Molded article comprising a polycarbonate resin composition

Abstract

A molded article comprising a polycarbonate resin composition, the polycarbonate resin composition comprising a polycarbonate-polysiloxane copolymer (A) and at least one compound (B) selected from the group consisting of antioxidants, dyes, mold release agents, light diffusing agents, flame retardants, ultraviolet absorbers, silicone compounds, epoxy compounds, and polyether compounds, the polycarbonate-polysiloxane copolymer (A) comprising a polycarbonate block (A-1) and a polysiloxane block (A-2), and the content of the polysiloxane block (A-2) being 20 to 70% by mass, the molded article having a durometer hardness based on a Type D durometer measured according to JIS K6253-3:2012 of 25 to 72.

Description

Technical Field

[0001] The present invention relates to a polycarbonate-based resin composition and a molded article having flexibility and excellent transparency. Background Art

[0002] As lighting covers for streetlights etc. and optical lenses, there is a demand for resin molded articles having flexibility that can be attached to various shapes or deformed and processed according to various designs for use. In such applications, flexibility is required, and at the same time, transparency and mechanical properties are required.

[0003] As such a resin, from the viewpoints of high transparency and optical properties, acrylic resins have been widely studied (Patent Document 1). Although acrylic resins have excellent transparency and flexibility, they have drawbacks such as poor mechanical strength, moldability, and processability.

[0004] Prior Art Documents

[0005] Patent Documents

[0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2003-277574 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] Compared with acrylic resins, polycarbonate-based resins are excellent in mechanical strength and moldability, but tend to be poor in flexibility.

[0009] An object of the present invention is to provide a molded article that contains a polycarbonate-based resin composition containing a polycarbonate-polyorganosiloxane copolymer and has both excellent flexibility and transparency.

[0010] Means for Solving the Problems

[0011] The present inventors have found that by making a polycarbonate-based resin composition contain a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes simply referred to as a PC-POS copolymer) having a specific structural unit and specific conditions, a molded article having flexibility and excellent transparency can be obtained.

[0012] That is, the present invention relates to the following [1] to

[15] .

[0013] [1] A molded article comprising a polycarbonate-based resin composition, the polycarbonate-based resin composition comprising a polycarbonate-polyorganosiloxane copolymer (A) and at least one compound (B) selected from the group consisting of antioxidants, dyes, mold release agents, light diffusing agents, flame retardants, ultraviolet absorbers, silicone-based compounds, epoxy compounds, and polyether compounds.

[0014] The above-mentioned polycarbonate-polysiloxane copolymer (A) contains a polycarbonate block (A-1) containing repeating units represented by the following general formula (I) and a polysiloxane block (A-2) containing repeating units represented by the following general formula (II), and the content of the above-mentioned polysiloxane block (A-2) is 20% by mass or more and 70% by mass or less.

[0015] The durometer hardness of the molded article measured according to JIS K6253-3:2012 using a Type D durometer is 25 or more and 72 or less.

[0016] [Chemical formula 1]

[0017]

[0018] [In the formula, R 1 and R 2 each independently represent 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, an arylene group having 6 to 12 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 -, -O-, or -CO-. R 3 and R 4 each independently represent 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] [2] A molded article comprising a polycarbonate resin composition, the polycarbonate resin composition comprising a polycarbonate-polysiloxane copolymer (A) and at least one compound (B) selected from the group consisting of an antioxidant, a dye, a mold release agent, a light diffusing agent, a flame retardant, an ultraviolet absorber, a silicone compound, an epoxy compound, and a polyether compound.

[0020] The above-mentioned polycarbonate-polysiloxane copolymer (A) contains a polycarbonate block (A-1) containing repeating units represented by the following general formula (I) and a polysiloxane block (A-2) containing repeating units represented by the following general formula (II).

[0021] The content of the polysiloxane block (A-2) contained in the molded article is 25% by mass or more and 70% by mass or less.

[0022] [Chemical formula 2]

[0023]

[0024] [In the formula, R 1 and R 2 each independently represent 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, an arylene group having 6 to 12 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 -, -O-, or -CO-. R 3 and R 4 each independently represent 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.]

[0025] [3] The molded article according to the above [1] or [2], wherein, based on 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A), it contains 0.001 to 0.5 parts by mass of an antioxidant, 0.00001 to 0.05 parts by mass of a dye, 0.001 to 0.5 parts by mass of a mold release agent, 0.1 to 5 parts by mass of a light diffusing agent, 0.001 to 20 parts by mass of a flame retardant, 0.01 to 1 part by mass of an ultraviolet absorber, 0.01 to 0.25 parts by mass of a silicone compound, 0 to 0.2 parts by mass of an epoxy compound and / or 0.2 to 1 part by mass of a polyether compound.

[0026] [4] The molded article according to any one of the above [1] to [3], wherein the content of the unit represented by the following general formula (III) in the polyorganosiloxane block (A-2) is 0.1 mol% or less.

[0027] [Chemical formula 3]

[0028]

[0029] [In the formula, R 33 and R 34 each independently represent 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. R 31 represents 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, an arylene group having 6 to 12 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms. R 35Represents 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. t represents the average chain length of the polyorganosiloxane.

[0030] [5] The shaped body according to any one of the above [1] to [4], wherein the number of repetitions of the polyorganosiloxane block (A-2) is 10 or more and less than 90.

[0031] [6] The shaped body according to any one of the above [1] to [5], wherein the polyorganosiloxane block (A-2) contains units represented by at least one of the following general formulas (II-I) to (II-III).

[0032] [Chemical formula 4]

[0033]

[0034] [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, and multiple R 3 ~R 6 May be the same or different from each other. Y represents -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 -O-, and multiple Y may be the same or different from each other. The above R 7 Represents a single bond, a straight-chain alkylene group, a branched-chain alkylene group, or a cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. R 8 Represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R 9 Represents a diarylene group. R 10 Represents a straight-chain alkylene group, a branched-chain alkylene group, or a 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 halide of a dicarboxylic acid. n represents the chain length of the polyorganosiloxane, and n-1, p, and q are each an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit, and the sum of p and q is n-2.

[0035] [7] The shaped body according to any one of the above [1] to [6], wherein the polyorganosiloxane block (A-2) contains units represented by the following general formula (V).

[0036] [Chemical Formula 5]

[0037]

[0038] [In the formula, R 3 ~R 6 and n-1 are the same as R 3 ~R 6 and n-1 described in the above general formulas (II-I) to (II-III). R 15 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.]

[0039] [8] The molded article according to any one of the above [1] to [7], wherein the viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is 10,000 or more and 23,000 or less.

[0040] [9] The molded article according to any one of the above [1] to [8], wherein the molecular weight distribution of the polycarbonate-polyorganosiloxane copolymer (A) is 2.1 or more and 3.9 or less.

[0041]

[10] The molded article according to any one of the above [1] to [9], wherein the content of the polyorganosiloxane block (A-2) in the molded article exceeds 40% by mass and is 70% by mass or less.

[0042]

[11] The molded article according to any one of the above [1] to

[10] , which does not contain a polycarbonate resin other than the polycarbonate-polyorganosiloxane copolymer (A).

[0043]

[12] The molded article according to the above [2], wherein the durometer hardness based on a Type D durometer measured according to JIS K6253-3:2012 is 25 or more and 72 or less.

[0044]

[13] The molded article according to any one of the above [1] to

[12] , wherein the total light transmittance at a thickness of 2 mm measured according to JIS K7361-1:1997 is 75% or more.

[0045]

[14] The molded article according to any one of the above [1] to

[13] , which is an optical member.

[0046]

[15] The molded article according to any one of [1] to

[14] above is at least one selected from a flexible display, a light guide plate, a housing, a water / oil repellent film, an optical adhesive, a switch cover, a heat sealant, a water blocking material, a sealant, a connector, an adapter, a smartphone cover, a lens, glasses / sunglasses parts, optical fiber parts, a buffer material for in-vehicle batteries, a wiper blade, a curved mirror, a side mirror, a rearview mirror, a lamp shade, a bumper, a window, an exterior decorative material, an interior decorative material, a sound absorbing material, a steering wheel cover, a sensor cover, a watch part, stationery, a cosmetic container, an aquarium for aquatic organisms, a sole, a cup, a nail painting, a toy, a fishing lure, a suction cup, a cooking utensil such as a steamer, clothes, a silicone wiping sheet, a remote control cover, an umbrella, a lining for a metal container, a building material covering, a door, a window, an interlayer of glass, a tent, a mirror, a display case, a plastic greenhouse, a housing for medical equipment, an infusion bag, an infusion tube, a syringe, a baby bottle, a mask, a face shield, a filter part, a shock absorbing part, a housing for a robot, a housing for a drone, a shield, a bulletproof shield, a sports cushioning equipment, a window for an aircraft, a resin compatibilizer, a lighting cover, a light guide, a light guide panel, a lighting unit, a prism panel, a flat lens, a Fresnel lens, a microlens array, and a collimating lens.

[0047] Effects of the Invention

[0048] According to the present invention, a molded article can be obtained which contains a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer and has both excellent flexibility and transparency. Detailed Description of the Invention

[0049] Hereinafter, the molded article containing the polycarbonate resin composition of the present invention will be described in detail. In this specification, preferred regulations can be arbitrarily adopted, and a combination of preferred regulations with each other can be said to be more preferred. In this specification, the description of "XX to YY" means "XX or more and YY or less".

[0050] In one aspect of the present invention, the molded article of the present invention is characterized in that it contains a polycarbonate resin composition, the polycarbonate resin composition contains a polycarbonate-polyorganosiloxane copolymer (A) and at least one compound (B) selected from an antioxidant, a dye, a release agent, a light diffusing agent, a flame retardant, an ultraviolet absorber, a silicone compound, an epoxy compound, and a polyether compound, the polycarbonate-polyorganosiloxane copolymer (A) contains 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 the content of the polyorganosiloxane block (A-2) is 20% by mass or more and 70% by mass or less, and the durometer hardness of the molded article measured according to JIS K6253-3:2012 using a Type D durometer is 25 or more and 72 or less.

[0051] [Chemical Formula 6]

[0052]

[0053] [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, an arylene group having 6 to 12 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 -, -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.]

[0054] In other embodiments of the present invention, the molded article of the present invention is characterized by comprising a polycarbonate resin composition, the polycarbonate resin composition comprising a polycarbonate-polyorganosiloxane copolymer (A) and at least one compound (B) selected from the group consisting of antioxidants, dyes, mold release agents, light diffusing agents, flame retardants, ultraviolet absorbers, silicone compounds, epoxy compounds, and polyether compounds,

[0055] The above polycarbonate-polyorganosiloxane copolymer (A) contains a polycarbonate block (A-1) containing repeating units represented by the above general formula (I) and a polyorganosiloxane block (A-2) containing repeating units represented by the above general formula (II), and the content of the polyorganosiloxane block (A-2) contained in the molded article is 25% by mass or more and 70% by mass or less.

[0056] Hereinafter, first, the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate resin composition contained in the molded article of the present invention will be described. First, the polycarbonate block (A-1) represented by the general formula (I) will be described in detail. In the above general formula (I), as R 1 and R 2 each independently represents a halogen atom, examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0057] As R 1 and R 2The alkyl groups each independently represented may include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups (the term "various" means including both linear and all branched groups, the same hereinafter), various pentyl groups, and various hexyl groups. As R 1 and R 2 The alkoxy groups each independently represented may include the case where the alkyl moiety is the above alkyl group.

[0058] Examples of the alkylene group represented by X may include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, etc., and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X may include an ethylidene group, an isopropylidene group, etc. Examples of the cycloalkylene group represented by X may include a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, etc., and a cycloalkylene group having 5 to 10 carbon atoms is preferred. Examples of the arylene group represented by X may include a phenylene group, a naphthylene group, a biphenylene group, etc. Examples of the cycloalkylidene group represented by X may include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group, etc., and a cycloalkylidene group having 5 to 10 carbon atoms is preferred, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferred. Examples of the aryl moiety of the arylalkylene group represented by X may include an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc. Examples of the aryl moiety of the arylalkylidene group represented by X may include an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc.

[0059] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

[0060] Among them, it is suitable that a and b are 0 and the block where X is a single bond or an alkylene group having 1 to 8 carbon atoms, or the block where a and b are 0 and X is an alkylidene group, especially an isopropylidene group. As the polycarbonate block (A-1), a plurality of polycarbonate blocks may be included.

[0061] In the case of including a plurality of polycarbonate blocks as the polycarbonate block (A-1), from the viewpoint of transparency, it is preferred that a and b are 0, and the block where X is an isopropylidene group is preferably 90% by mass or more, more preferably 90.9% by mass or more, further preferably 93.3% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[0062] Next, the polyorganosiloxane block (A-2) represented by the general formula (II) will be described in detail.

[0063] In the above general formula (II), as the halogen atom represented by R 3 or R 4 each independently represented, examples may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. As R 3 or R 4The alkyl groups each independently represented include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. As for R 3 or R 4 The alkoxy groups each independently represented include the case where the alkyl moiety is the above alkyl group. As for R 3 or R 4 The aryl groups each independently represented include phenyl, naphthyl, etc.

[0064] As for R 3 and R 4 , they are preferably both hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or aryl groups having 6 to 12 carbon atoms, and more preferably both are methyl groups.

[0065] The polyorganosiloxane block (A-2) containing the repeating unit represented by the general formula (II) preferably has the units represented by the following general formulas (II-I) to (II-III).

[0066] [Chemical formula 7]

[0067]

[0068] [In the formula, R 3 to R 6 each independently represent 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 to R 6 may be the same or different from each other. Y represents -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 -O-, and a plurality of Y may be the same or different from each other. The above R 7 represents a single bond, a straight-chain alkylene group, a branched-chain alkylene group, or a cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R 9 , and the diarylene group is represented. R 10represents a linear alkylene group, a branched alkylene group or a 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 halide of a dicarboxylic acid. n represents the average chain length of the polyorganosiloxane, n - 1, p and q are each an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit, and the sum of p and q is n - 2.

[0069] As R 3 ~R 6 Each independently represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As R 3 ~R 6 Each independently represents an alkyl group, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups. As R 3 ~R 6 Each independently represents an alkoxy group, and examples thereof include cases where the alkyl moiety is the above alkyl group. As R 3 ~R 6 Each independently represents an aryl group, and examples thereof include a phenyl group, a naphthyl group and the like.

[0070] As R 3 ~R 6 , each 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.

[0071] In the general formulas (II-I), (II-II) and / or (II-III), R 3 ~R 6 are each preferably a methyl group.

[0072] As the -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 -O- in which R 7 represents a linear or branched alkylene group, examples thereof include an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and as the cyclic alkylene group, examples thereof include a cycloalkylene group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

[0073] As R 7The aryl-substituted alkylene group shown may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring, and its specific structure may be, for example, the structure of the following general formula (i) or (ii). In the case of an aryl-substituted alkylene group, the alkylene group is bonded to Si.

