JP6541082B2 - Polycarbonate-based resin composition and molded article - Google Patents

Description

  The present invention relates to a polycarbonate-based resin composition, a molded article obtained by molding the resin composition, and a current breaker structural member for an automobile comprising the molded article.

BACKGROUND ART In recent years, development of next-generation vehicles, such as electric vehicles (EVs), hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs) and the like, which can be expected to reduce carbon dioxide and reduce dependence on oil has been actively promoted. A large current flows frequently in these vehicles, and a device for interrupting the current is also required to prevent secondary damage such as fire, short circuit or electric shock due to an accident or the like. There is known a gas pressure type electric circuit breaker which explodes or burns explosives and shuts off the electric circuit by the generated pressure (for example, JP-A-2010-86653).
Inflator-using gas pressure circuit breakers installed in automobiles must meet the ISO 12097 test and the test requirements of automobile manufacturers that comply with the ISO 12097 test. For example, ISO 12097-3 has requirements for impact tests at -35 ° C, 23 ° C, and 85 ° C. Further, when assuming a very cold place as in JIS D 204 which is a JIS standard of automobile parts, a low temperature test at -30 ° C or -40 ° C is required. In order to satisfy such a demand, metal and ceramic are used for the case of the gas pressure type electric circuit breaker for motor vehicles. However, in order to reduce the weight of the automobile and to reduce the fuel consumption, it is a problem to replace a member made of metal or ceramic with resin (make it resin). For resinification, general engineering plastics with heat resistance of 100 ° C or higher can satisfy the test requirements under the environment at 85 ° C, but at the same time tests under the low temperature environment such as -35 to -40 ° C Requirements are also required to be satisfied. Not only that, there are also cases where high flame resistance is required in preparation for high environmental characteristics (for example, long-term heat resistance (high temperature resistance to high temperature) of 100 ° C. or higher) and ignition.

On the other hand, a polycarbonate-polyorganosiloxane copolymer (hereinafter, also referred to as a PC-POS copolymer) which is a polycarbonate-based material is known as a resin material having a high degree of low temperature impact properties.
As such a PC-POS copolymer, for example, in JP 2009-7487 A resin composition containing polyorganosiloxane-acrylic composite rubber, phosphorus-based flame retardant, and anti-dripping agent in aromatic polycarbonate resin Objects are disclosed. However, a polycarbonate resin composition using a phosphorus-based flame retardant has a problem that the heat resistance is significantly inferior both in the short and long term.

JP-A-2008-101117 discloses a resin composition containing an aromatic polycarbonate resin and a polyorganosiloxane-acrylic composite rubber. However, this aromatic polycarbonate resin composition has a problem in that although the initial low temperature impact properties are improved, the low temperature impact properties after long-term high temperature aging are significantly inferior.
JP 2005-126711 A discloses a resin composition containing a polyorganosiloxane-acrylic composite rubber in a resin composition of a polyester and a polycarbonate containing a polycarbonate-polyorganosiloxane copolymer. However, polycarbonate resin compositions using polyester have a problem that the low temperature impact properties are significantly inferior to those using no polyester. In addition, although it is described that the average repeating number n of a preferred orino-siloxane constitutional unit of the polycarbonate-polyorganosiloxane copolymer is 40 to 60, the low-temperature impact properties of this polycarbonate-polyorganosiloxane copolymer are It is insufficient, and the low temperature impact characteristics after long-term high temperature aging have not been studied.
JP-A-2000-191897 discloses a resin composition containing a polyorganosiloxane-acrylic composite rubber in a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer. Although the average number of repetitions of preferred origanosiloxane structural units is not described, the examples have an average number of repetitions n of 30. However, the low temperature impact properties after long-term high temperature aging of this polycarbonate-polyorganosiloxane copolymer have not been studied, and there is room for further improvement in the low temperature impact properties.

  As described above, in a conventional polycarbonate resin composition containing a PC-POS copolymer, the low temperature impact characteristics after long-term high temperature aging are degraded, and a resin composition having excellent low temperature impact strength after high temperature aging is obtained. I could not

JP, 2010-86653, A JP, 2009-7487, A JP 2008-101117 A JP, 2005-126711, A JP 2000-191897 A

A polycarbonate resin composition containing a PC-POS copolymer is excellent in impact resistance under a low temperature environment, but has a problem that its performance is deteriorated after long-term high temperature aging.
The present invention relates to a polycarbonate resin composition having the property of maintaining the low temperature impact property of a PC-POS copolymer even after long-term high temperature aging, a molded article obtained by molding the resin composition, and a molded article thereof It is an object of the present invention to provide an automotive current breaker structural member comprising:

  The present inventors have found that the above object can be achieved by blending a polyorganosiloxane-acrylic composite rubber with a polycarbonate-polyorganosiloxane copolymer having a repeating number of a specific organosiloxane constituent unit. , Completed the present invention.

