dihydric phenol compound is a compound having two phenolic hydroxyl groups in the molecule, and examples thereof include those represented by the following general formula (III'):

[0093] [In the formula, R 9 , R 10 , X′, d, and e are as defined above, and the preferred values ​​are also the same.]

[0094] Specific examples of the dihydric phenol compound include those described above in the production method for PC-POS (S-1), and preferred examples are also the same. Among them, bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred.

[0095] (Physical Properties of Polycarbonate Resin (S)) Viscosity Average Molecular Weight Mv of Polycarbonate Resin (S) ＰＣThe viscosity average molecular weight Mv is 20,000 or more and 30,000 or less. ＰＣ When the viscosity average molecular weight Mv of the polycarbonate resin (S) is within the above range, a polycarbonate resin composition having excellent transparency, impact resistance, and chemical resistance can be obtained. ＰＣ is preferably 20,000 or more and 27,000 or less, more preferably 20,000 or more and 25,000 or less, even more preferably 20,000 or more and 22,000 or less, and still more preferably 21,000 or more and 22,000 or less.

[0096] Since the polycarbonate resin (S) contains PC-POS (S-1) and an aromatic polycarbonate resin (S-2) other than the PC-POS copolymer (S-1), the viscosity average molecular weight Mv ＰＣ and the viscosity average molecular weight Mv of the PC-POS copolymer (S-1) Ｓｉ The viscosity average molecular weight Mv of the polycarbonate resin (S) may not necessarily coincide with the viscosity average molecular weight Mv of the polycarbonate resin (S). ＰＣ and the viscosity average molecular weight Mv of the PC-POS copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ is between -3,100 and 6,000. Ｓｉ -Mv ＰＣ When the viscosity average molecular weight Mv of the polycarbonate resin (S) is within the above range, a polycarbonate resin composition having excellent transparency and impact resistance can be obtained. ＰＣ and the viscosity average molecular weight Mv of the PC-POS copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ is preferably −1,500 or more and 6,000 or less, more preferably −500 or more and 6,000 or less, even more preferably −500 or more and 4,000 or less, and particularly preferably −500 or more and 3,000 or less. Ｓｉ -Mv ＰＣ Within the above range, a polycarbonate resin composition having better transparency and impact resistance, particularly impact resistance at low temperatures, and further chemical resistance can be obtained.

[0097] The content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin (S) is preferably 0.5% by mass or more but less than 8% by mass, more preferably 1% by mass or more but less than 6% by mass, even more preferably 2.7% by mass or more but less than 5% by mass, and particularly preferably 3.1% by mass or more but less than 5% by mass. When the content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin (S) is within the above range, a polycarbonate-based resin composition having superior transparency and impact resistance, particularly impact resistance at low temperatures, can be obtained. The content of the polyorganosiloxane block (A-2) in the polycarbonate-based resin (S) is calculated by nuclear magnetic resonance (NMR) measurement, similar to the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) described above.

[0098] Viscosity average molecular weight Mv of polycarbonate resin (S) ＰＣ The content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) can be adjusted, for example, by adjusting the content ratio of the PC-POS copolymer (S-1) to the aromatic polycarbonate resin (S-2). The content of the PC-POS copolymer (S-1) in the polycarbonate resin (S) is preferably 5% by mass or more and 99% by mass or less, more preferably 15% by mass or more and 90% by mass or less, even more preferably 30% by mass or more and 80% by mass or less, still more preferably 40% by mass or more and 70% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less. The content of the aromatic polycarbonate resin (S-2) in the polycarbonate resin (S) is preferably 1% by mass or more and 95% by mass or less, more preferably 10% by mass or more and 85% by mass or less, even more preferably 20% by mass or more and 70% by mass or less, still more preferably 30% by mass or more and 60% by mass or less, and particularly preferably 30% by mass or more and 50% by mass or less.

[0099] <Other Additives> The polycarbonate resin composition of the present invention may further contain other additives within the range that does not impair the effects of the present invention. Examples of other components include hydrolysis stabilizers, antioxidants, ultraviolet absorbers, flame retardants, flame retardant auxiliaries, reinforcing materials, fillers, impact-improving elastomers, pigments, dyes, etc.