[0074] [Chemical formula 8]

[0075]

[0076] (In the formula, c represents a positive integer, usually an integer from 1 to 6)

[0077] R 7 , R 9 and R 10 The diarylene group shown in the figure is a group in which two arylene groups are linked directly or via a divalent organic group. Specifically, it is a group having -Ar 1 -W-Ar 2 - a group of the structure shown. 1 and Ar 2 W represents an arylene group, and W represents a single bond or a divalent organic group. Examples of the divalent organic group represented by W include isopropylidene, methylene, dimethylene, and trimethylene.

[0078] As R 7 ,Ar 1 and Ar 2 The arylene group shown in the formula (a) includes arylene groups having 6 to 14 ring carbon atoms such as phenylene, naphthylene, biphenylene, and anthracene. These arylene groups may have an optional substituent such as an alkoxy group or an alkyl group.

[0079] Can have R 8 The alkyl group shown is a straight chain or branched group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a straight chain or branched group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include phenyl and naphthyl. Examples of the aralkyl group include phenylmethyl and phenylethyl.

[0080] R 10 The straight chain alkylene group, branched chain alkylene group or cyclic alkylene group shown in R 7 same.

[0081] As Y, -R 7 O-, R 7 It is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, and more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.

[0082] With regard to p and q in formula (II-II), p=q is preferred.

[0083] β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. Examples thereof include divalent groups represented by the following general formulas (iii) to (vii).

[0084] [Chemical formula 9]

[0085]

[0086] The PC-POS copolymer (A) more preferably has a polyorganosiloxane block (A-2) containing units represented by the following general formula (V).

[0087] [Chemical formula 10]

[0088]

[0089] [In the formula, R 3 ~R 6 and n are the same as described in the above general formulas (II-I) to (II-III). R 15 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.]

[0090] The number of repetitions of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably 10 or more and less than 90, more preferably 10 or more and 40 or less. Specifically, it is preferably 10 or more, more preferably 15 or more, particularly preferably 20 or more, preferably less than 90, more preferably 80 or less, further preferably 60 or less, further preferably 45 or less, further preferably 40 or less, and particularly preferably less than 40.

[0091] This number of repetitions is calculated by nuclear magnetic resonance (NMR) measurement. By setting the number of repetitions of the polyorganosiloxane block (A-2) within the above range, excellent transparency and flexibility can be achieved simultaneously, and peeling after forming the molded body can be suppressed.

[0092] In one aspect of the present invention, it is important that the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is 20% by mass or more and 70% by mass or less. By setting the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) to 20% by mass or more, a copolymer with excellent flexibility can be obtained. If the content of the polyorganosiloxane block (A-2) is 70% by mass or less, the copolymer will have no significant stickiness and can maintain the shape of a soft molded body.

[0093] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, for example, exceeding 50% by mass, preferably 65% by mass or less, more preferably 62% by mass or less, still more preferably 55% by mass or less.

[0094] The viscosity-average molecular weight of the PC-POS copolymer (A) is preferably 10,000 or more and 23,000 or less. The above viscosity-average molecular weight (Mv) can be adjusted by using a molecular weight regulator (capping agent) or the like or by means of reaction conditions. By setting the viscosity-average molecular weight within the above range, a copolymer with excellent moldability is formed, and melt fracture of the molded body can be further suppressed, so it is preferred.

[0095] The viscosity-average molecular weight (Mv) is more preferably 12,000 or more, still more preferably 14,000 or more, still more preferably 16,000 or more, more preferably 21,500 or less, still more preferably 20,500 or less, still more preferably 19,500 or less, still more preferably 18,500 or less, and particularly preferably 18,000 or less. If the viscosity-average molecular weight is 10,000 or more, sufficient strength of the molded product can be obtained.

[0096] The viscosity-average molecular weight (Mv) is a value calculated by measuring the intrinsic viscosity [η] of a dichloromethane solution at 20 °C and according to the following Schnell formula.

[0097] [Mathematical formula 1]

[0098] [η]=1.23×10 -5 ×Mv 0.83

[0099] The weight-average molecular weight (Mw) of the PC-POS copolymer (A) is preferably 40,000 or less. By making the weight-average molecular weight (Mw) within the above range, a PC-POS copolymer with excellent flexibility can be obtained. The weight-average molecular weight (Mw) of the PC-POS copolymer (A) is more preferably 37,000 or less, still more preferably 35,000 or less, still more preferably 30,000 or less. In addition, the weight-average molecular weight (Mw) is preferably 20,000 or more, more preferably 23,000 or more.

[0100] The PC-POS copolymer (A) further preferably has a molecular weight distribution (Mw / Mn) of 2.1 or more and 3.9 or less. By making the molecular weight distribution Mw / Mn of the PC-POS copolymer within the above range, non-uniformity caused by irregular flow and phase separation during molding can be suppressed, and a molded body with high transparency and easy control of flexibility can be obtained, so it is preferred.

[0101] The above-mentioned molecular weight distribution Mw / Mn of the PC-POS copolymer (A) is more preferably 2.3 or more, further preferably 2.4 or more, still further preferably 2.5 or more, still further preferably 2.7 or more, particularly preferably 2.8 or more, more preferably 3.5 or less, further preferably 3.0 or less, and particularly preferably 2.9 or less.

[0102] The above-mentioned PC-POS copolymer (A) can be produced by known production methods such as the interfacial polymerization method (phosgene method), the pyridine method, and the transesterification method. In particular, if the interfacial polymerization method in which a polyorganosiloxane is added to a reaction system for polymerizing a diphenol and a carbonate precursor is adopted, separation of the organic phase containing the PC-POS copolymer and the aqueous phase containing unreacted substances, catalyst residues, etc. can be carried out in the oil-water separation step after polymerization and in each cleaning step based on alkali cleaning, acid cleaning, and pure water (ion-exchanged water) cleaning, and the PC-POS copolymer can be obtained efficiently, and thus it is preferred. As a method for producing the PC-POS copolymer, for example, the method described in JP-A-2014-80462 can be referred to.

[0103] Specifically, it can be produced by dissolving a polycarbonate oligomer and a polyorganosiloxane, which are pre-produced as described below, in a water-insoluble organic solvent (such as dichloromethane), adding an aqueous solution of an alkaline compound (such as an aqueous sodium hydroxide solution) of a diphenol compound (such as bisphenol A), and carrying out an interfacial polycondensation reaction in the presence of a polymerization catalyst such as a tertiary amine (such as triethylamine) and a quaternary ammonium salt (such as trimethylbenzylammonium chloride) and a terminator (such as a monophenol like p-tert-butylphenol). The PC-POS copolymer (A) can also be produced by copolymerizing a polyorganosiloxane with a diphenol and phosgene, a carbonate, or a chloroformate.

[0104] For example, in the case of producing the PC-POS copolymer (A) by reacting a polycarbonate oligomer with a polyorganosiloxane raw material in an organic solvent and then reacting with a diphenol, from the viewpoint of the transparency of the obtained PC-POS copolymer, the solid content weight (g / L) of the polycarbonate oligomer in 1 L of the mixed solution of the above-mentioned organic solvent and the polycarbonate oligomer is preferably in the range of 200 g / L or less. More preferably, it is 180 g / L or less, still further preferably 170 g / L or less, still further preferably 150 g / L or less, and particularly preferably 120 g / L or less.

[0105] The lower the solid content weight (g / L) of the polycarbonate oligomer in 1 L of the mixed solution of the above-mentioned organic solvent and the polycarbonate oligomer, the better the transparency of the obtained copolymer. Therefore, the lower limit is not particularly limited, but from the viewpoint of efficiently producing the PC-POS copolymer, it is preferably 20 g / L or more, more preferably 30 g / L or more, and still further preferably 40 g / L or more.

[0106] As the polyorganosiloxane used as a raw material, polyorganosiloxanes represented by the following general formula (1), (2) and / or (3) can be used.

[0107] [Chemical formula 11]

[0108]

[0109] In the above formula, R 3 ~R 6 , Y, β, n-1, p and q are as described above, and specific examples and preferred examples are the same.

[0110] Z represents a hydrogen atom or a halogen atom, and a plurality of Zs may be the same or different from each other.

[0111] For example, as the polyorganosiloxane represented by the general formula (1), compounds represented by the following general formula (1-1) to (1-11) can be cited.

[0112] [Chemical formula 12]

[0113]

[0114] In the above general formula (1-1) to (1-11), R 3 ~R 6 , n and R 8 are defined as above, and the preferred examples are the same. c represents a positive integer, usually an integer of 1 to 6.

[0115] Among them, from the viewpoint of the ease of polymerization when obtaining the polyorganosiloxane, the phenol-modified polyorganosiloxane represented by the above general formula (1-1) is preferred. From the viewpoint of the ease of obtaining, 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.

[0116] In addition, as the polyorganosiloxane raw material, a substance having the following general formula (4) can also be used.

[0117] [Chemical formula 13]

[0118]

[0119] In the above formula, R 3 and R 4 are the same as above. The average chain length of the polyorganosiloxane block represented by the general formula (4) is (r×m), and the range of (r×m) is the same as n above.

[0120] When using the above (4) as the polyorganosiloxane raw material, the polyorganosiloxane block (A-2) preferably has units represented by the following general formulas (II-IV).

[0121] [Chemical formula 14]

[0122]

[0123] [In the formula, R 3 , R 4 , r and m are as described above]

[0124] As the polyorganosiloxane block (A-2), it may have a structure represented by the following general formula (II-V).

[0125] [Chemical formula 15]

[0126]

[0127] [In the formula, R 18 ~R 21 are each independently a hydrogen atom or an alkyl group having 1 to 13 carbon atoms. R 22 is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Q 2 is a divalent aliphatic group having 1 to 10 carbon atoms. n-1 represents the repetition number of the polyorganosiloxane block, and its range is as described above.]

[0128] In the general formula (II-V), as the alkyl group having 1 to 13 carbon atoms represented by R 18 ~R 21 each independently, examples include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, 2-ethylhexyl, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, and various tridecyl groups. Among them, as R 18 ~R 21 , it is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably all are methyl groups.

[0129] As the alkyl group having 1 to 6 carbon atoms represented by R 22 , examples include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups. As the halogen atom represented by R 22 , examples include fluorine atom, chlorine atom, bromine atom, iodine atom. As the alkoxy group having 1 to 6 carbon atoms represented by R 22 , the case where the alkyl part is the above alkyl group can be cited. As the aryl group having 6 to 14 carbon atoms represented by R 22 , examples include phenyl, tolyl, dimethylphenyl, naphthyl, etc.

[0130] Among the above, R 22 is preferably a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom.

[0131] As Q 2 the divalent aliphatic group having 1 to 10 carbon atoms shown, a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms is preferred. The number of carbon atoms of the saturated aliphatic group is preferably 1 to 8, more preferably 2 to 6, still more preferably 3 to 6, and still more preferably 4 to 6. The repeat number n-1 is as described above.

[0132] As a preferred mode of the structural unit (II-V), the structure shown by the following formula (II-VI) can be mentioned.

[0133] [Chemical formula 16]

[0134]

[0135] [In the formula, n-1 is the same as above.]

[0136] The polyorganosiloxane block (A-2) shown by the above general formula (II-V) or (II-VI) can be obtained by using a polyorganosiloxane raw material shown by the following general formula (5) or (6).

[0137] [Chemical formula 17]

[0138]

[0139] [In the formula, R 18 ~R 22 , Q 2 and n-1 are as described above.]

[0140] [Chemical formula 18]

[0141]

[0142] [In the formula, n-1 is as described above.]

[0143] The method for producing the above polyorganosiloxane is not particularly limited. For example, according to the method described in Japanese Patent Laid-Open No. 11-217390, a cyclic trisiloxane and a disiloxane are reacted in the presence of an acidic catalyst to synthesize an α,ω-dihydroorganopentasiloxane. Next, in the presence of a hydrosilylation reaction catalyst, the α,ω-dihydroorganopentasiloxane is subjected to an addition reaction with a phenolic compound (such as 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.), whereby a crude polyorganosiloxane can be obtained. 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-dihydroorganopolysiloxane is subjected to an addition reaction with a phenolic compound or the like in the presence of a hydrosilylation reaction catalyst in the same manner as above, whereby a crude polyorganosiloxane can be obtained. The chain length n of the α,ω-dihydroorganopolysiloxane can be appropriately adjusted by its polymerization conditions before use, or a commercially available α,ω-dihydroorganopolysiloxane can be used. As the hydrosilylation catalyst, specifically, the hydrosilylation catalyst described in Japanese Patent Laid-Open No. 2016-098292 can be used.

[0144] The polycarbonate oligomer can be produced by reacting a bisphenol with a carbonate precursor such as carbonyl chloride or tricarbonyl chloride in an organic solvent such as dichloromethane, chlorobenzene, or chloroform. When the polycarbonate oligomer is produced by the transesterification method, it can also be produced by reacting a bisphenol with a carbonate precursor such as diphenyl carbonate.

[0145] As the bisphenol, the bisphenol represented by the following general formula (viii) is preferably used.

[0146] [Chemical formula 19]

[0147]

[0148] [In the formula, R 1 , R 2 , a, b, and X are as described above.]

[0149] As the bisphenol represented by the above general formula (viii), for example, 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane and other bis(hydroxyphenyl)alkane series, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, etc. can be cited. These bisphenols can be used alone or in combination of two or more.

[0150] Among them, bis(hydroxyphenyl)alkane-based diphenols are preferred, and bisphenol A is more preferred. When bisphenol A is used as the diphenol, a PC-POS copolymer in which X in the above general formula (i) is an isopropylidene group and a = b = 0 is formed.

[0151] Examples of diphenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxybiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, etc. These diphenols can be used alone or in combination of two or more.

[0152] 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, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, etc.

[0153] 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.

[0154] 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.

[0155] As dihydroxybiphenyls, 4,4'-dihydroxybiphenyl etc. can be cited, for example. As dihydroxydiarylfluorenes, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene etc. can be cited, for example. As dihydroxydiaryladamantanes, 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane etc. can be cited, for example.

[0156] As diphenols other than the above, 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxolane etc. can be cited, for example.

[0157] In order to adjust the molecular weight of the obtained PC-POS copolymer, a capping agent (molecular weight regulator) can be used. As the capping agent, monophenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol etc. can be cited, for example. These monophenols can be used alone or in combination of two or more.

[0158] After the above interfacial polycondensation reaction, a PC-POS copolymer (A) can be obtained through the following steps, that is, performing appropriate standing to separate into an aqueous phase and an organic solvent phase [separation step], washing the organic solvent phase (preferably washing in the order of an alkaline aqueous solution, an acidic aqueous solution, and water) [washing step], concentrating the obtained organic phase [concentration step], and performing drying [drying step].

