JP5988971B2 - Polycarbonate resin composition and molded body using the same - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded body using the same. More specifically, a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, electrical conductivity and molded appearance, and further heat conductivity, and the resin composition, The present invention relates to a molded article having properties.

  In recent years, information processing apparatuses and electronic office equipment are rapidly spreading due to the development of electronics technology. With the widespread use of electronic devices, troubles such as electromagnetic interference, malfunctions due to static electricity, etc., in which noise generated from electronic components affects peripheral devices are increasing, becoming a major problem. In order to solve these problems, materials with excellent electrical conductivity and antistatic properties are required, and as products become thinner, higher rigidity and flame retardance have been required. .

Conventionally, a conductive polymer material in which a conductive filler or the like is blended with a low-conductivity polymer material has been widely used. As the conductive filler, metal fiber, metal powder, carbon black, carbon fiber and the like are generally used. However, when the metal fiber and metal powder are used as the conductive filler, there is an excellent conductivity imparting effect, but the corrosion resistance. There is a disadvantage that the mechanical strength is difficult to obtain. When carbon black is used as a conductive filler, conductive carbon black such as ketjen black, Vulcan XC72, and acetylene black, which can obtain high conductivity with a small amount of addition, is used. Is bad. Since the dispersibility of carbon black affects the conductivity of the resin composition, a unique blending and mixing technique is required to obtain stable conductivity.
In addition, when carbon fibers are used as conductive fillers, desired strength and elastic modulus can be obtained with ordinary reinforcing carbon fibers, but high filling is required to impart conductivity, and the resin itself The physical properties of the are reduced.

  Patent Document 1 discloses a technique for adding carbon nanotubes to a polycarbonate-polyorganosiloxane copolymer (sometimes abbreviated as PC-PDMS) to improve conductivity and flame retardancy, and Patent Document 2 includes A technique for blending graphite with polycarbonate to impart thermal conductivity, and Patent Document 3 disclose a technique for blending functional graphene with a resin.

JP 2003-221508 A JP 2011-16937 A Special table 2010-506013 gazette

However, in the technique described in Patent Document 1, the required rigidity cannot be sufficiently provided, and further, it cannot respond to the demand for further thin-walled flame retardant, and is not always satisfactory. .
Patent Document 2 is a technique of blending graphite with polycarbonate to impart thermal conductivity. However, unless it is used in combination with a flame retardant, flame retardancy is not manifested, and description of conductivity and rigidity is provided. There is no. In Patent Document 2, there is no description of graphene having a nano-order thickness, and dispersion of graphene having a nano-order thickness is difficult to produce using an ordinary extruder. The performance has not been fully developed. Furthermore, although patent document 3 is a technique which mix | blends functional graphene, in the polycarbonate material, there is no description about the graphene optimal for a flame retardance and electroconductivity.
The present invention has been made under such circumstances, and a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity and molded appearance, and further in thermal conductivity and the like, and It is an object of the present invention to provide a molded article having the above-mentioned properties formed by molding the resin composition.

  As a result of intensive studies to achieve the above object, the present inventor has obtained a polycarbonate organosiloxane copolymer containing a polyorganosiloxane block composed of a specific structural unit at a predetermined ratio, and other aromatic polycarbonates. It has been found that a resin composition containing a predetermined amount of a graphene sheet can be adapted to the purpose with respect to a polycarbonate-based resin contained at a specific ratio. The present invention has been completed based on such findings.

That is, the present invention provides the following (1) to (8).
(1) A polycarbonate resin in which the mass ratio of the polycarbonate-polyorganosiloxane copolymer (A-1) to the aromatic polycarbonate (A-2) other than (A-1) is 5:95 to 100: 0. A polycarbonate resin composition comprising (A) 70 to 99.5 mass% and a graphene sheet (B) 30 to 0.5 mass%.
(2) The polycarbonate resin composition according to (1), wherein the graphene sheet (B) has a thickness of 5 to 10 nm and a size of 3 μm or more.
(3) The polycarbonate-polyorganosiloxane copolymer (A-1) includes a structural unit having a main chain represented by the general formula (I) and a structural unit represented by the general formula (II). The polycarbonate resin composition according to the above (1) or (2), comprising 2 to 40% by mass of a polyorganosiloxane block comprising a structural unit represented by the formula (II).