[0100] <Antioxidant> A specific example of the other additives is an antioxidant. By blending an antioxidant into the polycarbonate resin composition, it is possible to suppress oxidative degradation of the polycarbonate resin composition when it is melted, and to suppress coloration and the like due to oxidative degradation. As the antioxidant, a phosphorus-based antioxidant and / or a phenol-based antioxidant is preferably used.

[0101] Examples of phenolic antioxidants include hindered phenols such as n-octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and pentaerythrityl tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Among these antioxidants, those having a pentaerythritol diphosphite structure, such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and triphenylphosphine are preferred.

[0102] Examples of commercially available phenolic antioxidants include Irganox 1010 (trade name, manufactured by BASF Japan Ltd.), Irganox 1076 (trademark, manufactured by BASF Japan Ltd.), Irganox 1330 (trade name, manufactured by BASF Japan Ltd.), Irganox 3114 (trade name, manufactured by BASF Japan Ltd.), BHT (trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), CYANOX 1790 (trade name, manufactured by SOLVAY), and Sumilizer GA-80 (trade name, manufactured by Sumitomo Chemical Co., Ltd.).

[0103] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl(2-ethylhexyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, diphenyl isooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono(tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-ethylhexyl) phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 4,4'-isopropylidenediphenol dodecyl phosphite, sphite, 4,4'-isopropylidenediphenol tridecyl phosphite, 4,4'-isopropylidenediphenol tetradecyl phosphite, 4,4'-isopropylidenediphenol pentadecyl phosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)ditridecyl phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl -4-methylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris(2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl)butane, 3,4,5,6-dibenzo-1,Examples of such phosphine include 2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, and phenylnaphthylbenzylphosphine.

[0104] Examples of commercially available phosphorus-based antioxidants include Irgafos 168 (trade name, manufactured by BASF Japan Ltd.), Irgafos 12 (trade name, manufactured by BASF Japan Ltd.), Irgafos 38 (trade name, manufactured by BASF Japan Ltd.), Adeka STAB 2112 (trade name, manufactured by ADEKA Corporation), Adeka STAB C (trade name, manufactured by ADEKA Corporation), Adeka STAB 329K (trade name, manufactured by ADEKA Corporation), Adeka STAB PEP36 (trade name, manufactured by ADEKA Corporation), JC-263 (trade name, manufactured by Johoku Chemical Industry Co., Ltd.), Sandstab P-EPQ (trade name, manufactured by Clariant), and Doverphos S-9228PC (trade name, manufactured by Dover Chemical Co., Ltd.).

[0105] The antioxidants can be used alone or in combination of two or more. The content of the antioxidant in the polycarbonate resin composition of the present invention is preferably 0.001 to 0.5 parts by mass, preferably 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.3 parts by mass, per 100 parts by mass of the polycarbonate resin (S). When the content of the antioxidant per 100 parts by mass of the polycarbonate resin (S) is within the above range, a sufficient antioxidant effect can be obtained and mold contamination during molding can be suppressed.

[0106] <Ultraviolet Absorber> Another specific example of the other additives is an ultraviolet absorber. Suitable examples of the ultraviolet absorber include benzotriazole compounds, benzoxazine compounds, salicylate compounds, malonic acid ester compounds, oxalyl alanide compounds, triazine compounds, benzophenone compounds, and cyanoacrylate compounds.

[0107] Specific examples of benzotriazole compounds include 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-[2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2,2'-methylene-bis[4-methyl-6-(benzotriazol-2-yl)phenol], and 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol).

[0108] Specific examples of triazine compounds include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-bis-2,4-dimethylphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, etc. Specific examples of benzophenone compounds include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-ethoxy-benzophenone, etc. Specific examples of cyanoacrylate compounds include 2-ethyl-2-cyano-3,3-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate, 1,3-bis-[2'-cyano-3,3'-diphenylacryloyloxy]-2,2-bis-[(2-cyano-3',3'-diphenylacryloyl)oxy]methylpropane, and the like.