[0159] Regarding the PC-POS copolymer (A) in the polycarbonate-based resin composition contained in the molded article of the present invention, the content of the unit represented by the following general formula (III) in the above polyorganosiloxane block (A-2) is preferably 0.1 mol% or less.

[0160] [Chemical formula 20]

[0161]

[0162] [In the formula, R 33 and R 34 each independently represent 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. R 31 represents 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, an arylene group having 6 to 12 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms.35 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. t represents the average chain length of the polyorganosiloxane.

[0163] By making the block represented by the above general formula (III) 0.1 mol% or less, precise control can be carried out between the raw material polyorganosiloxane used in the production of the PC-POS copolymer and the chain length of the copolymer, and a molded article having both the desired high flexibility and transparency can be obtained.

[0164] Specifically, by adopting the above interfacial polymerization method, a PC-POS copolymer in which the block represented by the above general formula (III) reaches 0.1 mol% or less can be obtained. In the PC-POS copolymer (A), theoretically, it cannot contain the block represented by the above general formula (III) according to the synthesis steps, and substantially its content is 0.0 mol%.

[0165] will be described in detail. The content of the block represented by the above general formula (III) in the above PC-POS copolymer (A) is based on 13 the peak of 13C-NMR for quantification. The specific quantification method is as shown in the examples. Regarding the lower limit of quantification of this quantification method, according to 13 the signal-to-noise ratio of the baseline of the 13C-NMR spectrum, it is less than 0.1 mol%. Regarding the region less than 0.1 mol%, although quantification is impossible, semi-quantification can be carried out. When performing semi-quantification, a relative comparison of the peak heights corresponding to (III) is carried out. When it is difficult to carry out a relative comparison of the peak heights, by further increasing the number of accumulations to improve the signal-to-noise ratio, the lower limit for which semi-quantification can be carried out can be further reduced.

[0166] The content of the block represented by the above general formula (III) in the PC-POS copolymer (A) determined by the above quantification method and semi-quantification method is more preferably 0.08 mol% or less, further preferably 0.05 mol% or less, and particularly preferably substantially 0.0 mol%.

[0167] In the conventionally known synthesis methods, a carbonyl chloride gas having polymerization activity is reacted with a mixture of a bisphenol monomer and a polyorganosiloxane monomer or a polyorganosiloxane. Therefore, even if the addition method and contact time of the carbonyl chloride gas are improved to reduce the amount of the block represented by the above general formula (III), it is impossible to avoid the contact of multiple polyorganosiloxane monomer molecules with the carbonyl chloride gas having polymerization activity, and thus it is impossible to make the amount of the block represented by the general formula (III) substantially reach 0.0 mol%.

[0168] On the other hand, the PC-POS copolymer (A) is preferably synthesized as follows. First, a bisphenol monomer is reacted with phosgene gas to synthesize a bisphenol monomer or a bisphenol polycarbonate oligomer having chloroformate structures at both ends. Then, a polymerization-inert polysiloxane monomer, or a polymerization-inert polysiloxane monomer and a polymerization-inert bisphenol monomer are reacted with the bisphenol monomer having polymerizable chloroformate groups at both ends, or the bisphenol polycarbonate oligomer having polymerizable chloroformate groups at both ends. Therefore, the above general formula (III) is substantially not formed.

[0169] [Compound (B)]

[0170] The polycarbonate resin composition contained in the molded article of the present invention contains, in addition to the above PC-POS copolymer, at least one compound selected from antioxidants, dyes, mold release agents, light diffusing agents, flame retardants, ultraviolet absorbers, silicone compounds, epoxy compounds, and polyether compounds as component (B). In one embodiment of the present invention, the above polycarbonate resin composition contained in the molded article contains 0.001 to 0.5 parts by mass of an antioxidant, 0.00001 to 0.05 parts by mass of a dye, 0.001 to 0.5 parts by mass of a mold release agent, 0.1 to 5 parts by mass of a light diffusing agent, 0.001 to 20 parts by mass of a flame retardant, 0.01 to 1 part by mass of an ultraviolet absorber, 0.01 to 0.25 parts by mass of a silicone compound, 0 to 0.2 parts by mass of an epoxy compound, and / or 0.2 to 1 part by mass of a polyether compound as component (B) based on 100 parts by mass of the PC-POS copolymer (A). Details are described below.

[0171] <Antioxidant>

[0172] The compound (B) contained in the polycarbonate resin composition preferably contains an antioxidant. By containing an antioxidant, oxidative degradation during melting of the polycarbonate resin composition can be prevented, and coloring and the like caused by oxidative degradation can be prevented. As the antioxidant, a phosphorus-based antioxidant and / or a phenol-based antioxidant are preferably used.

[0173] 1. Phosphorus-based antioxidant

[0174] As the phosphorus-based antioxidant, from the viewpoint of obtaining a resin composition that can suppress the occurrence of discoloration and the like even when staying at a high temperature, a phosphite-based antioxidant or a phosphine-based antioxidant is preferred.

[0175] As phosphite antioxidants, for example, tris(nonylphenyl) phosphite, triphenyl phosphite, tridecyl phosphite, tris(octadecyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite (trade name "Irgafos 168" manufactured by BASF Corporation, etc.), bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (trade name "Irgafos 126" manufactured by BASF Corporation, trade name "ADEKA STAB PEP-24G" manufactured by ADEKA Corporation, etc.), bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite (trade name "Irgafos 38" manufactured by BASF Corporation, etc.), bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (trade name "ADEKA STAB PEP-36" manufactured by ADEKA Corporation, etc.), distearyl pentaerythritol diphosphite (trade name "ADEKA STAB PEP-8" manufactured by ADEKA Corporation, trade name "JPP-2000" manufactured by Johoku Chemical Co., Ltd., etc.), [bis(2,4-di-tert-butyl-5-methylphenoxy)phosphino]biphenyl (trade name "GSY-P101" manufactured by Osaki Kogyo Co., Ltd., etc.), 2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetra-tert-butylbenzo[d][1,3,2]dioxaphosphepin-6-yl)oxypropyl]phenol (trade name "Sumilizer GP" manufactured by Sumitomo Chemical Co., Ltd., etc.), tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine (trade name "Irgafos 12" manufactured by BASF Corporation, etc.) and the like.

[0176] In addition, compounds represented by the following formulas (12) to (15) can also be mentioned.

[0177] [Chemical formula 21]

[0178]

[0179] Among these phosphite antioxidants, from the viewpoint of hydrolysis resistance, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Doverphos S-9228PC) are more preferred.

[0180] As phosphine antioxidants, for example, triphenylphosphine ("JC263" manufactured by Johoku Chemical Co., Ltd.) can be mentioned.

[0181] When using a phosphorus-based antioxidant as the antioxidant, the content is preferably 0.002 to 0.2 parts by mass, more preferably 0.003 to 0.1 parts by mass, and still more preferably 0.003 to 0.1 parts by mass, relative to 100 parts by mass of the PC-POS copolymer (A). If it is within the above range, discoloration and silver streak generation of the resin composition during retention at high temperature can be sufficiently suppressed.

[0182] 2. Phenolic antioxidant

[0183] Examples of the phenolic antioxidant 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-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0184] Examples of the phenolic antioxidant include commercially available products such as Irganox 1010 (manufactured by BASF Japan Ltd., trademark), Irganox 1076 (manufactured by BASF Japan Ltd., trademark), Irganox 1330 (manufactured by BASF Japan Ltd., trademark), Irganox 3114 (manufactured by BASF Japan Ltd., trademark), Irganox 3125 (manufactured by BASF Japan Ltd., trademark), BHT (manufactured by Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (manufactured by Cyanamid, trademark), and Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd., trademark).

[0185] Except for the antioxidants described in the part of the above 1. Phosphorus-based antioxidant, the content of the above antioxidant is about 0.001 part by mass or more and 0.5 part by mass or less, preferably 0.01 part by mass or more and 0.3 part by mass or less, and more preferably 0.02 part by mass or more and 0.3 part by mass or less, relative to 100 parts by mass of the PC-POS copolymer (A). If the content of the above antioxidant is 0.001 part by mass or more, a sufficient antioxidant effect can be obtained, and if it is 0.5 part by mass or less, contamination of the mold used during molding can be sufficiently suppressed.

[0186] <Dye>

[0187] Compound (B) contained in the polycarbonate resin composition may include dyes (pigments). The dyes are not particularly limited as long as they are compounds classified as dyes in the Colour Index (published by The Society of Dyers and Colourists). For example, water-soluble acid dyes, metal-containing dyes, basic dyes, cationic dyes, direct dyes, reactive dyes, and non-water-soluble disperse dyes, sulfur dyes, vat dyes, etc. of red, blue, green, yellow, orange, purple, brown, and black can be cited. The dye can be any of organic dyes and inorganic dyes. More specifically, metal phthalocyanine pigments, cyanine dyes, anthracene pigments, bisazo pigments, pyrene pigments, polycyclic quinone pigments, quinacridone pigments, indigo pigments, perylene pigments, pyranylium dyes, squarylium pigments, anthraquinone pigments, benzimidazole pigments, azo pigments, thioindigo pigments, quinoline pigments, lake pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments, azulenium dyes, triarylmethane dyes, xanthine dyes, thiazine dyes, thianium dyes, polyvinylcarbazole, bisbenzimidazole pigments, anthraquinone-based dyes, etc. can be cited.

[0188] The content of the dye in the polycarbonate resin composition is about 0.00001 parts by mass or more and 0.05 parts by mass or less, preferably 0.0001 parts by mass or more and 0.005 parts by mass or less, more preferably 0.0001 parts by mass or more and 0.0005 parts by mass or less, relative to 100 parts by mass of the above PC-POS copolymer (A).

[0189] <Release agent>

[0190] Compound (B) contained in the polycarbonate resin composition may include a release agent. As the release agent, fatty acid esters, polyolefin waxes, fluorinated oils, paraffin waxes, etc. can be used. Among them, fatty acid esters are preferred. For example, partial esters such as glycerol monostearate, glycerol distearate, sorbitan monostearate, glycerol monobehenate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, propylene glycol monostearate, and sorbitan anhydride monostearate are preferred.

[0191] The content of the dye or the release agent in the polycarbonate resin composition is about 0.001 parts by mass or more and 0.5 parts by mass or less, preferably 0.01 parts by mass or more and 0.3 parts by mass or less, more preferably 0.03 parts by mass or more and 0.3 parts by mass or less, relative to 100 parts by mass of the above PC-POS copolymer (A).

[0192] <Light diffusing agent>

[0193] The compound (B) contained in the polycarbonate resin composition may include a light diffusing agent. The light diffusing agent is compounded to impart a light diffusion effect and is not particularly limited, and known light diffusing agents can be used. For example, crosslinked acrylic resins, crosslinked polystyrene resins, silicone resins, fluorine-based resins, silica, quartz, titanium oxide, zinc oxide, etc. can be cited.

[0194] Among them, from the aspect of being able to impart assistance to flame retardancy and a light diffusion effect, Si-based light diffusing agents are preferred. The Si-based light diffusing agent is not particularly limited as long as it contains silicon (Si), and known Si-based light diffusing agents can be used. For example, silicone-based elastomers, silicone resins, etc. can be cited. Among them, from the aspect of good retention heat stability in molding, etc. and having an effect of improving flame retardancy, organic fine particles containing silicone resin are preferred, and the preferred particle size is 0.5 to 10 μm, more preferably 1 to 5 μm.

[0195] The content of the light diffusing agent in the polycarbonate resin composition varies depending on the thickness of the molded product. Relative to 100 parts by mass of the PC-POS copolymer (A), it is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 4 parts by mass, and further preferably 0.1 to 3 parts by mass. If the content of the light diffusing agent is within the above range, sufficient diffusion performance can be obtained, and the strength of the molded product can be sufficiently maintained. When the light diffusing agent is added, the total light transmittance decreases as a whole according to its addition amount, but even in this case, according to the present invention, the difference in transmittance caused by the thickness of the test piece is small, and excellent transmittance can be maintained.

[0196] Specifically, the following diffusing agents can be used.

[0197] Bead-shaped crosslinked silicone (manufactured by Momentive Performance Materials Japan LLC: TSR9002 (trade name), average particle size 2 μm)

[0198] Bead-shaped crosslinked acrylic particles (manufactured by Sekisui Chemical Co., Ltd.: MBX-5 (trade name), average particle size 5 μm)

[0199] Bead-shaped crosslinked acrylic particles (manufactured by Toagosei Co., Ltd.: SDP-S225 (trade name), average particle size 2 μm)

[0200] <Flame retardant>

[0201] The compound (B) contained in the polycarbonate resin composition may contain a flame retardant. Examples of the flame retardant include organic alkali metal salts, organic alkaline earth metal salts, phosphorus-based flame retardants, silicone-based flame retardants, and expandable graphite, and one kind can be used alone or two or more kinds can be used in combination. As the flame retardant, any one of organic alkali metal salts, organic alkaline earth metal salts (hereinafter sometimes collectively referred to as organic alkali (earth) metal salts), and phosphorus-based flame retardants is preferred. More preferably, it is an organic alkali metal salt or a phosphorus-based flame retardant.

[0202] As the organic alkali (earth) metal salts, various salts can be cited, and alkali metal salts and organic alkaline earth metal salts of organic acids having at least one carbon atom or organic acid esters can be used.

[0203] The organic acid or organic acid ester is an organic sulfonic acid, an organic carboxylic acid, etc. Examples of the alkali metal include lithium, sodium, potassium, cesium, etc., and examples of the alkaline earth metal include magnesium, calcium, strontium, barium, etc. From the viewpoints of flame retardancy and thermal stability, among the alkali metals, sodium and potassium are preferred, and potassium is particularly preferred. In addition, the salts of the organic acid can be substituted with halogens such as fluorine, chlorine, and bromine. One kind of the alkali (earth) metal salt can be used alone or two or more kinds can be used in combination.

[0204] Among the above various organic alkali (earth) metal salts, for example, in the case of organic sulfonic acids, alkali (earth) metal salts of perfluoroalkane sulfonic acids represented by the following formula (11) are preferably used.

[0205] (C e F 2e+1 SO 3 ) f M (11)

[0206] In the formula, e represents an integer of 1 to 10, M represents an alkali metal such as lithium, sodium, potassium, cesium, etc., an alkaline earth metal such as magnesium, calcium, strontium, barium, etc., and f represents the valence of M.

[0207] As these compounds, for example, the compounds described in Japanese Patent Publication No. 47-40445 are equivalent to this compound.