[Wherein, R ¹ and R ² are each independently an alkyl group or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, carbon A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—, and R ^{3 to} R ⁶ are each independently , A hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y represents an organic residue containing aliphatic or aromatic , N is an average number of repetitions and represents an integer of 1 to 600, and a and b represent integers of 0 to 4. ]
(4) The polycarbonate resin composition according to the above (3), wherein Y is an organic residue from allylphenol or eugenol.
(5) The polycarbonate resin composition according to the above (3) or (4), wherein the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A.
(6) The polycarbonate resin composition according to any one of the above (3) to (5), wherein R ³ and R ⁴ in the structural unit represented by the general formula (II) are both methyl groups.
(7) Further, the polytetrafluoroethylene (C) containing 0.01 to 1 part by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B) (1) to (1) The polycarbonate resin composition according to any one of 6).
(8) A molded article formed by molding the polycarbonate resin composition according to any one of (1) to (7).

According to the present invention, a polycarbonate resin composition that gives a molded article excellent in flame retardancy, rigidity, impact resistance, electrical conductivity and molded appearance, as well as thermal conductivity, and the above-mentioned molded resin composition. A molded body having properties can be provided.
In addition, the molded body of the present invention has the above-mentioned properties and does not cause contamination of semiconductors and the like due to the dropping of carbon. Therefore, the housing of electrical / electronic equipment such as OA equipment, information equipment, home appliances, The application fields such as parts, films, and automobile parts are expected to expand.

First, the polycarbonate resin composition of the present invention will be described.
[Polycarbonate resin composition]
In the polycarbonate resin composition of the present invention, the mass ratio of the polycarbonate-polyorganosiloxane copolymer (A-1) to the aromatic polycarbonate (A-2) other than (A-1) is 5:95 to 100: It comprises 70 to 99.5% by mass of a polycarbonate-based resin (A) consisting of 0 and 30 to 0.5% by mass of a graphene sheet (B).
Hereinafter, each component in the polycarbonate resin composition of the present invention will be described.

[Polycarbonate-polyorganosiloxane copolymer (A-1)]
The polycarbonate-polyorganosiloxane copolymer (A-1) used in the present invention includes a structural unit whose main chain is represented by the following general formula (I) and a structural unit represented by the following general formula (II), And what contains 2-40 mass% of polyorganosiloxane blocks which consist of a structural unit represented by this general formula (II) is preferable. In the present specification, the polycarbonate-polyorganosiloxane copolymer may be referred to as “PC-PDMS copolymer”.

Here, R ¹ and R ² are each independently an alkyl group or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, or a carbon number. A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—, and R ^{3 to} R ⁶ are each independently A hydrogen atom, a halogen atom or 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, Y represents an organic residue containing aliphatic or aromatic, n is an average number of repetitions and represents an integer of 1 to 600, and a and b represent integers of 0 to 4. Y is preferably an organic residue from allylphenol or eugenol. Moreover, as said n, from a viewpoint of the performance of the polycarbonate resin composition obtained, it is preferable that it is an integer of 1-500, and it is more preferable that it is 5-200.

In the PC-PDMS copolymer (A-1), the content of the polyorganosiloxane block is preferably 2 to 40% by mass from the viewpoint of flame retardancy and impact resistance. More preferably, it is 25 mass%.
Further, from the viewpoint of the performance of the obtained polycarbonate resin composition, the structural unit represented by the general formula (I) is preferably a structural unit derived from bisphenol A, and represented by the general formula (II). In the structural unit, R ³ and R ⁴ are preferably both methyl groups.

In general, in order to develop impact resistance, it is effective that the viscosity average molecular weight of the PC-PDMS copolymer (A-1) is large. However, when the viscosity average molecular weight is large, it is difficult to form a thin member. Become.
It is possible to lower the viscosity of the resin composition by raising the molding temperature, but in that case, the molding cycle becomes longer and inferior in economic efficiency. Decreases.
Therefore, the viscosity average molecular weight of the PC-PDMS copolymer (A-1) is preferably 15000 to 24000, more preferably 16000 to 22500, and further preferably 17000 to 21000.
When the viscosity average molecular weight is 15000 or more, the strength of the molded product is sufficient. When the viscosity average molecular weight is 24000 or less, the viscosity of the copolymer becomes small, so that the productivity during production is good and the thin-wall molding is also good. .

  The PC-PDMS copolymer (A-1) is composed of a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), phosgene, carbonate, or chloro It is obtained by using a formate and a molecular weight regulator used as necessary.

Here, in the general formula (1), R ¹ and R ^2, X, a and b are the same as the above general formula (I), the general formula ^{(2), R 3 ~R 6} , Y, n Is the same as in the general formula (II), m represents 0 or 1, Z represents halogen, —R ⁷ OH, —R ⁷ COOH, —R ⁷ NH ₂ , —COOH or —SH; ⁷ represents a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group which may have an alkoxy group on the ring, or an arylene group.