[0109] Among these, at least one selected from the group consisting of benzotriazole-based compounds, malonic acid ester-based compounds, triazine-based compounds, and benzoxazine-based compounds is preferred. Examples of commercially available ultraviolet absorbers include SEESORB 709 (manufactured by Shipro Chemical Co., Ltd., trade name), KEMISORB 79 (manufactured by Chemipro Chemical Co., Ltd., trade name), KEMISORB 279 (manufactured by Chemipro Chemical Co., Ltd., trade name), HOSTAVIN B-CAP (manufactured by Clariant, trade name), Tinuvin 234 (manufactured by BASF Japan Ltd., trade name), Tinuvin 1577 (manufactured by BASF Japan Ltd., trademark), and CYASORB UV-3638 F (manufactured by SOLVAY).

[0110] The above ultraviolet absorbers can be used alone or in combination of two or more. The content of the ultraviolet absorber in the polycarbonate resin composition of the present invention is preferably 0.01 parts by mass or more and 1 part by mass or less, more preferably 0.05 parts by mass or more and 0.7 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin (S). If the content of the ultraviolet absorber is within the above range, sufficient light resistance can be obtained, and if it is 1 part by mass or less, mold contamination used during molding can be sufficiently suppressed.

[0111] <Physical Properties of Polycarbonate Resin Composition> The polycarbonate resin composition of the present invention has the above-described composition, and thus can exhibit both excellent transparency and impact resistance.

[0112] The polycarbonate resin composition of the present invention has excellent transparency. Transparency can be evaluated, for example, by haze value. The polycarbonate resin composition of the present invention has a haze value of preferably 0.1 to 1.0, more preferably 0.2 to 0.9, and even more preferably 0.3 to 0.6, measured in accordance with ISO 14782:1999 (JIS K 7136:2000) for a 3 mm-thick molded article.

[0113] The polycarbonate resin composition of the present invention has excellent impact resistance, particularly excellent impact resistance at low temperatures. The impact resistance can be evaluated by Charpy impact strength, for example, as shown in the Examples described later. The polycarbonate resin composition of the present invention has excellent chemical resistance. The chemical resistance can be evaluated by, for example, the method shown in the Examples described later.

[0114] In a preferred embodiment of the polycarbonate resin composition of the present invention, domains (d) containing the polyorganosiloxane blocks (A-2) are present in a matrix primarily composed of the aromatic polycarbonate resin (S-2). The normalized variance of the average domain size of the domains (d) is preferably 40% or less, more preferably 20% or less, and even more preferably 18% or less. The average domain size and normalized variance of the domains (d) can be evaluated by small angle X-ray scattering (SAXS) according to the description in JP 2011-102364 A. The average domain size refers to the number average of the sizes of the individual domains (d). The normalized variance refers to a parameter obtained by normalizing the spread of the particle size distribution by the average domain size. Specifically, it is the value obtained by normalizing the variance of the size of the domains (d) by the average domain size, and is expressed by the following formula (X): Normalized variance (%) = σ / D ＡＶ (X) [wherein σ represents the standard deviation of the domain size of the domain (d), and D ＡＶrepresents the average domain size.] "Average domain size" and "normalized variance" refer to measurements obtained by small-angle X-ray scattering using a 1.0 mm-thick molded article formed by injection molding. Specifically, using a three-level injection-molded plate (width 50 mm, length 90 mm, thicknesses from the gate side of 3.0 mm (length 20 mm), 2.0 mm (length 45 mm), and 1.0 mm (length 25 mm), with a surface arithmetic mean roughness (Ra) of 0.03 μm), the average size and particle size distribution (normalized variance) of polydiorganosiloxane domains were measured by small-angle X-ray scattering at the intersections 5 mm from the end and 5 mm from the side of the 1.0 mm-thick section.

[0115] The content of the polyorganosiloxane block (A-2) in the polycarbonate resin composition is preferably 0.5% by mass or more and less than 8% by mass, more preferably 1% by mass or more and 6% by mass or less, even more preferably 2.7% by mass or more and 5% by mass or less, and particularly preferably 3.1% by mass or more and 5% by mass or less. When the content of the polyorganosiloxane block (A-2) in the polycarbonate resin composition is within the above range, a polycarbonate resin composition having better transparency and impact resistance at low temperatures can be obtained. The content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is calculated by nuclear magnetic resonance (NMR) measurement, similar to the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (S-1) described above.