[0208] As the perfluoroalkane sulfonic acid represented by the above formula (11), for example, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. can be cited. Their potassium salts are particularly preferably used. And alkali metal salts of organic sulfonic acids such as p-toluenesulfonic acid, 2,5-dichlorobenzenesulfonic acid; 2,4,5-trichlorobenzenesulfonic acid; diphenyl sulfone-3-sulfonic acid; diphenyl sulfone-3,3'-disulfonic acid; naphthalenetrisulfonic acid, etc. can be cited.

[0209] As organic carboxylic acids, for example, perfluoromethanoic acid, perfluoromethylmethanoic acid, perfluoroethanoic acid, perfluoropropanoic acid, perfluorobutanoic acid, perfluoromethylbutanoic acid, perfluorohexanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, etc. can be cited, and the alkali metal salts of these organic carboxylic acids can be used.

[0210] When the flame retardant is an organic base (earth) metal salt, its compounding amount is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.02 part by mass or more, preferably 1 part by mass or less, more preferably 0.1 part by mass or less, and further preferably 0.08 part by mass or less with respect to 100 parts by mass of the PC-POS copolymer (A). If it is within the above range, more excellent flame retardancy can be obtained.

[0211] As the phosphorus-based flame retardant, red phosphorus and phosphate-based flame retardants can be cited.

[0212] As the phosphate-based flame retardant, a halogen-free flame retardant is particularly preferably used, and flame retardants formed from monomers, oligomers, polymers of phosphates or mixtures thereof can be cited. Specifically, triphenyl phosphate, tricresyl phosphate, tolyldiphenyl phosphate, tris(dimethylphenyl) phosphate, tris(isopropylphenyl) phosphate, trisnaphthyl phosphate, biphenol diphosphate, bisphenol A diphosphate, hydroquinone diphosphate, resorcinol diphosphate, resorcinol diphenyl phosphate, pyrogallol triphosphate, etc., or their substituents, condensates, etc. can be cited. The phosphorus-based flame retardants can be used alone or in combination of two or more.

[0213] When the flame retardant is a phosphorus-based flame retardant, its compounding amount is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less with respect to 100 parts by mass of the PC-POS copolymer (A). If it is 0.1 part by mass or more, more excellent flame retardancy can be obtained, and if it is 20 parts by mass or less, the reduction of chemical resistance, heat resistance, tensile elongation, impact resistance, etc. can be further suppressed.

[0214] <Ultraviolet absorber>

[0215] The compound (B) contained in the polycarbonate resin composition may contain an ultraviolet absorber.

[0216] As the ultraviolet absorber, benzotriazole-based compounds, benzoxazine-based compounds, salicylate-based compounds, malonate-based compounds, oxalylanilide-based compounds, triazine-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, etc. can be cited, and these can be used alone or in combination of two or more.

[0217] As benzotriazole compounds, specifically, for example, 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'-methylenebis[4-methyl-6-(benzotriazol-2-yl)phenol], 2,2'-methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol), etc. can be cited.

[0218] As triazine compounds, specifically, for example, 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. can be cited.

[0219] As benzophenone compounds, specifically, for example, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-ethoxy-benzophenone, etc. can be cited.

[0220] As cyanoacrylate compounds, specifically, for example, 2-ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis-[2'-cyano-3,3'-diphenylacryloyloxy]-2,2-bis-[(2-cyano-3',3'-diphenylacryloyl)oxy]methylpropane, etc. can be cited.

[0221] As benzoxazine compounds, at least one compound represented by the following general formula (21) can be cited.

[0222] [Chemical formula 22]

[0223]

[0224] [In the formula, R 111 ~R 122 are each independently selected from the group consisting of a hydrogen atom, a hydroxyl group, a C1-C8 alkyl group, a C1-C8 alkoxy group, an aryl group, a carboxyl group, a sulfonic acid group, a thiol group, a mercapto group, a cyano group, a thiocyanic acid group, an amino group, a C1-C8 alkyl ester group, a nitro group, and a halogen atom.]

[0225] The compound represented by the general formula (21) is a compound having a structure with two benzoxazinone skeletons at the para-position of the benzene ring, and the carbon at the 2-position of the benzoxazinone skeleton is bonded to the carbon at the para-position of the benzene ring. Each of the three benzene rings in this structure may have 1 to 4 substituents, or may have no substituents. There is no restriction on the position of the substituents. The types of substituents can also be selected independently of each other, and can be the same or different.

[0226] R in the general formula (21) 111 ~R 122 are each independently preferably selected from the group consisting of a hydrogen atom, a hydroxyl group, a C1-C8 alkyl group, a C1-C8 alkoxy group, an aryl group, a carboxyl group, and a sulfonic acid group, more preferably selected from the group consisting of a hydrogen atom, a hydroxyl group, a carboxyl group, and a sulfonic acid group, and further preferably selected from the group consisting of a hydrogen atom and a sulfonic acid group. The compound (2,2'-(1,4-phenylene)bis[4H-3,1-benzoxazin-4-one]) represented by the general formula (I) in which all of R 111 ~R 122 are hydrogen atoms can be preferably used.

[0227] As the compound represented by the general formula (21), commercially available products can be used. Examples of commercially available products include "Cyasorb (registered trademark) UV-3638F" (trade name) manufactured by CYTEC Corporation, "ELECUT ZA-101" (trade name) manufactured by Takemoto Yushi Co., Ltd., "KEMISORB500" (trade name) manufactured by CHEMIPRO KASEI Co., Ltd., etc.

[0228] Among them, at least one selected from benzotriazole-based compounds, malonic ester-based compounds, triazine-based compounds, and benzoxazine-based compounds is preferably selected.

[0229] Examples of the ultraviolet absorber include commercially available products such as Seesorb 709 (manufactured by SHIPRO KASEI Co., Ltd., trademark), KEMISORB 79 (manufactured by CHEMIPRO KASEI Co., Ltd., trademark), KEMISORB 279 (manufactured by CHEMIPRO KASEI Co., Ltd., trademark), Hostavin B-CAP (manufactured by Clariant Corporation, trademark), Tinuvin 234 (manufactured by BASF Japan Ltd., trademark), Tinuvin 1577 (manufactured by BASF Japan Ltd., trademark), Cyasorb UV-3638F (manufactured by CYTEC Corporation), etc.

[0230] The content of the above ultraviolet absorber is about 0.01 to 1 part by mass, preferably 0.05 to 0.7 part by mass, and more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the above PC-POS copolymer. If the content of the above ultraviolet absorber is 0.01 part by mass or more, sufficient light resistance characteristics can be obtained, and if it is 1 part by mass or less, contamination of the mold used in molding can be sufficiently suppressed.

[0231] <Silicone compound>

[0232] Compound (B) contained in the polycarbonate resin composition may include a silicone compound.

[0233] The silicone compound has the effect of suppressing yellowing by acting as a lubricant when granulating the polycarbonate resin composition, and the effect of preventing appearance defects such as silver streaks during molding. As the silicone compound, silicone compounds having a hydrocarbon group with 1 to 12 carbon atoms on the silicon atom, such as polydimethylsiloxane, polymethylethylsiloxane, and polymethylphenylsiloxane, can be used, and silicone compounds having functional groups are particularly preferably used. The silicone compound having a functional group is a polymer or copolymer having a structural unit represented by (R 1 ) a (R 2 ) b SiO (4-a-b) / 2 〔In the formula, R 1 represents a functional group, and R 2 represents a hydrocarbon group having 1 to 12 carbon atoms. In addition, a and b are integers satisfying 0 < a ≤ 3, 0 ≤ b < 3, and 0 < a + b ≤ 3.〕. As the functional group represented by R 1 , alkoxy group, aryloxy group, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, silanol group, amino group, mercapto group, epoxy group, vinyl group, etc. can be cited. Among these, alkoxy group, hydrogen group, hydroxyl group, epoxy group, and vinyl group are preferred, and methoxy group and vinyl group are more preferred. As the hydrocarbon group represented by R 2 , methyl group, ethyl group, phenyl group, etc. can be cited.

[0234] Among the above silicone compounds having functional groups, a silicone compound having a functional group formed by a structural unit containing phenyl as the hydrocarbon group represented by R 2 in the above formula is particularly useful. As the functional group represented by R 1 in the above formula, one kind of functional group can be contained, different kinds of multiple functional groups can be contained, or a mixture thereof can be used. It is preferably used that the functional group (R 1 ) / hydrocarbon group (R 2) The value is 0.1 to 3, preferably 0.3 to 2. The silicone-based compound containing a functional group can be liquid or powdery. In the case of being liquid, its viscosity at room temperature is preferably about 10 to 500000 cst. When using the polycarbonate resin composition for optical applications, it is preferable to reduce the refractive index difference from the polycarbonate resin. The refractive index of the silicone-based compound is preferably 1.45 to 1.65, more preferably 1.48 to 1.60.

[0235] In the polycarbonate resin composition, the sodium content of the silicone-based compound is preferably 15 mass ppm or less. If the sodium content in the silicone-based compound is 15 mass ppm or less, when using the polycarbonate resin composition to produce a molded article, an increase in the yellowness of the molded article can be suppressed. The sodium content in the silicone-based compound is preferably 10 mass ppm or less. As the silicone-based compound, commercially available compounds can be used. However, even for commercially available compounds, and even for products of the same manufacturer and the same grade, the sodium content sometimes varies. Therefore, when using the silicone-based compound, it is preferable to investigate the sodium content rate in advance and use a silicone-based compound with a low sodium content rate, or use it after reducing the sodium content rate. The silicone-based compound sometimes colors light yellow, and it is preferable to use a silicone-based compound with less coloring. As a method for reducing metal components such as sodium, a method of adsorption treatment using aluminum hydroxide, synthetic hydrotalcite, magnesium silicate, aluminum silicate, activated carbon, etc. is known.

[0236] In the polycarbonate-based resin composition, relative to 100 parts by mass of the PC-POS copolymer (A), the silicone-based compound can be contained in an amount of 0.01 to 0.25 parts by mass. If the content of the silicone-based compound is within the above range, the thermal stability during molding of the polycarbonate-based resin composition is excellent, and the appearance of the surface of the molded article can also be maintained well. The content of the silicone-based compound in the polycarbonate-based resin composition is preferably 0.03 to 0.2 parts by mass, more preferably 0.05 to 0.15 parts by mass, relative to 100 parts by mass of the PC-POS copolymer (A). The content of the silicone-based compound in the polycarbonate-based resin composition can be measured by gas chromatography, and the content does not change significantly compared with the compounding amount before melt-kneading.

[0237] <Epoxy compound>

[0238] For the polycarbonate-based resin composition, when using a phosphite-based antioxidant as the compound (B), it is basically preferable to contain an epoxy compound.

[0239] The phosphite-based antioxidant is more easily hydrolyzed than the polycarbonate resin in a humid and hot environment. In addition, decomposition products such as phosphoric acids and phenols generated during hydrolysis sometimes significantly promote the hydrolysis of the polycarbonate resin.

[0240] The present inventors have the following views: Epoxy compounds have the effect of inhibiting the hydrolysis of phosphite antioxidants or detoxifying the decomposition products generated by the hydrolysis of phosphite antioxidants. Even when 0.02 parts by mass or more of a phosphite antioxidant is added to the PC-POS copolymer (A), if an epoxy compound is used in combination, the reduction rate of the viscosity-average molecular weight can also be adjusted to a value below a specified value.

[0241] Examples of the epoxy compound include compounds in which a part of the structure is epoxidized.

[0242] Among epoxy compounds, from the above viewpoints, alicyclic epoxy compounds, or epoxidized natural oils or epoxidized synthetic oils having an epoxyethane oxygen concentration of 4% or more are preferred.

[0243] When a molded article formed from a resin composition is used for applications such as food containers, from the viewpoint of producing a molded article capable of safely storing food, epoxidized natural oils or epoxidized synthetic oils having an epoxyethane oxygen concentration of 4% or more are more preferred.

[0244] Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate (trade name "CELLOXIDE 2021P" manufactured by Daicel Chemical Industries, Ltd., etc.), 1,2-epoxy-4-(2-epoxyethyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (trade name "EHPE 3150" manufactured by Daicel Chemical Industries, Ltd., etc.), and a mixture of these two (trade name EHPE 3150CE manufactured by Daicel Chemical Industries, Ltd.).

[0245] Examples of the epoxidized natural oil having an epoxyethane oxygen concentration of 4% or more include SANSO CIZER E-2000H (trade name, manufactured by Shin Nippon Rika Co., Ltd., epoxidized soybean oil, epoxyethane oxygen concentration 6.7% or more), SANSOCIZER E-9000H (trade name, manufactured by Shin Nippon Rika Co., Ltd., epoxidized linseed oil, epoxyethane oxygen concentration 8.5% or more), etc.

[0246] Examples of the epoxidized synthetic oil having an epoxyethane oxygen concentration of 4% or more include SANSO CIZER E-PO (trade name, manufactured by Shin Nippon Rika Co., Ltd., diepoxy stearyl hexahydrophthalate, epoxyethane oxygen concentration 5.5% or more), SANSO CIZER E-4030 (trade name, manufactured by Shin Nippon Rika Co., Ltd., epoxidized fatty acid butyl ester, epoxyethane oxygen concentration 4.5% or more), etc.

[0247] The epoxyethane oxygen concentration of the epoxidized natural oil or epoxidized synthetic oil is 4% or more, preferably 5% or more, more preferably 6% or more, and further preferably 7% or more. If the epoxyethane oxygen concentration is less than 4%, the hydrolysis of the phosphite antioxidant or the effect of detoxifying the decomposition products generated by hydrolysis is low. As a result, the hydrolysis of the polycarbonate cannot be inhibited, and it is difficult to adjust the molecular weight reduction rate to below a specified value.

[0248] It should be noted that the above epoxyethane oxygen concentration refers to the value measured using an acetic acid solution of hydrogen bromide based on the provisions of ASTM-1652.

[0249] The content of the epoxy compound is 0 to 0.2 parts by mass with respect to 100 parts by mass of the PC-POS copolymer (A) component. If the content is within the above range, the fluidity of the polycarbonate resin composition is well maintained, and no problems occur during the molding process.

[0250] <Polyether compound>

[0251] The polycarbonate resin composition may contain a polyether compound having a polyoxyalkylene group structure as the compound (B). The polyether compound can improve the initial color tone during the molding of the polycarbonate resin composition. The polyether compound having a polyoxyalkylene group structure preferably has a polyoxyalkylene group structure represented by (R C1 O) m and a polyoxyalkylene group structure represented by (R C2 O) n . Here, R C1 and R C2 each independently represent an alkylene group having 1 or more carbon atoms. m + n is 5 or more and less than 300, preferably 10 to 200, and more preferably 20 to 100.

[0252] As the alkylene group represented by R C1 and R C2 , for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, etc. can be cited, and an alkylene group having 1 to 5 carbon atoms is preferred.