In the polycarbonate resin composition of the present invention, the dihydric phenol represented by the general formula (1) used as a raw material for the PC-PDMS copolymer (A-1) is not particularly limited, but 2,2-bis (4-Hydroxyphenyl) propane (common name: bisphenol A) is preferred. When bisphenol A is used as the dihydric phenol, a PC-PDMS copolymer in which X is an isopropylidene group and a = b = 0 in the general formula (I) is obtained.
Examples of dihydric phenols other than bisphenol A 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-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-) 3,5-tetramethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophene) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2, Bis (hydroxyaryl) cycloalkanes such as 2-bis (4-hydroxyphenyl) norbornane and 1,1-bis (4-hydroxyphenyl) cyclododecane, 4,4′-dihydroxyphenyl ether, 4,4′-dihydroxy Dihydroxy aryl ethers such as 3,3′-dimethylphenyl ether, 4,4′-di Droxydiphenyl sulfide, dihydroxydiaryl sulfides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl Dihydroxydiaryl sulfoxides such as sulfoxide, 4,4'-dihydroxydiphenylsulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, dihydroxydiphenyl such as 4,4'-dihydroxydiphenyl Dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenyl Dihydroxydiaryl such as tan, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane Adamantanes, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenyl) Thio) -2,3-dioxapentaene and the like.
These dihydric phenols may be used alone or in admixture of two or more.

  The polyorganosiloxane represented by the general formula (2) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, eugenol, isopropenylphenol or the like having a predetermined polymerization degree n. It can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain. The phenols are more preferably allylphenol or eugenol. In this case, Y in the general formula (II) of the component (A-1) is an organic residue derived from allylphenol or eugenol.

As the polyorganosiloxane represented by the general formula (2), those in which R ³ and R ⁴ are both methyl groups are preferable, and examples thereof include compounds of the following general formulas (3) to (11).

In the general formulas (3) to (11), R ^{3 to} R ⁶ are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, 6 represents an alkoxy group having 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and n represents an average number of repeating units of the organosiloxane constitutional unit and represents 1 to 600. R ⁸ represents an alkyl, alkenyl, aryl or aralkyl group, c represents a positive integer, and is generally an integer of 1 to 6.
Among these, from the viewpoint of ease of polymerization, a phenol-modified polyorganosiloxane represented by the general formula (3) is preferable. In terms of availability, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is a kind of the compound represented by the general formula (4), is represented by the general formula (5). Α, ω-bis [3- (4-hydroxy-2-methoxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds shown, is preferred.

The phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example.
First, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α, ω-dihydrogenorganopolysiloxane. At this time, α, ω-dihydrogenorganopolysiloxane having a desired average repeating unit can be synthesized by changing the charging ratio of cyclotrisiloxane and disiloxane. Next, in the presence of a hydrosilylation reaction catalyst, the α, ω-dihydrogenorganopolysiloxane is subjected to an addition reaction with a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol. A phenol-modified polyorganosiloxane having an average repeating unit can be produced.
Further, at this stage, since low molecular weight cyclic polyorganosiloxane and an excessive amount of the phenol compound remain as impurities, it is preferable to distill off these low molecular compounds by heating under reduced pressure.

[Aromatic polycarbonate other than (A-1) (A-2)]
In the polycarbonate resin composition of the present invention, the component (A-2) which is an aromatic polycarbonate other than the above (A-1) is a dihydric phenol compound and an organic solvent inert to the reaction, in the presence of an alkaline aqueous solution. After reacting with phosgene, interfacial polymerization method in which polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to polymerize, or dihydric phenol compound is dissolved in pyridine or mixed solution of pyridine and inert solvent In addition, those obtained by a conventional method for producing an aromatic polycarbonate such as a pyridine method in which phosgene is directly introduced can be used.

  As the dihydric phenol compound used in the production of the component (A-2) aromatic polycarbonate, 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A], 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-t -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 Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 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) ) Bis (hydroxyaryl) cycloalkanes such as cyclododecane, 4,4′-dihydroxyphenylamine Dihydroxy aryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide, etc. Dihydroxydiaryl sulfoxides, 4,4′-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfone, 4,4′- Dihydroxy diaryl sulfones such as dihydroxy-3,3′-dimethyldiphenyl sulfone, dihydroxy diphenyls such as 4,4′-dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis ( 4- Dihydroxydiarylfluorenes such as droxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, Dihydroxydiaryladamantanes such as 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10- Bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and the like can be mentioned. These dihydric phenols may be used alone or in admixture of two or more.

In producing the aromatic polycarbonate as the component (A-2), a molecular weight regulator, a terminal terminator, and the like may be used as necessary. Any of these can be used as long as they are usually used for polymerization of polycarbonate resin.
Specific molecular weight regulators include, for example, monohydric phenols such as phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, and p-isobutylphenol. , Ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn -Hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o n-nonylphenol, m-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5 -Di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, Tribromophenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho, meta or para position, 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) ) Fluorene, 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy 3-methylphenyl) fluorene, 4- (1-adamantyl) phenol, and the like.
Among these monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferable. Moreover, these compounds can be used individually or in combination of 2 or more types.