[0116] [Molded Articles] Various molded articles can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, and the like using the melt-kneaded polycarbonate resin composition of the present invention or the resulting pellets as a raw material. In particular, the melt-kneaded pellets can be suitably used to produce injection-molded articles by injection molding and injection compression molding. Molded articles made from the polycarbonate resin composition of the present invention can be suitably used, for example, as exterior and internal parts of electric and electronic equipment such as televisions, radios, cameras, video cameras, audio players, DVD players, air conditioners, mobile phones, smartphones, transceivers, displays, computers, tablet devices, portable game consoles, stationary game consoles, wearable electronic devices, cash registers, calculators, copiers, printers, facsimiles, communication base stations, batteries, and robots; as well as exterior and internal parts of automobiles, railways, ships, aircraft, space industry equipment, and medical equipment; and as building material parts.

[0117] The present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples. The characteristic values ​​and evaluation results in each example were determined according to the following procedures.

[0118] (1) Average chain length and content of polyorganosiloxane block (A-2) 1 The average chain length and content of the polyorganosiloxane block (A-2) were calculated from the ratio of integral values ​​of methyl groups in the polydimethylsiloxane constituting the polyorganosiloxane block (A-2) by H-NMR measurement. In this specification, polydimethylsiloxane may be abbreviated as PDMS. <Method for Quantifying the Average Chain Length of the Polyorganosiloxane Block (A-2)> 1 H-NMR measurement conditions NMR device: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: 50TH5AT / FG2 Measurement nucleus: 1H Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5φ Sample amount: 30 to 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature Number of accumulations: 256 For allylphenol-terminated polydimethylsiloxane A: Integral value of the methyl group of the dimethylsiloxane portion observed around δ -0.02 to 0.5 B: Integral value of the methylene group of allylphenol observed around δ 2.50 to 2.75 Chain length of polydimethylsiloxane = (A / 6) / (B / 4) For eugenol-terminated polydimethylsiloxane A: Integral value of the methyl group of the dimethylsiloxane portion observed around δ -0.02 to 0.5 B: Integral value of the methylene group of eugenol observed around δ 2.40 to 2.70 Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0119] <Method for Quantifying the Content of Polyorganosiloxane Block (A-2)> Method for Quantifying the Amount of Polydimethylsiloxane Copolymerized in PTBP-Terminated Polycarbonate Copolymerized with Allylphenol-Terminated Polydimethylsiloxane 1 H-NMR measurement conditions NMR device: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: 50TH5AT / FG2 Measurement nucleus: 1 H Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of integrations: 256 NMR sample tube: 5φ Sample amount: 30 to 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature A: Integrated value of the methyl group of the BPA part observed around δ 1.5 to 1.9 B: -Si(CH ３ ) ２ C: Integrated value of methyl group in - moiety C: Integrated value of butyl group in p-tert-butylphenyl moiety observed around δ 1.2 to 1.4 a = A / 6 b = B / 6 c = C / 9 T = a + b + c f = a / T × 100 g = b / T × 100 h = c / T × 100 TW = f × 254 + g × 74.1 + h × 149 PDMS (wt%) = g × 74.1 / TW × 100

[0120] (2) Viscosity Average Molecular Weight The viscosity average molecular weight (Mv) was calculated by measuring the viscosity of a methylene chloride solution at 20°C using an Ubbelohde viscometer, determining the intrinsic viscosity [η] from the viscosity, and then using the following formula (Schnell formula):

[0121]

[0122] <Production Example 1: Production of Polycarbonate-Polyorganosiloxane Copolymer (S-1-1) (PC-PDMS (S-1-1))> (Step 1: Production of Polycarbonate Oligomer) Sodium dithionite was added to a 5.6% by mass aqueous solution of sodium hydroxide so that the concentration was 2000 ppm relative to the bisphenol A (BPA) to be dissolved later. BPA was dissolved in this so that the BPA concentration was 13.5% by mass, and an aqueous sodium hydroxide solution of BPA was prepared. This aqueous sodium hydroxide solution of BPA was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L / hr, methylene chloride at 15 L / hr, and phosgene at 4.0 kg / hr. The tubular reactor had a jacket, and cooling water was passed through the jacket to maintain the temperature of the reaction solution at 40 ° C. or less. The reaction solution leaving the tubular reactor was continuously introduced into a 40 L baffled tank reactor equipped with swept-back blades, and a reaction was carried out by adding an aqueous sodium hydroxide solution of BPA at a flow rate of 2.8 L / hr, a 25% by mass aqueous sodium hydroxide solution at a flow rate of 0.07 L / hr, water at a flow rate of 17 L / hr, and a 1% by mass aqueous triethylamine solution at a flow rate of 0.64 L / hr. The reaction solution overflowing from the tank reactor was continuously withdrawn and allowed to stand, allowing the aqueous phase to be separated and removed, and the methylene chloride phase to be collected. The polycarbonate oligomer thus obtained had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.