[0253] Among the m R C1 O groups, the plurality of R C1 can be the same alkylene group as each other or alkylene groups having different carbon atom numbers. That is, the polyoxyalkylene group represented by (R C1 O) m is not limited to the case where a single oxyalkylene group unit such as a polyoxyethylene group or a polyoxypropylene group is used as a repeating unit, and may have a plurality of oxyalkylene group units having different carbon atom numbers such as an oxyethylene group unit and an oxypropylene group unit as repeating units.

[0254] R C2is also the same as R C1 are the same, and n R C2 in the O groups, multiple R C2 can be alkylene groups that are the same as each other or alkylene groups with different numbers of carbon atoms.

[0255] Regarding the above R C1 and R C2 in the alkylene groups shown, from the viewpoint of improving the initial hue, R C1 and R C2 are preferably alkylene groups selected from ethylene group, propylene group, and tetramethylene group, and at least one of R C1 and R C2 is any one of an ethylene group or a propylene group.

[0256] In addition, the polyether compound is preferably at least one selected from the compounds represented by the following general formula (IX), the alkylene oxide adducts of polyols and their esters, and cyclic polyether compounds.

[0257] R C3 O-(R C1 O) m -A-(R C2 O) n -R C4 (IX)

[0258] (In the formula, R C1 and R C2 each independently represent an alkylene group having 1 or more carbon atoms. m + n is 5 or more and less than 300. R C3 and R C4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkanoyl group having 1 to 30 carbon atoms, an alkenoyl group having 2 to 30 carbon atoms, or a glycidyl group. A represents a single bond or a divalent organic group.)

[0259] Regarding the alkylene groups represented by R C1 and R C2 , it is as described above. In addition, regarding the polyoxyalkylene group structure represented by (R C1 O) m and the polyoxyalkylene group structure represented by (R C2 O) n , it is also as described above.

[0260] As the hydrocarbon group having 1 to 30 carbon atoms represented by R C3 and R C4 , examples include an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, etc.

[0261] The alkyl and alkenyl groups can be linear, branched, or cyclic, and examples thereof include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, cyclopentyl, cyclohexyl, allyl, propenyl, various butenyl groups, various hexenyl groups, various octenyl groups, cyclopentenyl, cyclohexenyl, etc. As the aryl group, examples include phenyl, tolyl, xylyl, etc. As the aralkyl group, examples include benzyl, phenethyl, methylbenzyl, etc.

[0262] As R C3 and R C4 The alkanoyl group having 1 to 30 carbon atoms represented by can be linear or branched, and examples thereof include formyl, acetyl, n-propionyl, isopropionyl, n-butyryl, tert-butyryl, n-hexanoyl, n-octanoyl, n-decanoyl, n-dodecanoyl, benzoyl, etc. Among them, from the viewpoints of compatibility, thermal stability, and ease of production, an alkanoyl group having 1 to 20 carbon atoms is preferred.

[0263] As R C3 and R C4 The alkenoyl group having 2 to 30 carbon atoms represented by can be linear or branched, and examples thereof include vinylcarbonyl, n-propenoyl, isopropenoyl, n-butenoyl, tert-butenoyl, n-hexenoyl, n-octenoyl, n-decenoyl, n-dodecenoyl, etc. Among them, from the viewpoints of obtaining a low molecular weight, compatibility, solubility, and ease of production, an alkenoyl group having 2 to 10 carbon atoms is preferred, and an alkenoyl group having 2 to 6 carbon atoms is more preferred.

[0264] As the divalent organic group represented by A, for example, a group represented by the following formula (a) can be mentioned.

[0265] [Chemical formula 23]

[0266]

[0267] As specific examples of the polyether compound represented by the above general formula (IX), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxytetramethylene polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene monomethyl ether, polyoxyethylene dimethyl ether, polyoxyethylene-bisphenol A ether, polyoxypropylene-bisphenol A ether, polyoxyethylene-polyoxypropylene-bisphenol A ether, polyethylene glycol-allyl ether, polyethylene glycol-diallyl ether, polypropylene glycol-allyl ether, polypropylene glycol-diallyl ether, polyethylene glycol-polypropylene glycol-allyl ether, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, polypropylene glycol distearate, etc. can be mentioned. They can be obtained as commercially available products. For example, "Uniox (registered trademark)", "UNIOL (registered trademark)", "UNILUBE (registered trademark)", "UNISAFE (registered trademark)", "Polycerin (registered trademark)", "EPIOL (registered trademark)", etc. manufactured by NOF Corporation can be used.

[0268] As the polyol in the alkylene oxide adduct of polyol and its ester, glycerin, diglycerol ether, sorbitol, etc. can be mentioned.

[0269] As specific examples of the cyclic polyether compound, 18-crown-6, dibenzo-18-crown-6, etc. can be mentioned.

[0270] As the above polyether compound, at least 1 kind selected from polyethylene glycol, polypropylene glycol, and polyoxyethylene glycol-polyoxypropylene glycol is preferably used.

[0271] The number average molecular weight of the above polyether compound is not particularly limited, and is preferably 200 to 10,000, more preferably 500 to 8,000, and further preferably 1,000 to 5,000.

[0272] The content of the polyether compound in the polycarbonate resin composition is preferably 0.2 to 1 part by mass, more preferably 0.2 to 0.9 part by mass, and further preferably 0.3 to 0.8 part by mass with respect to 100 parts by mass of the PC-POS copolymer (A). If the content of the polyether compound is 0.2 part by mass or more, the initial YI value of the molded body can be maintained well. If the content of the polyether compound is 1 part by mass or less, the YI value of the molded product can be maintained well when kept at high temperature and when kept at high humidity, the hue is excellent, and it will not have an adverse effect on the transparency of optical molded products such as light guide plates.

[0273] By melt-kneading the obtained PC-POS copolymer, raw material pellets can be obtained. The above compound (B) can be added during melt-kneading. As other additives, reinforcing materials, fillers, elastomers for improving impact resistance, antistatic agents, other resins other than polycarbonate, etc. can be mentioned, and the addition amounts can also be appropriately selected and added in appropriate proportions.

[0274] In the molded article of the present invention, as a polycarbonate resin component, it is preferred that no polycarbonate resin other than the PC-POS copolymer (A) is contained. By using only the polycarbonate-polyorganosiloxane copolymer (A) as a polycarbonate resin component, the molded article of the present invention can maintain high transparency while having high flexibility.

[0275] According to one embodiment of the present invention, the content of the polyorganosiloxane block (A-2) contained in the polycarbonate resin composition is preferably greater than 40% by mass and less than 70% by mass. The content of the polyorganosiloxane block (A-2) contained in the above-mentioned resin composition is more preferably greater than 41% by mass, more preferably greater than 45% by mass, for example greater than 50% by mass, preferably less than 65% by mass, more preferably less than 62% by mass.

[0276] According to another embodiment of the present invention, the content of the polyorganosiloxane block (A-2) contained in the polycarbonate resin composition is preferably 25% by mass or more and 70% by mass or less. The content of the polyorganosiloxane block (A-2) contained in the above-mentioned resin composition is more preferably 30% by mass or more, further preferably more than 40% by mass, further preferably more than 41% by mass, further preferably more than 45% by mass, for example more than 50% by mass, more preferably less than 65% by mass, further preferably less than 62% by mass.

[0277] Melt kneading can be carried out by the following method: after premixing with commonly used equipment such as a ribbon mixer, a drum roller, etc., a method using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder and a kneader (Japanese original: コニ一ゲ) etc. The heating temperature during kneading is usually appropriately selected in the range of more than 240° C. and less than 320° C. As the melt kneading, an extruder is preferably used, and a vented extruder is particularly preferably used.

[0278] <molded body>

[0279] The molded body of the present invention can be manufactured by using the above-mentioned melt-kneaded polycarbonate resin composition or the obtained pellets as raw materials, and utilizing injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum forming, and foaming molding. In particular, the molded body of the present invention is preferably a molded body obtained by using pellets of a polycarbonate resin composition containing the above-mentioned PC-POS copolymer (A) obtained by melt kneading. As described above, the polycarbonate resin composition preferably contains only the PC-POS copolymer (A) as a polycarbonate resin component, and does not contain other polycarbonate resins.

[0280] In other aspects of the present invention, it is important that the content of the polyorganosiloxane block (A-2) contained in the shaped body is 25% by mass or more and 70% by mass or less.

[0281] By making the content of the polyorganosiloxane block (A-2) in the shaped body 25% by mass or more, a resin composition excellent in flexibility and mechanical strength can be obtained. If the content of the polyorganosiloxane block (A-2) in the shaped body is 70% by mass or less, there is no significant stickiness, and a soft shaped body can be obtained.

[0282] Here, the "content of the polyorganosiloxane block (A-2) in the shaped body" has the same meaning as the amount of the polyorganosiloxane block (A-2) in the resin composition. It refers to the amount of the polyorganosiloxane block in the shaped body obtained by granulating the resin composition and subjecting the granule to various shaping methods described below.

[0283] The content of the polyorganosiloxane block (A-2) in the shaped body is preferably 30% by mass or more, more preferably more than 40% by mass, further preferably 41% by mass or more, further preferably 45% by mass or more, for example, more than 50% by mass, preferably 65% by mass or less, and more preferably 62% by mass or less.

[0284] The shaped body of the present invention is characterized by having both excellent flexibility and transparency. Each property will be described in detail.

[0285] The flexibility will be described in detail. The shaped body of the present invention needs to have a durometer hardness based on a Type D durometer of 25 or more and 72 or less as measured by the method described in the examples in accordance with JIS K6253-3:2012.

[0286] The durometer hardness is an index indicating the indentation hardness. In order to obtain a molded article having high flexibility while maintaining a certain degree of mechanical strength, the durometer hardness of the D-type durometer needs to be within the above range. The molded article of the present invention containing a specific PC-POS copolymer (A) in the polycarbonate resin composition has excellent flexibility, so it can be used as a lighting cover without the aid of a sealing member and can cope with a light guide having a complex shape, which can dramatically improve the ease of construction. In addition, even in the case of an optical member having an internal void structure with an undercut draft angle, it can be integrally molded without performing an internal cutting process, so it can be suitably used for a collimating lens. Because of its excellent transparency and flexibility, it can be suitably used in household appliances for substrates of flexible displays, light guide plates, housings, and water / oil repellent films, optical adhesives, switch covers, heat sealants, water blocking materials, sealants, connectors, adapters, smartphone covers, etc.; in optical applications for lenses, glasses / sunglasses parts, optical fiber parts; in automobiles for buffer materials for in-vehicle batteries, wiper blades, curved mirrors, side mirrors, rearview mirrors, lamp housings, bumpers, windows, interlayer glass, exterior decorative materials, interior decorative materials, sound absorbing materials, steering wheel covers, sensor covers, etc.; in daily necessities for watch parts, stationery, cosmetic containers, aquariums for raising aquatic organisms, soles, cups, nail polishes, toys, lures, suction cups, cooking utensils such as steamers, clothes, silicone wiping sheets, remote control covers, umbrellas, linings for metal containers, etc.; in building materials for building material claddings, doors, windows, interlayer glass, tents, mirrors, display cabinets, plastic greenhouses, etc.; in medical applications for medical device housings, infusion bags, infusion tubes, syringes, baby bottles, masks, face shields, filter parts, etc.; in other applications for shock-absorbing parts, robot housings, drone housings, shields, bulletproof shields, sports cushioning equipment, aircraft windows, resin compatibilizers, etc.

[0287] The durometer hardness of the molded article of the present invention based on the D-type durometer is more preferably 30 or more, further preferably 40 or more, more preferably 70 or less, and further preferably 68 or less.

[0288] According to the use of the molded article of the present invention, the preferred range of the durometer hardness may sometimes change. For example, in the case of a use that emphasizes flexibility, it is more preferably 28 or more and more preferably 33 or less. In the case of a use that emphasizes mechanical strength, it is more preferably 60 or more and more preferably 65 or less. In addition, in the case of a use that emphasizes both flexibility and mechanical strength, it is more preferably 45 or more and more preferably 50 or less.

[0289] Depending on the shape of the molded article, it may sometimes be impossible to measure the durometer hardness. In such cases, the molded article can be temporarily melted and remolded into a shape capable of measuring the durometer hardness, and thus the durometer hardness can be measured. The molding conditions at this time are the same as the molding method described in the examples.

[0290] As a raw material for obtaining such a molded article, a raw material obtained by cutting, decomposing, destroying, etc. the molded article and the member containing the molded article can be used.

[0291] The transparency will be described in detail. The molded article of the present invention preferably has a total light transmittance of 75% or more when measured at a thickness of 2 mm according to JIS K7361-1:1997. By making the total light transmittance based on the above conditions 75% or more, the transparency is excellent, and thus it can be suitably used as the above-mentioned optically transparent member.

[0292] The total light transmittance of the molded article of the present invention at a thickness of 2 mm is more preferably 85% or more, further preferably 89% or more, further preferably 90% or more, further preferably 91% or more, and particularly preferably 92% or more.

[0293] The molded article of the present invention can be used as an optical member or a transparent member. Specifically, it can be suitably used for at least one selected from flexible displays, light guide plates, housings, water / oil repellent films, optical adhesives, switch covers, heat sealants, water blocking materials, sealants, connectors, adapters, smartphone covers, lenses, glasses / sunglasses parts, optical fiber parts, buffer materials for in-vehicle batteries, wiper blades, curved mirrors, side mirrors, rearview mirrors, lamp shades, bumpers, windows, exterior decorative materials, interior decorative materials, sound absorbing materials, steering wheel covers, sensor covers, watch parts, stationery, cosmetic containers, aquariums for raising aquatic organisms, soles, cups, nail paintings, toys, fishing lures, suction cups, cooking utensils such as steamers, clothes, silicone wiping sheets, remote control covers, umbrellas, linings for metal containers, building material claddings, doors, windows, glass interlayers, tents, mirrors, display cabinets, plastic greenhouses, medical device housings, infusion bags, infusion tubes, syringes, baby bottles, masks, face shields, filter parts, shock absorbing parts, robot housings, drone housings, shields, bulletproof shields, sports cushioning equipment, aircraft windows, resin compatibilizers, lighting covers, light guides, light guide panels, lighting units, prism panels, flat lenses, Fresnel lenses, microlens arrays, and collimating lenses.

[0294] Examples

[0295] Next, the present invention will be further specifically described by way of examples, but the present invention is not limited by any of these examples. The characteristic values and evaluation results in each example are obtained according to the following points.

[0296] (1) Polydimethylsiloxane chain length and content

[0297] Measured by NMR and calculated based on the integral value ratio of the methyl groups of polydimethylsiloxane. In this specification, polydimethylsiloxane is sometimes abbreviated as PDMS.