  As the terminal terminator, monovalent carboxylic acid and derivatives thereof, or monovalent phenol can be used. For example, pt-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, pt -Perfluorobutylphenol, 1- (p-hydroxybenzyl) perfluorodecane, p- [2- (1H, 1H-perfluorotridodecyloxy) -1,1,1,3,3,3-hexafluoropropyl] Phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol, 2H, 2H, 9H-perfluorononanoic acid, 1,1,1,3,3,3-tetrafluoro-2-pro Nord, and the like.

Furthermore, a branched polycarbonate can be obtained by using a branching agent for the above dihydric phenol compound. The addition amount of the branching agent is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the dihydric phenol compound.
Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane and 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl. ] Ethylidene] bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl]- Examples include compounds having three or more functional groups such as 4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, phloroglysin, trimellitic acid, and isatin bis (o-cresol).

In the polycarbonate resin (A) comprising the component (A-1) and the component (A-2), the content of (A-1) is 5 to 100% by mass, preferably 70 to 100% by mass. Preferably it is 50-100 mass%, and content of (A-2) is 95-0 mass%, Preferably it is 30-0 mass%, More preferably, it is 50-0 mass%.
When the content of (A-1) is 5% by mass or more, or the content of (A-2) is 95% by mass or less, the content of the polyorganosiloxane block part in the polycarbonate resin (A) is increased. In order to improve the low temperature impact strength, it is not necessary to increase the content of the polyorganosiloxane block part containing the structural unit represented by the general formula (II) during the production of the component (A-1), and therefore In the production of the component (A-1), the uniformity of the reaction is not lowered in the polymerization step, and the separation property between the polymer and the washing water is not deteriorated in the washing step of the polymer, (A-1) Productivity of a component becomes favorable.
The content of the polyorganosiloxane block portion having the structural unit of the general formula (II) is preferably 0.1 to 40 in the polycarbonate resin (A) composed of the component (A-1) and the component (A-2). It is 0.5 mass%, More preferably, it is 0.5-25 mass%, More preferably, it is 0.5-15 mass%, More preferably, it is 0.5-10 mass%. If it is 0.1 mass% or more, the effect of improving impact strength is sufficient, while if it is 40 mass% or less, it has sufficient flame retardancy and heat resistance.

[Graphene sheet (B)]
In the polycarbonate resin composition of the present invention, in order to impart properties such as flame retardancy, conductivity, rigidity, molded appearance, and thermal conductivity to the molded body, it is necessary to contain a graphene sheet as the component (B). Cost.
A graphene sheet is a graphene plate having one or more layers of graphene surfaces, and is usually sliced using ultrasonic energy, and the level of flaking is to adjust the sound generation time (sonification) time Can be controlled by.
The graphene sheet used in the present invention preferably has a thickness of 5 to 10 nm and a size of 3 μm or more. If the graphene sheet used in the present invention has a thickness of 5 to 10 nm and a size of 3 μm or more, the dispersibility of the graphene sheet is improved, it is easy to be combined with a resin, flame retardancy, conductivity, rigidity, molded appearance, Furthermore, a molded body having excellent thermal conductivity can be obtained. From the above viewpoint, the thickness of the graphene sheet is preferably 6 to 8 nm, and the size of the graphene sheet is preferably 3 to 30 μm, more preferably 5 to 25 μm, and still more preferably 5 to 20 μm. From the viewpoint of imparting higher conductivity among the properties described above, the size of the graphene sheet is preferably 5 to 30 μm, and more preferably 5 to 20 μm.
In the present invention, the graphene sheet has a plate-like shape, and its thickness is the size in the thickness direction formed by overlapping the graphene sheets. The size is the size of the graphene structure itself. It can be measured by the method described in 1.
Products include “xGnP” (graphene nanoplatelet) manufactured by XG Sciences. In contrast to carbon nanotubes, it has an open and flat shape, so it is possible to introduce functional groups at the peripheral edges and to apply an interfacial treatment to the surface.

  In the polycarbonate resin composition of the present invention, the above-mentioned polycarbonate resin (A) is added in an amount of 70 to 99.5% by mass and the graphene in order to impart properties such as conductivity, rigidity, flame retardancy, and thermal conductivity. It is necessary to contain the sheet (B) at a ratio of 30 to 0.5% by mass. When the content of the graphene sheet (B) is less than 0.5% by mass, the effect of imparting the properties is difficult to be exhibited. On the other hand, when the content exceeds 30% by mass, the impact strength is remarkably lowered and the molded appearance is also lowered. From the above viewpoint, the preferable content of the graphene sheet (B) is 1 to 30% by mass, and more preferably 1 to 20% by mass with respect to the total amount with the polycarbonate resin (A).