[0123] (Step 2: Production of PC-PDMS) A 50 L tank-type reactor equipped with a baffle, a paddle-type stirring blade, and a cooling jacket was charged with 15 L (i) of the polycarbonate oligomer solution (PCO) produced in the above Production Example, 8.6 L (ii) of methylene chloride (MC), a solution of 380 g (iv) of o-allylphenol-terminated polydimethylsiloxane (PDMS) having an average chain length n of 37 (iii) dissolved in 2 L of methylene chloride (v), and 11.2 mL (vi) of triethylamine (TEA). To this was added an aqueous sodium hydroxide solution (a solution of 170 g (vii) of sodium hydroxide in 2 L of pure water (viii)) with stirring, and the polycarbonate oligomer and the allylphenol-terminated PDMS were reacted for 20 minutes. This polymerization solution was mixed with a solution of p-tert-butylphenol (PTBP) in methylene chloride (PTBP 146.8 g (ix) dissolved in methylene chloride 0.5 L (x)), a sodium hydroxide solution of bisphenol A (sodium hydroxide 562 g (xi) and sodium dithionite (Na ２ S ２ O ４1.7 g (xii) of bisphenol A (xii) dissolved in 8.2 L (xiii) of purified water was added to an aqueous solution containing 826 g (xiv) of bisphenol A, and the resulting solution was polymerized for 40 minutes. 10 L (xv) of methylene chloride was added for dilution and the mixture was stirred for 20 minutes. The mixture was then separated into an organic phase containing polycarbonate-polydimethylsiloxane copolymer (PC-PDMS) and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was isolated. The resulting methylene chloride solution of PC-PDMS was washed sequentially with a 15% by volume solution of 0.03 mol / L sodium hydroxide and 0.2 mol / L hydrochloric acid, and then repeatedly washed with pure water until the electrical conductivity of the aqueous phase after washing was 5 μS / cm or less. The methylene chloride solution of PC-POS copolymer obtained by washing was concentrated and pulverized, and the resulting flakes were dried at 120°C under reduced pressure to produce PC-PDMS (S-1-1). The content of polyorganosiloxane block (A-2) determined by NMR of the obtained PC-PDMS (S-1-1) was 6.0% by mass, the average chain length of polyorganosiloxane block (A-2) was 37, and the viscosity average molecular weight Mv was 17,700.

[0124] <Production Examples 2 to 9: Production of PC-PDMS (S-1-2) to (S-1-9)> PC-PDMS (S-1-2) to (S-1-9) were produced in the same manner as in Production Example 1, except that the values ​​of (i) to (xv) shown in Table 1 were changed as shown in the same table. Table 1 shows the content of polyorganosiloxane block (A-2) of each PC-PDMS, the average chain length of the polyorganosiloxane block (A-2), and the viscosity average molecular weight Mv.

[0125]

[0126] <Aromatic Polycarbonate Resins (S-2)> (S-2-1): Toughlon FN1300 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 11,500] (S-2-2): Toughlon FN1500 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 14,500] (S-2-3): Toughlon FN1700 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 17,700] (S-2-4): Toughlon FN1900 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 19,100] (S-2-5): Toughlon FN2200 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 21,200] (S-2-6): Toughlon FN2500 (trade name) [manufactured by Idemitsu Kosan Co., Ltd., viscosity average molecular weight = 23,400] (S-2-7): Iupilon E-2000 (trade name) [manufactured by Mitsubishi Engineering-Plastics Corporation, viscosity average molecular weight = 25,500] (S-2-8): Novarex 7030PJ (trade name) [manufactured by Mitsubishi Engineering-Plastics Corporation, viscosity average molecular weight = 29,500]

[0127] <Other Components> Antioxidant: IRGAFOS 168 (trade name) [tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Japan Ltd.] Ultraviolet absorber: CYASORB UV-3638 F (trade name) [2,2'-(p-phenylene)di-3,1-benzoxazin-4-one, manufactured by SOLVAY] Ultraviolet absorber: KEMISORB 79 (trade name) [2-benzotriazolyl-4-tert-octylphenol, manufactured by Chemipro Chemical Co., Ltd.]