[0298] <Quantification method for the chain length of polydimethylsiloxane>

[0299] 1 H-NMR measurement conditions

[0300] NMR apparatus: ECA500 manufactured by JEOL RESONANCE Co., Ltd.

[0301] Probe: 50TH5AT / FG2

[0302] Observation range: -5 to 15 ppm

[0303] Observation center: 5 ppm

[0304] Pulse repetition time: 9 seconds

[0305] Pulse width: 45°

[0306] NMR sample tube: 5φ

[0307] Sample amount: 30 - 40 mg

[0308] Solvent: deuterated chloroform

[0309] Measurement temperature: room temperature

[0310] Number of accumulations: 256 times

[0311] In the case of allylphenol-terminated polydimethylsiloxane

[0312] A: Integral value of the methyl groups in the dimethylsiloxane part observed around δ -0.02 to 0.5

[0313] B: Integral value of the methylene groups of allylphenol observed around δ 2.50 to 2.75

[0314] Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0315] In the case of eugenol-terminated polydimethylsiloxane

[0316] A: Integral value of the methyl groups in the dimethylsiloxane part observed around δ -0.02 to 0.5

[0317] B: Integral value of the methylene groups of eugenol observed around δ 2.40 to 2.70

[0318] Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0319] <Quantitative method for polydimethylsiloxane content>

[0320] Quantitative method for the amount of polydimethylsiloxane copolymerized in PTBP-capped polycarbonate obtained by copolymerizing allylphenol-capped polydimethylsiloxane

[0321] NMR apparatus: ECA500 manufactured by JEOL RESONANCE Co., Ltd.

[0322] Probe: 50TH5AT / FG2

[0323] Observation range: -5 to 15 ppm

[0324] Observation center: 5 ppm

[0325] Pulse repetition time: 9 seconds

[0326] Pulse width: 45°

[0327] Number of accumulations: 256 times

[0328] NMR sample tube: 5φ

[0329] Sample amount: 30 - 40 mg

[0330] Solvent: Deuterated chloroform

[0331] Measurement temperature: Room temperature

[0332] A: Integral value of the methyl group of the BPA part observed around δ 1.5 - 1.9

[0333] B: Integral value of the methyl group of the dimethylsiloxane part observed around δ -0.02 - 0.3

[0334] C: Integral value of the butyl group of the p-tert-butylphenyl part observed around δ 1.2 - 1.4

[0335] a = A / 6

[0336] b = B / 6

[0337] c = C / 9

[0338] T = a + b + c

[0339] f = a / T × 100

[0340] g = b / T × 100

[0341] h = c / T × 100

[0342] TW = f × 254 + g × 74.1 + h × 149

[0343] PDMS (wt%) = g × 74.1 / TW × 100

[0344] <Quantification method for the block amount shown in Formula (III)>

[0345] 13 C-NMR measurement conditions

[0346] NMR apparatus: ECA500 manufactured by JEOL RESONANCE, Ltd.

[0347] Probe: C5HPD / FG probe

[0348] Observation range: -25 to 225 ppm

[0349] Observation center: 100 ppm

[0350] Pulse repetition time: 4 seconds

[0351] Pulse width: 45°

[0352] NMR sample tube: 10φ

[0353] Sample amount: 250 - 300 mg

[0354] Solvent: Deuterochloroform

[0355] Measurement temperature: Room temperature

[0356] Number of accumulations: 10,000 times

[0357] Measured under the above conditions 13 In the C-NMR spectrum, based on tetramethylsilane (TMS), according to the area A of the signal peak of the carbonate bond of the block shown in Formula (III) detected at 150.9 ppm and the area B of the signal peak detected at 152.1 ppm where the carbonate bonds of the blocks shown in Formula (I-a) and (III-a) overlap, it is calculated using the calculation formula of A / (A + B) (unit: mol%).

[0358] Regarding the lower limit of quantification of this quantification method, according to 13 the SN ratio of the baseline of the C-NMR spectrum, it is calculated to be less than 0.1 mol%.

[0359] [Chemical formula 24]

[0360]

[0361] [In the above formula, R 1 、R 2 、R 31 ~R 35 、X, a, b and t are as described above]

[0362] (2) Viscosity-average molecular weight

[0363] The viscosity-average molecular weight (Mv) can be determined by measuring the viscosity of a dichloromethane solution at 20 °C using an Ubbelohde viscometer, from which the intrinsic viscosity [η] is obtained, and then calculated using the following formula (Schnell formula).

[0364] [Mathematical formula 2]

[0365] [η] = 1.23×10 -5 ×Mv 0.83

[0366] (3) Weight-average molecular weight, molecular weight distribution

[0367] Regarding the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn), measurement is carried out using a high-performance GPC device HLC-8220GPC (manufactured by Tosoh Corporation) under the following conditions, and calculated based on the universal calibration curve prepared using a molecular weight standard sample.

[0368] Column temperature: 40 °C

[0369] Columns: TSK-GEL GMHXL-L, TSK-GEL G4000HXL, TSK-GEL G2000HXL (manufactured by Tosoh Corporation)

[0370] Mobile phase solvent: Tetrahydrofuran

[0371] Flow rate: 1.0 ml / minute

[0372] Detector: RI

[0373] Injection concentration: 10 mg / 10 ml

[0374] Injection volume: 0.1 ml

[0375] Molecular weight standard sample: Polycarbonate 18050 (manufactured by Idemitsu Kosan Co., Ltd., molecular weight error ±5% / 17148 - 18953), Polycarbonate 18100 (manufactured by Idemitsu Kosan Co., Ltd., molecular weight error ±5% / 17200 - 19100)

[0376] (4) Durometer hardness

[0377] Regarding the durometer hardness of Type A, a rubber durometer ESA type (manufactured by Elastron Co., Ltd.) and a constant pressure load applicator EDL-1 (manufactured by Elastron Co., Ltd.) are used, and measurement is carried out under a 1 kg load according to JIS K6253-3:2012 Type A and ISO7619 Type A.

[0378] Regarding the hardness of the D-type durometer, the rubber durometer ESD type (manufactured by Elastron Co., Ltd.) and the constant-pressure load applicator EDL-1 special type (equipped with an oil shock absorber, manufactured by Elastron Co., Ltd.) were used. According to JIS K6253-3:2012 D-type and ISO7619 D-type, the measurement was carried out under a 5 kg load.

[0379] (5) Total light transmittance

[0380] Using the haze meter NDH 5000 (manufactured by Nippon Denshoku Industries Co., Ltd.), the measurement was carried out with a thickness of 2 mm according to JIS K7361-1:1997.

[0381] (Manufacture of polycarbonate oligomer)

[0382] In a 5.6 mass% aqueous sodium hydroxide solution, sodium dithionite at 2000 ppm relative to bisphenol A (BPA) (dissolved later) was added. BPA was dissolved therein to make the BPA concentration reach 13.5 mass%, thereby preparing an aqueous sodium hydroxide solution of BPA. The aqueous sodium hydroxide solution of BPA was continuously introduced into a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 L / hour, dichloromethane at a flow rate of 15 L / hour, and phosgene at a flow rate of 4.0 kg / hour. The tubular reactor has a jacket part, and cooling water is passed through the jacket to keep the temperature of the reaction solution below 40 °C. The reaction solution coming out of the tubular reactor was continuously introduced into a baffled tank reactor with an internal volume of 40 L equipped with a swept wing, and further thereto, an aqueous sodium hydroxide solution of BPA was added at a flow rate of 2.8 L / hour, a 25 mass% aqueous sodium hydroxide solution at a flow rate of 0.07 L / hour, water at a flow rate of 17 L / hour, and a 1 mass% aqueous triethylamine solution at a flow rate of 0.64 L / hour, and the reaction was carried out. The reaction solution overflowing from the tank reactor was continuously withdrawn and allowed to stand, whereby the aqueous phase was separated and removed, and the dichloromethane phase was collected.

[0383] Regarding the polycarbonate oligomer thus obtained, its concentration was 341 g / L and the concentration of the chloroformate group was 0.71 mol / L.

[0384] Production Example 1

[0385] In a 1-L detachable flask equipped with a mechanical stirrer with baffles and stirring blades, 185 mL of the polycarbonate oligomer solution (PCO) prepared as described above, 445 mL of dichloromethane, 40.4 g of allylphenol-terminated modified polydimethylsiloxane with an average chain length n = 37, and 0.104 mL (0.75 mmol) of triethylamine (TEA) were added. Under stirring conditions, an aqueous sodium hydroxide solution A (NaOHaq) prepared in advance (1.9 g (47 mmol) of sodium hydroxide, 22 mL of ion-exchanged water) was added thereto, and the reaction of the polycarbonate oligomer with the allylphenol-terminated modified PDMS was carried out for 20 minutes. Then, an aqueous sodium hydroxide solution B prepared in advance [BisP-AP (manufactured by Honshu Chemical Industry Co., Ltd.): 4.8 g (16 mmol), sodium hydroxide: 2.9 g (73 mmol), ion-exchanged water: 42 mL, sodium sulfite (Na 2 S 2 O 4 ): 0.006 g (0.038 mmol)] was further added, and polymerization was carried out for 20 minutes.

[0386] To the obtained polymerization solution, a dichloromethane solution of p-tert-butylphenol (PTBP: manufactured by DIC Corporation) [a solution obtained by dissolving 1.5 g (10.0 mmol) of PTBP in 10 mL of dichloromethane], an aqueous sodium hydroxide solution C of BPA [a solution obtained by dissolving 3.0 g (10 mmol) of bisphenol A, 5.2 g (131 mmol) of NaOH, and Na 2 S 2 O 4 : 0.006 g (0.038 mmol) in 77 mL of ion-exchanged water] were added, and a polymerization reaction was carried out for 20 minutes.

[0387] After the polymerization was completed, the reaction solution was transferred to a separatory funnel, allowed to stand, separated into an organic phase and an aqueous phase, and then the organic layer was transferred to another separatory funnel. It was washed successively with 100 mL of a 0.03 mol / L aqueous NaOH solution and 100 mL of a 0.2 mol / L hydrochloric acid, and then washed repeatedly with ion-exchanged water until the conductivity of the washed aqueous phase reached 10 μS / m or less.

[0388] The washed organic layer was transferred to a vat, and dried overnight at 48 °C using an explosion-proof dryer (under a nitrogen atmosphere) to obtain a flaky PC-POS copolymer. By cutting the flaky PC-POS copolymer, a flaky PC-POS copolymer (a2) was obtained. The details of the PC-POS copolymer are shown in Table 1-1.

[0389] Production Example 2

[0390] 43.0 g of allylphenol-capped modified polydimethylsiloxane with an average chain length n = 23 was used, and aqueous sodium hydroxide solution A was a solution obtained by dissolving 3.7 g (94 mmol) of NaOH in 43 mL of ion-exchanged water. Aqueous sodium hydroxide solution B was a mixture of 5.5 g (19 mmol) of BisP-AP (manufactured by Honshu Chemical Industry Co., Ltd.), 2.3 g (57 mmol) of NaOH, 33 mL of ion-exchanged water, and 0.031 g (0.196 mmol) of Na 2 S 2 O 4 : 0.031 g (0.196 mmol). Aqueous sodium hydroxide solution C of BPA was a solution obtained by dissolving 2.5 g (8.7 mmol) of bisphenol A, 1.9 g (46.3 mmol) of NaOH, and Na 2 S 2 O 4 : 0.031 g (0.196 mmol) in 27 mL of ion-exchanged water. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain a PC-POS copolymer (a10). The details of the PC-POS copolymer are shown in Table 1-1.

[0391] Production Example 3

[0392] 46.0 g of allylphenol-capped modified polydimethylsiloxane with an average chain length n = 63 was used, and aqueous sodium hydroxide solution A was a solution obtained by dissolving 2.2 g (55.9 mmol) of NaOH in 26 mL of ion-exchanged water. Aqueous sodium hydroxide solution B was a mixture of 5.8 g (20 mmol) of BisP-AP (manufactured by Honshu Chemical Industry Co., Ltd.), 2.4 g (60 mmol) of NaOH, 35 mL of ion-exchanged water, and 0.031 g (0.196 mmol) of Na 2 S 2 O 4 : 0.031 g (0.196 mmol). Aqueous sodium hydroxide solution C of BPA was a solution obtained by dissolving 6.6 g (22.6 mmol) of bisphenol A, 3.2 g (80.9 mmol) of NaOH, and Na 2 S 2 O 4 : 0.031 g (0.196 mmol) in 47 mL of ion-exchanged water. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain a PC-POS copolymer (a14). The details of the PC-POS copolymer are shown in Table 1-1.

[0393] Production Example 4

[0394] The amount of allylphenol-terminated modified polydimethylsiloxane was set to 62.0 g. Aqueous sodium hydroxide solution A was a solution obtained by dissolving 3.1 g (77 mmol) of NaOH in 35 mL of ion-exchanged water. Aqueous sodium hydroxide solution B was a solution obtained by dissolving 6.0 g (21 mmol) of BisP-AP, 2.5 g (62 mmol) of NaOH, and 2 S 2 O 4 : 0.031 g (0.20 mmol) in 36 mL of ion-exchanged water. Aqueous sodium hydroxide solution C was a solution obtained by dissolving 4.0 g (14 mmol) of bisphenol A, 2.3 g (58 mmol) of NaOH, and 2 S 2 O 4 : 0.031 g (0.20 mmol) in 34 mL of ion-exchanged water. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain a PC-POS copolymer (a3). The details of the PC-POS copolymer are shown in Table 1-1.

[0395] Production Example 5

[0396] The amount of allylphenol-terminated modified polydimethylsiloxane was set to 96.0 g. Aqueous sodium hydroxide solution A was a solution obtained by dissolving 4.0 g (100 mmol) of NaOH in 46 mL of ion-exchanged water. Aqueous sodium hydroxide solution B was a solution obtained by dissolving 7.7 g (27 mmol) of BisP-AP, 4.7 g (118 mmol) of NaOH, and 2 S 2 O 4 : 0.031 g (0.20 mmol) in 69 mL of ion-exchanged water. Aqueous sodium hydroxide solution C was not added. Except for this, the production was carried out in the same manner as in Production Example 1 to obtain a PC-POS copolymer (a5). The details of the PC-POS copolymer are shown in Table 1-1.

[0397] Production Example 6

[0398] The amount of allylphenol-terminated modified polydimethylsiloxane was set to 4.0 g. Aqueous sodium hydroxide solution A was a solution obtained by dissolving 1.5 g (38 mmol) of NaOH in 18 mL of ion-exchanged water. 1.8 g (12.0 mmol) of PTBP was used. Aqueous sodium hydroxide solution C was a solution obtained by dissolving 13.2 g (45 mmol) of bisphenol A, 6.3 g (159 mmol) of NaOH, and 2 S 2 O 4: A solution obtained by dissolving 0.031 g (0.20 mmol) in 93 mL of ion-exchanged water. Without adding aqueous sodium hydroxide solution B, the production was carried out in the same manner as in Production Example 1 to obtain PC-POS copolymer (a9). Details of the PC-POS copolymer are shown in Table 1-2.