[Polytetrafluoroethylene (C)]
In the polycarbonate resin composition of the present invention, it is preferable to contain polytetrafluoroethylene as the component (C) in order to have a melt dripping preventing effect and to impart high flame retardancy.
The polytetrafluoroethylene (C) is polytetrafluoroethylene (hereinafter abbreviated as PTFE) having a fibril forming ability and an average molecular weight of 500,000 or more, and has an effect of preventing melt dripping and has high flame retardancy. Can be granted. The average molecular weight needs to be 500,000 or more, preferably 500,000 to 10,000,000, more preferably 1,000,000 to 10,000,000.
The PTFE having fibril forming ability is not particularly limited, and specifically, “Teflon (registered trademark)” 6-J (Mitsui / DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201, Polyflon MPA FA-100 (manufactured by Daikin Industries), CD076 (manufactured by Asahi Glass Fluoropolymers) and Argoflon F5 (manufactured by Montefluos) can be exemplified.

PTFE having the fibril-forming ability as described above is, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium or ammonium peroxydisulfide, at a pressure of 7 to 700 kPa, at a temperature of 0 to 200 ° C., preferably Can be obtained by polymerization at 20 to 100 ° C.
The content of the PTFE is usually 0.01 to 1 part by mass, preferably 0.05 to 1 part by mass with respect to 100 parts by mass as a total of the polycarbonate resin (A) and the graphene sheet (B). 0.9 mass part, More preferably, it is 0.1-0.8 mass part. When the content of the PTFE is within the above range, the melt dripping prevention property in the intended flame retardancy is sufficient.

In the polycarbonate resin composition of the present invention, a mixed powder composed of polytetrafluoroethylene particles and organic polymer particles can be contained instead of the PTFE.
The particle diameter of the polytetrafluoroethylene particles in the mixed powder is usually 10 μm or less, preferably 0.05 to 1.0 μm.
The polytetrafluoroethylene particles are prepared, for example, as an aqueous dispersion dispersed in water containing an emulsifier and the like. This aqueous dispersion of polytetrafluoroethylene particles is obtained by emulsion polymerization of a tetrafluoroethylene monomer using a fluorine-containing surfactant.

Fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether as copolymerization components, as long as the properties of polytetrafluoroethylene are not impaired during the emulsion polymerization of polytetrafluoroethylene particles, Fluorine-containing alkyl (meth) acrylates such as perfluoroalkyl (meth) acrylate can be used.
The content of the copolymer component is preferably 10% by mass or less with respect to tetrafluoroethylene in the polytetrafluoroethylene particles.
The organic polymer particles in the mixed powder are not particularly limited, but are compatible with the polycarbonate resin from the viewpoint of dispersibility of the polytetrafluoroethylene particles when blended with the polycarbonate resin (A). It is preferable that it has.
The content of the mixed powder composed of polytetrafluoroethylene particles and organic polymer particles is usually 0.1 to 1 with respect to 100 parts by mass of the total amount of the polycarbonate resin (A) and the graphene sheet (B). It is a mass part, Preferably it is 0.1-0.9 mass part, More preferably, it is 0.2-0.8 mass part.
When the content of the mixed powder is 0.1 parts by mass or more, drip performance is good and flame retardancy can be achieved. On the other hand, if it is 1 mass part or less, the ratio of the organic polymer in a composition does not increase too much, and a flame retardance can be achieved.

[Optional ingredients]
In the polycarbonate resin composition of the present invention, in addition to the above-mentioned (A) component, (B) component, and (C) component or mixed powder, as long as the effect of the present invention is not impaired, as necessary, Various known additive components conventionally added to polycarbonate resin compositions can be contained. Examples of such additives include phosphorus antioxidants, alkali (earth) metal salts of organic sulfonic acids as flame retardants, reinforcing materials, fillers, hindered amine light stabilizers, and oxidations other than phosphorus. Inhibitors, ultraviolet absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, elastomers for improving impact resistance, and the like.

(Phosphorus antioxidant)
There is no restriction | limiting in particular as phosphorus antioxidant used by this invention. Typical examples include tris (nonylphenyl) phosphite, 2-ethylhexidiphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl Trialkyl phosphites such as phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, and tricyclohexyl phosphite Tricycloalkyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (hydroxyphenyl) phosphite And triaryl phosphites such as tris (2,4-di-tert-butylphenyl) phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate , Trialkyl phosphates such as distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl-1-phosphate, And triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and the like. Of these, triaryl phosphites and triaryl phosphates are preferably used.