[0128] Examples 1 to 12, Comparative Examples 1 to 10 PC-PDMS (S-1-1) to (S-1-9) obtained in Production Examples 1 to 9 and other components were mixed in the blending ratios shown in Table 3, and fed to a vented twin-screw extruder (Toshiba Machine Co., Ltd., TEM35B), and melt-kneaded at a screw rotation speed of 150 rpm, a discharge rate of 20 kg / hr, and a resin temperature of 295 to 300 ° C. to obtain a pellet sample for evaluation. Using this pellet sample for evaluation, the content and Mv of the polyorganosiloxane block (A-2) in the polycarbonate resin composition were measured, and the transparency, impact resistance, and chemical resistance were evaluated by the following methods.

[0129] (1) Transparency: Haze Value The haze value of a 3 mm thick molded body was measured in accordance with ISO 14782:1999 (JIS K 7136:2000). The results are shown in Table 3. (2) Impact Resistance: Izod Impact Test The pellets obtained above were dried at 120 ° C for 8 hours, and then injection molded using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., NEX110, screw diameter 36 mm) at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C to prepare an IZOD test piece (63 × 13 × 3.2 mm). This test piece was notched by post-processing, and the Izod impact strength at -30 ° C and -40 ° C was measured in accordance with ASTM standard D-256. The results are shown in Table 3.

[0130] (3) Chemical Resistance: Sunscreen Resistance The pellets obtained above were dried at 120°C for 8 hours and then injection-molded using an injection molding machine (NEX110, manufactured by Nissei Plastic Industrial Co., Ltd., screw diameter 36 mm) at a cylinder temperature of 280°C and a mold temperature of 80°C to prepare test specimens having a longitudinal length of 95 mm and a cross section perpendicular to the longitudinal direction of the shape shown in Figure 1. Three test specimens were prepared from each pellet sample, with the thickness t in Figure 1, the vertical distance e from the centroid to the top surface, the length B in the short side direction of the top surface, and the acute angle θ formed between the plane perpendicular to the bottom surface and the side surface being the values ​​shown in Table 2 below.

[0131]

[0132] A jig was prepared in which three cylindrical shafts made of SUS304, each 10 mm in diameter and 70 mm in length, were aligned in the longitudinal direction and fixed parallel to each other so that their short-side cross sections were as shown in FIG. 2 . Specifically, one cylindrical shaft was designated the central shaft 22 and the other two were designated the end shafts 23. The perpendicular distance between the central axis 21 of the central shaft 22 and a plane containing the central axes 21 of the two end shafts 23 was 11.3 mm, and the distance L between the central axes 21 of the end shafts 23 was 60 mm. Each test specimen was fixed to the jig as shown in FIG. 3 . Specifically, each test specimen 31 was fixed to the jig so that the center of its bottom surface was in contact with the central shaft 32, its top surface was in contact with the end shafts 33, and the longitudinal direction of the test specimen 31 was perpendicular to the longitudinal direction of each shaft. The vertical distance G between the tangent plane 36 on the central shaft 32, including the contact point between the central shaft 32 and the test piece 31, and the tangent plane 35 on the end shafts 33, including the contact point between the end shafts 33 and the test piece 31, was 1.3 mm, and the distance L between the end shafts 33 was 60 mm. A sunscreen "NIVEA (trademark) SUN Protect and Moisture Lotion SPF30" (manufactured by Beiersdorf) was applied to the upper surface of the test piece in a width of 1 cm on each side in the longitudinal direction from the center. After 72 hours at 23°C, the presence or absence of cracks was visually confirmed, and changes in appearance were evaluated. Of the three test pieces prepared for each thickness t, the maximum test piece thickness t at which no cracks occurred in two or more test pieces was selected. ｍ The results are shown in Table 3.