[0399] Production Example 7

[0400] The amount of allylphenol-capped modified polydimethylsiloxane was set to 23.0 g. Aqueous sodium hydroxide solution A used a solution obtained by dissolving 2.0 g (50.8 mmol) of NaOH in 23 mL of ion-exchanged water. 1.8 g (12.0 mmol) of PTBP was used, and aqueous sodium hydroxide solution C used bisphenol A: 11.7 g (40.4 mmol), NaOH: 5.8 g (146.0 mmol), and Na 2 S 2 O 4 : A solution obtained by dissolving 0.031 g (0.20 mmol) in 85 mL of ion-exchanged water. Without adding aqueous sodium hydroxide solution B, the production was carried out in the same manner as in Production Example 1 to obtain PC-POS copolymer (a12). Details of the PC-POS copolymer are shown in Table 1-2.

[0401] Production Example 8

[0402] The amount of allylphenol-capped modified polydimethylsiloxane was set to 55 g. Aqueous sodium hydroxide solution A used a solution obtained by dissolving 2.9 g (72.1 mmol) of NaOH in 33 mL of ion-exchanged water. 1.8 g (12.0 mmol) of PTBP was used, and aqueous sodium hydroxide solution C used bisphenol A: 9.3 g (32.0 mmol), NaOH: 5.0 g (124.7 mmol), and Na 2 S 2 O 4 : A solution obtained by dissolving 0.031 g (0.20 mmol) in 73 mL of ion-exchanged water. Without adding aqueous sodium hydroxide solution B, the production was carried out in the same manner as in Production Example 1 to obtain PC-POS copolymer (a13). Details of the PC-POS copolymer are shown in Table 1-2.

[0403] Production Example 9

[0404] The amount of allylphenol-terminated modified polydimethylsiloxane was set to 78.0 g. Aqueous sodium hydroxide solution A was a solution obtained by dissolving 3.5 g (87 mmol) of NaOH in 40 mL of ion-exchanged water. 1.8 g (12.0 mmol) of PTBP was used. Aqueous sodium hydroxide solution C was a solution obtained by dissolving 7.5 g (26 mmol) of bisphenol A, 4.4 g (109 mmol) of NaOH, and 0.031 g (0.20 mmol) of 2 S 2 O 4 in 70 mL of ion-exchanged water. Aqueous sodium hydroxide solution B was not added, and otherwise, the production was carried out in the same manner as in Production Example 1 to obtain a PC-POS copolymer (a7). The details of the PC-POS copolymer are shown in Table 1-2.

[0405] [Table 1-1]

[0406] Table 1-1

[0407]

[0408] *1: BPA block: Represents the PC block derived from BPA.

[0409] *2: PC block other than BPA: Represents the PC block derived from a diphenol other than BPA.

[0410] [Table 1-2]

[0411] Table 1-2

[0412]

[0413] *1: BPA block: Represents the PC block derived from BPA.

[0414] *2: PC block other than BPA: Represents the PC block derived from a diphenol other than BPA.

[0415] Examples 1 to 49, Comparative Examples 1 to 3

[0416] The PC-POS copolymer (A) obtained in each production example and each compound (B) shown in Tables 3 to 7 were melt-kneaded and pelletized, and the resulting resin composition was formed using a vacuum press (manufactured by Iwamoto Seisakusho, manual hydraulic vacuum heating press). 7.0 g of the resin was placed into a mold with a longitudinal dimension of 5 cm × a lateral dimension of 5 cm × a thickness of 2 mm, and the surface in contact with the resin was clamped with a mirror-finished aluminum plate and placed into the vacuum press. The inside of the vacuum press tank was depressurized to -0.1 MPa or less relative to the atmospheric pressure. Thereafter, according to the PC-POS copolymer (A) contained in each resin composition, it was heated to the forming temperatures shown in Tables 2-1 and 2-2. After reaching the forming temperature, the pressing pressure was set to 2 MPa and then heated for 2 minutes. Next, the pressing pressure was increased over 3 minutes and formed for 5 minutes while maintaining 15 MPa. After forming, the formed body was taken out after returning to the atmospheric pressure and cooled until reaching room temperature. Thereafter, it was peeled off from the mirror-finished aluminum plate to obtain a measurement sample with a longitudinal dimension of 5 cm × a lateral dimension of 5 cm × a thickness of 2 mm. The evaluation results of the obtained formed bodies are shown in Tables 3 to 7.

[0417] [Table 2-1]

[0418] Table 2-1

[0419]

[0420] [Table 2-2]

[0421] Table 2-2

[0422]

[0423] [Table 3]

[0424]

[0425] [Table 4]

[0426] Table 4

[0427]

[0428] [Table 5]

[0429]

[0430] [Table 6]

[0431]

[0432] [Table 7]

[0433] Table 7

[0434]

[0435] Compound (B)

[0436] <Antioxidant>

[0437] · Irgafos 168: Tris(2,4 - di - tert - butylphenyl) phosphite; manufactured by BASF Corporation

[0438] · Doverphos S9228PC: Bis(2,4 - dicumylphenyl)pentaerythritol diphosphite, with Na content of 50 mass% or less; manufactured by Dover Chemical Co.

[0439] · PEP - 36: Bis - (2,6 - di - tert - butyl - 4 - methylphenyl)pentaerythritol diphosphite; manufactured by ADEKA Corporation

[0440] · Irganox1076: n - Octadecyl 3 - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate; manufactured by ADEKA Corporation

[0441] · JC263: Triphenylphosphine; manufactured by Johoku Chemical Co., Ltd.

[0442] <Dye>

[0443] · MACROLEX BLUE RR; manufactured by LANXESS Corporation

[0444] · MACROLEX VIOLET B; manufactured by LANXESS Corporation

[0445] <Release agent>

[0446] · RIKEMAL S - 100A: Glycerol monostearate; manufactured by RIKEN VITAMIN Co., Ltd.

[0447] · RikeSTER EW440A: Pentaerythritol tetrastearate, manufactured by RIKEN VITAMIN Co., Ltd.

[0448] <Ultraviolet absorber>

[0449] · Cyasorb UV - 3638F: (2,2’-(1,4 - phenylene)bis[4H - 3,1 - benzoxazin - 4 - one]; manufactured by CYTEC Corporation

[0450] · Seesorb 709: 2 - (2’ - hydroxy - 5’ - tert - octylphenyl)benzotriazole; manufactured by SHIPRO KASEI Co., Ltd.

[0451] · KEMISORB 279: 2,2'-Methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol); manufactured by CHEMIPRO KASEI CO., LTD.

[0452] · Tinuvin 234: 2-[2'-Hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole; manufactured by BASF Japan Ltd.

[0453] · Tinuvin 1577: 2-(4,6-Diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol; manufactured by BASF Japan Ltd.

[0454] · Hostavin B-CAP: Tetraethyl p-phenylenedi(methylenemalonate); manufactured by Clariant Chemicals Ltd.

[0455] <Flame Retardant>

[0456] · KFBS (Potassium perfluorobutanesulfonate, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.)

[0457] <Polyether Compound>

[0458] · UNILUBE 50DE-25R: Polyoxyethylene-polyoxypropylene-bisphenol A ether; manufactured by NOF Corporation

[0459] <Silicone Compound>

[0460] · KR-511: Reactive silicone compound; manufactured by Shin-Etsu Chemical Co., Ltd., containing phenyl, methoxy and vinyl, refractive index = 1.518

[0461] <Epoxy Compound>

[0462] · CELLOXIDE 2021P: 3,4-Epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate

[0463] <Light Diffusing Agent>

[0464] · TSR9002 (trade name): Bead-shaped crosslinked silicone, average particle size 2 μm; manufactured by Momentive Performance Materials Japan LLC

[0465] · MBX-5 (trade name): Bead-shaped crosslinked acrylic particles, average particle size 5 μm; manufactured by Sekisui Chemical Co., Ltd.

[0466] Industrial Applicability

[0467] According to the present invention, a molded article having both excellent flexibility and transparency can be obtained. The molded article of the present invention can be used as an optically transparent member, and specifically, can be suitably used for at least one selected from flexible displays, light guide plates, housings, water / oil repellent films, optical adhesives, switch covers, heat sealants, water blocking materials, sealants, connectors, adapters, smartphone covers, lenses, glasses / sunglasses parts, optical fiber parts, buffer materials for in-vehicle batteries, wiper blades, curved mirrors, side mirrors, rearview mirrors, lamp shades, bumpers, windows, exterior decorative materials, interior decorative materials, sound absorbing materials, steering wheel covers, sensor covers, watch parts, stationery, cosmetic containers, water tanks for breeding aquatic organisms, soles, cups, nail paintings, toys, fishing lures, suction cups, cooking utensils such as steamers, clothes, silicone wiping sheets, remote control covers, umbrellas, linings for metal containers, building material coverings, doors, windows, glass interlayers, tents, mirrors, display cases, plastic greenhouses, medical device housings, infusion bags, infusion tubes, syringes, baby bottles, masks, face shields, filter parts, shock absorbing parts, robot housings, drone housings, shields, bulletproof shields, sports cushioning equipment, aircraft windows, resin compatibilizers, lighting covers, light guides, light guide panels, lighting units, prism panels, flat lenses, Fresnel lenses, microlens arrays, and collimating lenses, etc.

Claims

1. A molded article comprising a polycarbonate resin composition, the polycarbonate resin composition comprising a polycarbonate-polysiloxane copolymer (A) and at least one compound (B) selected from the group consisting of an antioxidant, a dye, a mold release agent, a light diffusing agent, a flame retardant, an ultraviolet absorber, a silicone compound, an epoxy compound, and a polyether compound. The polycarbonate-polysiloxane copolymer (A) contains a polycarbonate block (A-1) containing repeating units represented by the following general formula (I) and a polysiloxane block (A-2) containing repeating units represented by the following general formula (II). The content of the polysiloxane block (A-2) is 30% by mass or more and 70% by mass or less, and the number of repetitions of the polysiloxane block (A-2) is 10 or more and less than 40. Based on 100 parts by mass of the polycarbonate-polysiloxane copolymer (A), it contains 0.001 to 0.5 parts by mass of an antioxidant, 0.00001 to 0.05 parts by mass of a dye, 0.001 to 0.5 parts by mass of a mold release agent, 0.1 to 5 parts by mass of a light diffusing agent, 0.001 to 20 parts by mass of a flame retardant, 0.01 to 1 part by mass of an ultraviolet absorber, 0.01 to 0.25 parts by mass of a silicone compound, 0 to 0.2 parts by mass of an epoxy compound, and / or 0.2 to 1 part by mass of a polyether compound. The durometer hardness of the molded article measured according to JIS K6253-3:2012 using a Type D durometer is 25 or more and 65 or less. In the formula, R 1 and R 2 each independently represent 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, an arylene group having 6 to 12 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 -, -O- or -CO-, R 3 and R 4 each independently represent 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 and b each independently represent an integer of 0 to 4.

2. A molded article comprising a polycarbonate resin composition, the polycarbonate resin composition comprising a polycarbonate-polysiloxane copolymer (A) and at least one compound (B) selected from the group consisting of an antioxidant, a dye, a mold release agent, a light diffusing agent, a flame retardant, an ultraviolet absorber, a silicone compound, an epoxy compound, and a polyether compound. The polycarbonate-polysiloxane copolymer (A) contains a polycarbonate block (A-1) containing repeating units represented by the following general formula (I) and a polysiloxane block (A-2) containing repeating units represented by the following general formula (II). The content of the polysiloxane block (A-2) contained in the molded article is 30% by mass or more and 70% by mass or less, and the number of repetitions of the polysiloxane block (A-2) is 10 or more and less than 40. Per 100 parts by mass of the polycarbonate - polyorganosiloxane copolymer (A), it contains 0.001 to 0.5 parts by mass of an antioxidant, 0.00001 to 0.05 parts by mass of a dye, 0.001 to 0.5 parts by mass of a mold release agent, 0.1 to 5 parts by mass of a light diffusing agent, 0.001 to 20 parts by mass of a flame retardant, 0.01 to 1 part by mass of an ultraviolet absorber, 0.01 to 0.25 parts by mass of a silicone compound, 0 to 0.2 parts by mass of an epoxy compound and / or 0.2 to 1 part by mass of a polyether compound, The durometer hardness of the molded article measured according to JIS K6253 - 3:2012 using a Type D durometer is 25 or more and 65 or less, In the formula, R 1 and R 2 each independently represent 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, an arylene group having 6 to 12 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 -, -O- or -CO-, R 3 and R 4 each independently represent 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 and b each independently represent an integer of 0 to 4.

3. The molded article according to claim 1 or 2, wherein, The content of the unit represented by the following general formula (III) in the polyorganosiloxane block (A - 2) is 0.1 mol% or less, In the formula, R 33 and R 34 each independently represent 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 R 31 represents 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, an arylene group having 6 to 12 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, or an arylalkylidene group having 7 to 15 carbon atoms, and R 35 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 t represents the average chain length of the polyorganosiloxane.

4. The molded article according to claim 3, wherein, The content of the block represented by the general formula (III) in the polycarbonate - polyorganosiloxane copolymer (A) is 0.08 mol% or less.

5. The molded article according to claim 3, wherein, The content of the block represented by the general formula (III) in the polycarbonate - polyorganosiloxane copolymer (A) is 0.0 mol%.

6. The molded article according to claim 1 or 2, wherein, The repeat number of the polyorganosiloxane block (A - 2) is 20 or more and less than 40.

7. The molded article according to claim 1 or 2, wherein, In the general formula (I), the alkylene group represented by X is an alkylene group having 1 to 5 carbon atoms.

8. The molded article according to claim 1 or 2, wherein, In the general formula (I), the alkylidene group represented by X is any one of ethylidene and isopropylidene.

9. The molded article according to claim 1 or 2, wherein, In the general formula (I), the cycloalkylene group represented by X is a cycloalkylene group having 5 to 10 carbon atoms.

10. The molded article according to claim 1 or 2, wherein, In the general formula (I), the arylene group represented by X is any one of phenylene, naphthylene and biphenylene.

11. The molded article according to claim 1 or 2, wherein, In the general formula (I), the cycloalkylidene group represented by X is a cycloalkylidene group having 5 to 10 carbon atoms.

12. The molded article according to claim 1 or 2, wherein, In the general formula (I), the cycloalkylidene group represented by X is a cycloalkylidene group having 5 to 8 carbon atoms.