  In the present invention, these phosphorus antioxidants may be used alone or in combination of two or more. Moreover, it is preferable that content of the said phosphorus antioxidant in a polycarbonate resin composition is 0.1-1 mass part with respect to 100 mass parts of polycarbonate-type resin (A). By containing the phosphorus antioxidant in the above range, a sufficient antioxidant effect can be obtained.

(Alkali (earth) metal salt of organic sulfonic acid)
In the polycarbonate resin composition of the present invention, in order to improve flame retardancy, an alkali metal salt and / or alkaline earth metal salt of organic sulfonic acid (hereinafter also referred to as alkali (earth) metal salt of organic sulfonate). ) Can be contained.
Examples of the organic sulfonic acid include perfluoroalkane sulfonic acid and polystyrene sulfonic acid.
Various organic sulfonic acid alkali (earth) metal salts include organic sulfonic acid alkali metal salts and alkaline earth metal salts having at least one carbon atom.
Examples of the alkali metal include sodium, potassium, lithium and cesium, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Of these, sodium, potassium and cesium salts are preferred.
As the component (C), an alkali metal salt and / or an alkaline earth metal salt of perfluoroalkanesulfonic acid or polystyrenesulfonic acid is preferable.

Examples of the alkali (earth) metal salt of perfluoroalkanesulfonic acid include those represented by the following general formula (12).
(C _d F _{2d + 1} SO ₃ ) _e M (12)
In formula (12), d represents an integer of 1 to 10, M represents an alkaline metal such as lithium, sodium, potassium and cesium, or an alkaline earth metal such as magnesium, calcium, strontium and barium, and e represents M The valence of is shown.
As these metal salts, for example, those described in Japanese Patent Publication No. 47-40445 are applicable.

In the general formula (12), examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluoro Examples include hexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, these potassium salts are preferably used.
In addition, alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone-3-sulfonic acid, Examples include diphenylsulfone-3,3′-disulfonic acid, naphthalene trisulfonic acid, fluorine-substituted products thereof, and alkali metal salts and alkaline earth metal salts of organic sulfonic acids such as polystyrene sulfonic acid. Among these, perfluoroalkanesulfonic acid and diphenylsulfonic acid are particularly preferable as the organic sulfonic acid.

  Examples of the alkali (earth) metal salt of polystyrene sulfonic acid include alkali (earth) metal salts of sulfonate group-containing aromatic vinyl resins represented by the following general formula (13).

In formula (13), Q represents a sulfonate group, and R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. s represents an integer of 1 to 5, t represents a mole fraction, and 0 <t ≦ 1.
Here, the sulfonate group of Q is an alkali metal salt and / or alkaline earth metal salt of sulfonic acid, and the metals include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium. Etc.
R ⁹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
s is an integer of 1 to 5, and t has a relationship of 0 <t ≦ 1. Therefore, the sulfonate group (Q) may include a fully substituted or partially substituted aromatic ring.

  (C) The content of the alkali (earth) metal salt of the organic sulfonic acid is preferably 0.01 to 0.15 parts by mass, more preferably 100 parts by mass of the polycarbonate resin (A). It is 0.02-0.13 mass part, More preferably, it is 0.03-0.12 mass part. When the content is 0.01 parts by mass or more and 0.15 parts by mass or less, the flame retardancy can be sufficiently improved.

  The polycarbonate resin composition of the present invention does not substantially contain any of an organic halogen flame retardant and an organic phosphate ester flame retardant. For this reason, there is no fear of generation of harmful gas, contamination of the molding machine, burning of the resin, and deterioration of heat resistance.

[Preparation method of polycarbonate resin composition]
The polycarbonate resin composition of the present invention comprises the components (A) [(A-1) and (A-2)], the component (B) and the component (C) or mixed powder used as necessary, Can be prepared by blending various components at a predetermined ratio and kneading.
In this case, blending and kneading are premixed with commonly used equipment such as a ribbon blender, a drum tumbler, etc., and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw screw. It can be carried out by a method using an extruder, a kneader or the like.
The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 300 ° C.
In addition, the components other than the polycarbonate-based resin can be added in advance as a master batch with melt-kneading with the polycarbonate-based resin.

The polycarbonate resin composition of the present invention uses the above-mentioned melt-kneading molding machine, or using the obtained pellets as a raw material, an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum Various molded articles can be produced by a molding method, a foam molding method, or the like.
In particular, a pellet-shaped molding raw material can be produced by the melt kneading method, and then the pellet can be used suitably for production of an injection molded product by injection molding or injection compression molding.
In addition, as an injection molding method, a gas injection molding method for preventing the appearance of sink marks or for reducing the weight can be adopted.

  The molded article of the present invention produced in this way is excellent in flame retardancy, rigidity, impact resistance, conductivity, molded appearance, thermal conductivity, and the like, and may cause contamination of semiconductors and the like due to carbon falling off. Therefore, it is suitably used for housings, parts, films, and automobile parts of electrical / electronic equipment such as OA equipment, information equipment, and home appliances.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.
In addition, the characteristic value in each example was calculated | required according to the point shown below.