[0133]

[0134]

[0135] Examples 13 to 14 Evaluation pellet samples were obtained in the same manner as in Example 1, except that the components were mixed in the proportions shown in Table 4. Using these evaluation pellet samples, the PDMS content and Mv of the polycarbonate resin composition were measured, and the transparency, impact resistance, and chemical resistance were evaluated in the same manner as in Example 1. Examples 13 and 14 also exhibited excellent transparency, impact resistance, and chemical resistance. Furthermore, Examples 13 and 14, which contain an ultraviolet absorber, are expected to exhibit lightfastness.

[0136]

[0137] 21 Central axis of shaft 22 Central shaft 23 End shafts 31 Test piece 32 Central shaft 33 End shafts 34 Center of test piece 35 Tangent plane on both end shafts including contact points between both end shafts and test piece 36 Tangent plane on the central shaft including contact points between the central shaft and test piece

Claims

1. A polycarbonate-based resin composition comprising a polycarbonate-based resin (S) including a polycarbonate-polyorganosiloxane copolymer (S-1) containing a polycarbonate block (A-1) containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), and an aromatic polycarbonate-based resin (S-2) other than the polycarbonate-polyorganosiloxane copolymer (S-1): Viscosity average molecular weight Mv of polycarbonate resin (S) ＰＣ is equal to or greater than 20,000 and equal to or less than 30,000, the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 9% by mass or less; the average chain length n of the polyorganosiloxane block (A-2) is 20 or more and less than 60; Viscosity average molecular weight Mv of polycarbonate resin (S) ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ The polycarbonate resin composition has a modulus of -3,100 or more and 6,000 or less. 【Chemistry 1】 [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O- or -CO-. 3 and R 4 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a and b each independently represent an integer of 0 to 4.

2. The viscosity average molecular weight Mv of the polycarbonate resin (S) ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ 2. The polycarbonate resin composition according to claim 1, wherein the modulus is -1,500 or more and 6,000 or less.

3. The viscosity average molecular weight Mv of the polycarbonate resin (S) ＰＣ and the viscosity average molecular weight Mv of the polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ Difference with Mv Ｓｉ -Mv ＰＣ The polycarbonate resin composition according to claim 2, wherein the modulus is -500 or more and 6,000 or less.

4. Viscosity average molecular weight Mv of polycarbonate-polyorganosiloxane copolymer (S-1) Ｓｉ The polycarbonate resin composition according to any one of claims 1 to 3, wherein the molecular weight of the polycarbonate resin composition is 18,500 or more and 25,000 or less.

5. The polycarbonate-based resin composition according to any one of claims 1 to 3, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (S-1) is 0.5% by mass or more and 8% by mass or less.

6. The polyorganosiloxane block (A-2) is a block unit represented by any one of the following general formulas (II-I), (II-II) and (II-III): The polycarbonate resin composition according to any one of claims 1 to 3. 【Chemistry 2】 [In the formula, R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different. Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O- or -R 7 O-R 10 The R represents —O—, and a plurality of Ys may be the same or different. 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 represents a diarylene group. 10 represents a linear, branched, or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. n is as defined above, and p is an integer of 1 or more and n-2 or less.]

7. The polycarbonate resin composition according to any one of claims 1 to 3, wherein a haze value of a molded article having a thickness of 3 mm, measured in accordance with ISO 14782:1999, is 0.1 or more and 1.0 or less.

8. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the polycarbonate-polyorganosiloxane copolymer (S-1) is substantially free of a block unit (A-3) represented by the following general formula (IV): 【Transformation 3】 [In the formula, R ２１ ~R ２４ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. ２５ is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. ２ is a divalent aliphatic group having 1 to 10 carbon atoms, and m represents the average chain length and is an integer of 10 or more.

9. The polycarbonate-based resin composition according to any one of claims 1 to 3, wherein the polycarbonate-polyorganosiloxane copolymer (S-1) consists solely of a polycarbonate block (A-1) and a polyorganosiloxane block (A-2).

10. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the average chain length n of the polyorganosiloxane block (A-2) is greater than 30 and less than 60.

11. The polycarbonate-based resin composition according to any one of claims 1 to 3, wherein the aromatic polycarbonate-based resin (S-2) has a viscosity average molecular weight of 11,000 or more and 30,000 or less.

12. A molded article obtained by molding the polycarbonate resin composition according to any one of claims 1 to 3.