13. The molded article according to claim 1 or 2, wherein, In the general formula (I), a and b are each independently 0 or 1.

14. The molded article according to claim 1 or 2, wherein, In the general formula (I), a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 0 and X is isopropylidene.

15. The molded article according to claim 1 or 2, wherein, As the polycarbonate block (A - 1), the content of the block where a and b are 0 and X is isopropylidene is 90 mass% or more.

16. The molded article according to claim 1 or 2, wherein, as the polycarbonate block (A-1), the content of the block where a and b are 0 and X is isopropylidene is 95% by mass or more.

17. The molded article according to claim 1 or 2, wherein, as the polycarbonate block (A-1), the content of the block where a and b are 0 and X is isopropylidene is 100% by mass.

18. The molded article according to claim 1 or 2, wherein, In general formula (II), R 3 and R 4 are each 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.

19. The molded article according to claim 1 or 2, wherein, In general formula (II), R 3 and R 4 are both methyl groups.

20. The molded article according to claim 1 or 2, wherein, the polyorganosiloxane block (A-2) contains units represented by at least one of the following general formulas (II-I) to (II-III), 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, and a plurality of R 3 ~R 6 may be the same or different from each other, Y represents -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 -O-, and a plurality of Y may be the same or different from each other, and the said R 7 represents a single bond, a linear alkylene group, a branched alkylene group, or a cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group, R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R 9 represents a diarylene group, R 10 represents a linear alkylene group, a branched alkylene group, or a 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 halide of a dicarboxylic acid, n represents the chain length of the polyorganosiloxane, n - 1 and p and q are each an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit, and the sum of p and q is n - 2.

21. The molded article according to claim 20, wherein, In general formulas (II-I), (II-II), and (II-III), R 3 ~R 6 are each 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.

22. The molded article according to claim 20, wherein, In general formulas (II-I), (II-II) and / or (II-III), R 3 ~R 6 are all methyl groups.

23. The molded article according to claim 20, wherein, Y is -R 7 O-, R 7 is aryl-substituted alkylene group.

24. The molded article according to claim 20, wherein, Y is -R 7 O-, R 7 is the residue of a phenolic compound having an alkyl group.

25. The molded article according to claim 20, wherein, Y is -R 7 O-, R 7 is an organic residue derived from allyl phenol or an organic residue derived from eugenol.

26. The molded article according to claim 20, wherein, in formula (II-II), p and q are p = q.

27. The molded article according to claim 1 or 2, wherein, the polyorganosiloxane block (A-2) contains units represented by the following general formula (V), In the formula, R 3 to 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, and a plurality of R 3 to R 6 may be the same as or different from each other, n - 1 is an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit, and R 15 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.

28. The molded article according to claim 1 or 2, wherein, the viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is 10,000 or more and 23,000 or less.

29. The molded article according to claim 1 or 2, wherein, the viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is 14,000 or more and 20,500 or less.

30. The molded article according to claim 1 or 2, wherein, the viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is 16,000 or more and 18,000 or less.

31. The molded article according to claim 1 or 2, wherein, the weight-average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is 40,000 or less.

32. The molded article according to claim 1 or 2, wherein, the weight-average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is 20,000 or more and 37,000 or less.

33. The molded article according to claim 1 or 2, wherein, the weight-average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is 23,000 or more and 30,000 or less.

34. The molded article according to claim 1 or 2, wherein, the molecular weight distribution of the polycarbonate-polyorganosiloxane copolymer (A) is 2.1 or more and 3.9 or less.

35. The molded article according to claim 1 or 2, wherein, the molecular weight distribution of the polycarbonate-polyorganosiloxane copolymer (A) is 2.5 or more and 3.5 or less.

36. The molded article according to claim 1 or 2, wherein, The molecular weight distribution of the polycarbonate-polyorganosiloxane copolymer (A) is 2.8 or more and 2.9 or less.

37. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) in the molded article exceeds 40% by mass and is 70% by mass or less.

38. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) in the molded article is 45% by mass or more and 62% by mass or less.

39. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 30% by mass or more and 65% by mass or less.

40. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 45% by mass or more and 62% by mass or less.

41. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 45% by mass or more and 55% by mass or less.

42. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) contained in the polycarbonate resin composition exceeds 40% by mass and is 70% by mass or less.

43. The molded article according to claim 1 or 2, wherein the content of the polyorganosiloxane block (A-2) contained in the polycarbonate resin composition is 45% by mass or more and 62% by mass or less.

44. The molded article according to claim 1 or 2, which does not contain a polycarbonate resin other than the polycarbonate-polyorganosiloxane copolymer (A).

45. The molded article according to claim 1 or 2, wherein the antioxidant is a phosphorus-based antioxidant and / or a phenolic antioxidant.

46. The molded article according to claim 45, wherein the phosphorus-based antioxidant is a phosphite-based antioxidant or a phosphine-based antioxidant.

47. The molded article according to claim 46, wherein the phosphite-based antioxidant is any one of tris(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite (Doverphos S-9228PC).

48. The molded article according to claim 46, wherein the phosphine-based antioxidant is triphenylphosphine.

49. The molded article according to claim 1 or 2, wherein when a phosphorus-based antioxidant is used as the antioxidant, the content is 0.002 parts by mass to 0.2 parts by mass relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

50. The molded article according to claim 1 or 2, wherein When using a phosphorus-based antioxidant as the antioxidant, the content is 0.003 to 0.1 parts by mass relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

51. The molded article according to claim 45, wherein, the phenolic antioxidant is a hindered phenol.

52. The molded article according to claim 1 or 2, wherein, when using an antioxidant other than the phosphorus-based antioxidant, the content of the antioxidant other than the phosphorus-based antioxidant is 0.02 parts by mass or more and 0.3 parts by mass or less relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

53. The molded article according to claim 1 or 2, wherein, the content of the dye is 0.0001 parts by mass or more and 0.0005 parts by mass or less relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

54. The molded article according to claim 1 or 2, wherein, the release agent is a fatty acid ester.

55. The molded article according to claim 1 or 2, wherein, the release agent is any one of glycerol monostearate, glycerol distearate, sorbitan monostearate, glyceryl monobehenate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tetrastearate, propylene glycol monostearate, and sorbitan anhydride monostearate.

56. The molded article according to claim 1 or 2, wherein, the content of the release agent is 0.03 parts by mass or more and 0.3 parts by mass or less relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

57. The molded article according to claim 1 or 2, wherein, the light diffusing agent is a Si-based light diffusing agent.

58. The molded article according to claim 1 or 2, wherein, the light diffusing agent is an organic fine particle containing a silicone resin.

59. The molded article according to claim 1 or 2, wherein, the particle size of the light diffusing agent is 1 μm to 5 μm.

60. The molded article according to claim 1 or 2, wherein, the content of the light diffusing agent is 0.1 parts by mass or more and 3 parts by mass or less relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

61. The molded article according to claim 1 or 2, wherein, the flame retardant is any one of an organic alkali metal salt, an organic alkaline earth metal salt, and a phosphorus-based flame retardant.

62. The molded article according to claim 1 or 2, wherein, the flame retardant is an organic alkali metal salt or a phosphorus-based flame retardant.

63. The molded article according to claim 1 or 2, wherein, the flame retardant is an alkali (earth) metal salt of perfluorooctanesulfonic acid represented by the following formula (11), (C e F 2e+1 SO 3 ) f M (11) wherein, e represents an integer from 1 to 10, M represents an alkali metal or alkaline earth metal selected from lithium, sodium, potassium, cesium, magnesium, calcium, strontium, and barium, and f represents the valence of M.

64. The molded article according to claim 63, wherein, in the formula (11), M is potassium.

65. The molded article according to claim 1 or 2, wherein, when the flame retardant is an organic alkali (earth) metal salt, its compounding amount is 0.02 parts by mass or more and 0.08 parts by mass or less relative to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

66. The molded article according to claim 1 or 2, wherein, when the flame retardant is a phosphorus-based flame retardant, its compounding amount is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

67. The molded article according to claim 1 or 2, wherein, the ultraviolet absorber is at least 1 selected from benzotriazole-based compounds, malonic ester-based compounds, triazine-based compounds, and benzoxazine-based compounds.

68. The molded article according to claim 1 or 2, wherein, the content of the ultraviolet absorber is 0.1 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

69. The molded article according to claim 1 or 2, wherein, The silicone-based compound is a polymer or copolymer containing a structural unit represented by (R 1 ), a (R 2 ), b SiO （4-a-b） / 2 as shown. In the formula, R 1 represents a functional group, and R 2 represents a hydrocarbon group having 1 to 12 carbon atoms. In addition, a and b are integers satisfying 0 < a ≤ 3, 0 ≤ b < 3, and 0 < a + b ≤ 3, respectively.

70. The molded article according to claim 69, wherein, R in the formula of the silicone-based compound 1 represents a functional group that is at least any one of an alkoxy group, a hydrogen group, a hydroxyl group, an epoxy group, and a vinyl group.

71. The molded article according to claim 69, wherein, R in the formula of the silicone-based compound 1 represents a functional group that is at least one of methoxy and vinyl.

72. The molded article according to claim 69, wherein, R in the formula of the silicone-based compound 2 represents a phenyl group as the hydrocarbon group.

73. The molded article according to claim 69, wherein, In the formula of the silicone compound, the value of (R 1 ) / (R 2 ) is 0.3 to 2.

74. The molded article according to claim 1 or 2, wherein, the refractive index of the silicone-based compound is 1.45 to 1.

65.

75. The molded article according to claim 1 or 2, wherein, the refractive index of the silicone-based compound is 1.48 to 1.

60.

76. The molded article according to claim 1 or 2, wherein, the sodium content of the silicone-based compound is 15 mass ppm or less.

77. The molded article according to claim 1 or 2, wherein, the sodium content of the silicone-based compound is 10 mass ppm or less.

78. The molded article according to claim 1 or 2, wherein, the content of the silicone-based compound is 0.05 part by mass to 0.15 part by mass with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

79. The molded article according to claim 1 or 2, wherein, when using a phosphite-based antioxidant as the compound (B), the polycarbonate-based resin composition contains an epoxy compound.

80. The molded article according to claim 1 or 2, wherein, the epoxy compound is an alicyclic epoxy compound, or an epoxidized natural oil or epoxidized synthetic oil having an ethylene oxide oxygen concentration of 4% or more.

81. The molded article according to claim 1 or 2, wherein, the epoxy compound is an epoxidized natural oil or epoxidized synthetic oil having an ethylene oxide oxygen concentration of 4% or more.

82. The molded article according to claim 80, wherein, the ethylene oxide oxygen concentration of the epoxidized natural oil or epoxidized synthetic oil is 7% or more.

83. The molded article according to claim 1 or 2, wherein, The polyether compound has a polyoxyalkylene group structure represented by (R C1 O) m and a polyoxyalkylene group structure represented by (R C2 O) n as shown, Here, R C1 and R C2 each independently represents an alkylene group having 1 or more carbon atoms, and m + n is 5 or more and less than 300.

84. The molded article according to claim 83, wherein, R C1 and R C2 is an alkylene group selected from ethylene, propylene, and tetramethylene, and at least one of R C1 and R C2 is either ethylene or propylene.

85. The molded article according to claim 1 or 2, wherein, the polyether compound is at least 1 selected from the compounds represented by the following general formula (IX), the alkylene oxide adducts of polyhydric alcohols and their esters, and cyclic polyether compounds, R C3 O-(R C1 O) m -A-(R C2 O) n -R C4 (IX) In the formula, R C1 and R C2 each independently represent an alkylene group having 1 or more carbon atoms, m + n is 5 or more and less than 300, R C3 and R C4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, an alkanoyl group having 1 to 30 carbon atoms, an alkenoyl group having 2 to 30 carbon atoms, or a glycidyl group, and A represents a single bond or a divalent organic group.

86. The molded article according to claim 1 or 2, wherein, the number average molecular weight of the polyether compound is 200 to 10,000.

87. The molded article according to claim 1 or 2, Among them, the number average molecular weight of the polyether compound is 1,000 to 5,000.

88. The molded article according to claim 1 or 2, wherein, the content of the polyether compound is 0.3 to 0.8 parts by mass with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

89. The molded article according to claim 1 or 2, having a durometer hardness based on a Type D durometer of 30 or more and 65 or less as measured according to JIS K6253-3:2012.

90. The molded article according to claim 1 or 2, having a durometer hardness based on a Type D durometer of 40 or more and 65 or less as measured according to JIS K6253-3:2012.

91. The molded article according to claim 1 or 2, wherein, the total light transmittance at a thickness of 2 mm as measured according to JIS K7361-1:1997 is 75% or more.

92. The molded article according to claim 1 or 2, wherein, the total light transmittance at a thickness of 2 mm as measured according to JIS K7361-1:1997 is 89% or more.

93. The molded article according to claim 1 or 2, wherein, the total light transmittance at a thickness of 2 mm as measured according to JIS K7361-1:1997 is 91% or more.

94. The molded article according to claim 1 or 2, which is an optical member.

95. The molded article according to claim 1 or 2, which is selected from the group consisting of a flexible display, a light guide plate, a housing, a water / oil repellent film, an optical adhesive, a switch cover, a heat sealant, a water blocking material, a sealant, a connector, an adapter, a smartphone cover, a lens, glasses / sunglasses parts, optical fiber parts, a buffer material for in-vehicle batteries, a wiper blade, a lamp shade, a bumper, a window, an exterior decorative material, an interior decorative material, a sound absorbing material, a steering wheel cover, a sensor cover, watch parts, stationery, a cosmetic container, an aquarium for aquatic organisms, a sole, a cup, a nail art, a toy, a fishing lure, a suction cup, a cooking appliance including a steamer, clothes, a silicone wiping sheet, a remote control cover, an umbrella, a lining for a metal container, a building material cladding, a door, a window, an interlayer for glass, a tent, a mirror, a display case, a plastic greenhouse, an infusion bag, an infusion tube, a syringe, a baby bottle, a mask, a face shield, a filter part, a shock absorbing part, a shield, a sports buffer device, a resin compatibilizer, a lighting cover, a light guide, a lighting unit, and a prism panel.

96. The molded article according to claim 95, wherein, the mirror is selected from a curved mirror, a side view mirror, and a rear view mirror.

97. The molded article according to claim 95, wherein, the housing is selected from a medical device housing, a robot housing, and a drone housing.

98. The molded article according to claim 95, wherein, the window is an aircraft window.

99. The molded article according to claim 95, wherein, the shield is a bulletproof shield.

100. The molded article according to claim 95, wherein, the light guide plate is a light guide panel.

101. The molded article according to claim 95, wherein, the lens is selected from a flat lens, a Fresnel lens, a microlens array, and a collimating lens.

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