<Viscosity average molecular weight of PC-PDMS copolymer (A-1) and aromatic polycarbonate (A-2)>
These viscosity average molecular weights (Mv) are obtained by measuring the viscosity of a methylene chloride solution at 20 ° C. using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating by the following formula.
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83

<Performance evaluation of polycarbonate resin composition (hereinafter sometimes abbreviated as PC composition)>
(Test piece preparation method)
Each component was mix | blended in the ratio shown to Table 1-Table 3, and it supplied to the extruder (model name: VS40, Tanabe Plastic Machine Co., Ltd. product), and melt-kneaded at 240 degreeC and pelletized. In all Examples and Comparative Examples, 0.2 part by mass of Irganox 1076 (manufactured by BASF Japan Ltd.) was blended as an antioxidant. The obtained pellets were dried at 120 ° C. for 12 hours, and then injection molded under the conditions of an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model: IS100N) cylinder temperature 260 ° C. and mold temperature 80 ° C. Obtained. Using the obtained test piece, the following measurements were performed to evaluate the performance.

(1) IZOD (Izod impact strength): conforming to ASTM D256, 23 ° C. (wall thickness 1/8 inch), unit: kJ / m ²
(2) Flexural modulus: compliant with ASTM D-790 (test conditions, etc .: 23 ° C., 4 mm), unit: MPa
(3) Volume resistivity value: Conforms to JIS K6911 (test plate: 80 × 80 × 3 mm), unit: Ω · cm
(4) Compliant with flame retardant UL94 combustion test (test specimen thickness: 1.5 mm, 1.0 mm, or 3.0 mm)
(5) Molding appearance: Evaluated according to the following criteria.
○: Good, ×: Defect appearance such as bumps on the surface

<Thickness and size of graphene sheet>
The thickness and size of the graphene sheet were measured by observation with an electron microscope.

Production Example 1 [Production of PC oligomer]
60 kg of bisphenol A was dissolved in 400 liters of 5 mass% sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A.
Next, this aqueous solution of bisphenol A in sodium hydroxide maintained at room temperature at a flow rate of 138 liter / hour and methylene chloride at a flow rate of 69 liter / hour was passed through an orifice plate through a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. It was introduced, and phosgene was co-flowed into it and blown in at a flow rate of 10.7 kg / hour, and reacted continuously for 3 hours. The tubular reactor used here was a double tube, and the discharge temperature of the reaction solution was maintained at 25 ° C. through the jacket portion through cooling water. The pH of the effluent was adjusted to 10-11.
The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / L.

Production Example 2 [Production of Reactive PDMS]
1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% by mass sulfuric acid were mixed and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, 25 g of sodium bicarbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr (4 × 10 ² Pa) to remove low-boiling substances to obtain oil.
To a mixture of 60 g 2-allylphenol and 0.0014 g platinum as platinum chloride-alcolate complex, 294 g of the oil obtained above was added at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature at 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80 wt% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and heated to 115 ° C. in vacuo to remove the solvent. The terminal phenol PDMS obtained had 30 repeats of dimethylsilanooxy units as measured by NMR.

Production Example 3 [Production of PC-PDMS copolymer]
182 g of reactive PDMS obtained in Production Example 2 was dissolved in 2 liters of methylene chloride, and 10 liters of PC oligomer obtained in Production Example 1 were mixed. Thereto, 26 g of sodium hydroxide dissolved in 1 liter of water and 5.7 cm ³ of triethylamine were added, and the mixture was stirred and reacted at room temperature at 500 rpm for 1 hour.
After completion of the reaction, to the above reaction system was added 600 g of bisphenol A dissolved in 5 liters of a 5.2% by weight aqueous sodium hydroxide solution, 8 liters of methylene chloride and 96 g of pt-butylphenol, and the mixture was brought to room temperature at 500 rpm. And stirred for 2 hours.
After the reaction, 5 liters of methylene chloride is added, and further washed with 5 liters of water, washed with 5 liters of 0.03 mol / L sodium hydroxide aqueous solution, washed with acid with 5 liters of 0.2 mol / L hydrochloric acid, and water 5 Two liters of water washing were sequentially performed, and finally methylene chloride was removed to obtain a flaky PC-PDMS copolymer. The obtained PC-PDMS copolymer was vacuum-dried at 120 ° C. for 24 hours. The viscosity average molecular weight was 17,000, and the PDMS content was 4.0% by mass.
The PDMS content is determined based on the intensity ratio between the isopropyl methyl group peak of bisphenol A found at 1.7 ppm by ¹ H-NMR and the methyl group peak of dimethylsiloxane found at 0.2 ppm. It was.

Examples 1-10 and Comparative Examples 1-13
In accordance with the above-described “Method for Producing Test Pieces”, the test pieces in each example were produced, and the performance was evaluated by various tests using the test pieces. The results are shown in Tables 1 to 3.

[note]
(A) component:
(A-1) PC-PDMS: PC-PDMS copolymer obtained in Production Example 3 having a viscosity average molecular weight of 17,000 and a PDMS content of 4.0% by mass (A-2) PC: “FN1900A (Idemitsu Kosan Co., Ltd.), viscosity average molecular weight 19,500
(B) component:
Graphene sheet 1: “graphene nanoplatelet xGnP” (manufactured by XG Sciences), thickness 6-8 nm, size (sheet size) 5 μm
Graphene sheet 2: “Graphene nanoplatelet xGnP” (manufactured by XG Sciences), thickness 6-8 nm, size (sheet size) 15 μm
Graphene sheet 3: “graphene nanoplatelet xGnP” (manufactured by XG Sciences), thickness 2 to 4 nm, size (sheet size) 2 μm
(C) component:
PTFE: PTFE “CD076” (Asahi Glass Fluoropolymers Co., Ltd.)
Other ingredients:
Carbon nanotube 1: multi-wall diameter 50-100 nm, length 1-10 μm, opening at both ends, amorphous carbon content 15% by mass (manufactured by Sun Nanotech)
Carbon nanotube 2: multi-wall diameter 10-30 nm, length 1-10 μm, opening at both ends, amorphous carbon amount 15 mass% (manufactured by Sun Nanotech)
Graphite: “PC99-300M” (manufactured by Ito Graphite Industries Co., Ltd.), average particle size 56 μm, thickness 1.7 μm

As can be seen from Tables 1 to 3, the polycarbonate resin composition belonging to the present invention contains a graphene sheet at a specific ratio, so that high flame retardancy is obtained and reduction in impact strength is reduced. It is also excellent in rigidity, conductivity and molded appearance. In particular, by including a PC-PDMS copolymer at a specific ratio, the impact strength and flame retardancy are excellent. Furthermore, by including PTFE, the flame retardance of a thin wall is attained. Further, by using a graphene sheet having a thickness of 5 to 10 nm and a size of 3 μm or more, higher flame retardancy, rigidity, and conductivity can be obtained.
On the other hand, the carbon nanotubes used in the comparative examples are inferior in rigidity and flame retardancy compared with the graphene sheet, and the micro-order graphite not only significantly reduces the impact strength but also reduces the flame retardancy. End up.

  The polycarbonate resin composition of the present invention can give a molded article excellent in flame retardancy, rigidity, impact resistance, conductivity, molded appearance, and thermal conductivity. This molded body is expected to expand its application fields such as housings, parts, films, and automobile parts of electrical / electronic equipment such as OA equipment, information equipment, and home appliances.

Claims (7)

A polycarbonate resin (A) having a mass ratio of 5:95 to 100: 0 of the polycarbonate-polyorganosiloxane copolymer (A-1) and the aromatic polycarbonate (A-2) other than (A-1). A polycarbonate resin composition comprising 70 to 99.5% by mass and 30 to 0.5% by mass of a graphene sheet (B) having a thickness of 5 to 10 nm and a size of 3 μm or more . The polycarbonate-polyorganosiloxane copolymer (A-1) includes a structural unit having a main chain represented by the general formula (I) and a structural unit represented by the general formula (II), and the general formula (II) The polycarbonate resin composition according to claim 1 , comprising 2 to 40% by mass of a polyorganosiloxane block comprising a structural unit represented by:

[Wherein, R ¹ and R ² are each independently an alkyl group or alkoxy group having 1 to 6 carbon atoms, X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, carbon A cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO—, —SO ₂ —, —O— or —CO—, and R ^{3 to} R ⁶ are each independently , A hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and Y represents an organic residue containing aliphatic or aromatic , N is an average number of repetitions and represents an integer of 1 to 600, and a and b represent integers of 0 to 4. ] The polycarbonate resin composition according to claim 2 , wherein Y is an organic residue derived from allylphenol or eugenol. The polycarbonate resin composition according to claim 2 or 3 , wherein the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A. The polycarbonate resin composition according to any one of claims 2 to 4 , wherein R ³ and R ⁴ in the structural unit represented by the general formula (II) are both methyl groups. Furthermore, polytetrafluoroethylene (C) contains 0.01-1 mass part with respect to 100 mass parts of total amounts of (A) component and (B) component, In any one of Claims 1-5 The polycarbonate resin composition as described. The molded object formed by shape | molding the polycarbonate resin composition in any one of Claims 1-6 .