［式中、Ｒ^１及びＲ^２は、それぞれ独立に炭素数１〜６のアルキル基又はアルコキシ基を示し、Ｘは単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、−Ｓ−、−ＳＯ−、−ＳＯ_２−、−Ｏ−又は−ＣＯ−を示し、ａ及びｂはそれぞれ独立に０〜４の整数を示す。Ｒ^３〜Ｒ^６は、それぞれ独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基もしくは炭素数６〜１２のアリール基を示し、Ｙは脂肪族または芳香族を含む有機残基を示し、ｎは平均繰り返し数を示す。］
また、上記のポリカーボネート系樹脂組成物には、（Ｃ）有機スルホン酸のアルカリ金属塩及び／又はアルカリ土類金属塩や、（Ｄ）フィブリル形成能を有するポリテトラフルオロエチレン系ドリップ防止剤を配合することができ、これらを含有することで難燃性がさらに向上したポリカーボネート系樹脂組成物とすることができる。さらに、上記のポリカーボネート系樹脂組成物には、（Ｅ）ポリオルガノシロキサンを配合することもでき、これにより、樹脂組成物の劣化を防止し、機械的強度や耐熱性などが維持されたポリカーボネート系樹脂組成物とすることもできる。
（２）上記のポリカーボネート系樹脂組成物を成形してなる成形品。
（３）上記の成形品を含む電流遮断器構造部材。 That is, the present invention is as follows.
(1) (A) A structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and an average repeating number n of organosiloxane constitutional units in the general formula (II) Resin which is 30 to 100 mass% of polycarbonate polyorganosiloxane copolymer (A-1) which is 50-500, and 0 to 70 mass% of aromatic polycarbonate (A-2) other than (A-1) A polycarbonate resin composition comprising 1 to 5.5 parts by mass of (B) polyorganosiloxane-acrylic composite rubber with respect to 100 parts by mass of the mixture, and having a viscosity average molecular weight of 1700 to 23000.

[Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an alkylidene group having 2 to 8 carbon atoms] And 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 a and b are each independently Represents an integer of 0-4. 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 Y is aliphatic Or an organic residue containing an aromatic group, and n represents an average number of repetitions. ]
Further, the polycarbonate resin composition described above contains (C) an alkali metal salt of an organic sulfonic acid and / or an alkaline earth metal salt, and (D) a polytetrafluoroethylene drip inhibitor having a fibril forming ability. It is possible to obtain a polycarbonate resin composition in which the flame retardancy is further improved by containing these. Furthermore, (E) polyorganosiloxane can also be mix | blended with said polycarbonate-type resin composition, and, thereby, deterioration of a resin composition is prevented and the polycarbonate-type in which mechanical strength, heat resistance, etc. were maintained. It can also be a resin composition.
(2) A molded article formed by molding the above-mentioned polycarbonate resin composition.
(3) A current breaker structural member including the above-mentioned molded article.

  The carbonate-based resin composition of the present invention is a resin mixture comprising a polycarbonate-polyorganosiloxane copolymer or a polycarbonate-polyorganosiloxane copolymer, and an aromatic polycarbonate other than the polycarbonate-polyorganosiloxane copolymer. In addition, since the polyorganosiloxane-acrylic composite rubber is blended, it is excellent in impact resistance at low temperatures, and has excellent low temperature impact strength even after high temperature aging.

  The present invention comprises (A) a structural unit represented by the above general formula (I) and a structural unit represented by the general formula (II), and an average of organosiloxane constitutional units in the general formula (II) Polycarbonate-polyorganosiloxane copolymer (A-1) 30-100 mass% whose repeating number n is 50-500, and aromatic polycarbonate (A-2) 0-70 mass% other than (A-1) It is a polycarbonate-type resin composition which contains 1-5.5 mass parts of (B) polyorganosiloxane-acrylic-type composite rubber with respect to 100 mass parts of resin mixtures which are, and whose viscosity average molecular weights are 1700-23000. Hereinafter, each component of the polycarbonate-type resin composition of this invention is demonstrated.

[(A-1) PC-POS copolymer]
The PC-POS copolymer used in the present invention is a copolymer containing the structural units represented by the above general formulas (I) and (II). The content of the constituent unit represented by the above general formula (I) is preferably 70 to 98% by mass, more preferably 85 to 97.5% by mass, in the (A-1) PC-POS copolymer. Preferably it is 90-97 mass%. The content of the constituent unit represented by the above general formula (II) is preferably 2 to 30% by mass, more preferably 2.5 to 15% by mass, in the (A-1) PC-POS copolymer. More preferably, it is 3 to 10% by mass. If it is 2 mass% or more, the effect of an impact-resistant strength improvement will be enough, and if it is 30 mass% or less, it will have sufficient heat resistance. In addition, content of the structural unit in (A-1) PC-POS is the value calculated by nuclear magnetic resonance (NMR) measurement.

  In the present invention, the average repeating number n of the organosiloxane constituent unit in the general formula (II) is 50 to 500, more preferably 70 to 400, still more preferably 80 to 250, and still more preferably 85. ~ 190. If n is less than 50, the effect of improving the impact properties at low temperatures is insufficient, and if it is 500 or less, there is no problem with the handleability of the polyorganosiloxane, on the production of PC-POS copolymer It is preferable from the viewpoint. The value of the average number of repetitions n is a value calculated by nuclear magnetic resonance (NMR) measurement.

The viscosity average molecular weight (Mv) of the PC-POS copolymer of the component (A-1) is preferably 12,000 to 50,000, more preferably from the viewpoint of the balance between the strength of the molded article and the productivity. Is 14,000 to 30,000, and more preferably 16,000 to 25,000. It is to be noted that the above viscosity average molecular weight is preferable because the component (A-1) is combined with an aromatic polycarbonate (A-2) component other than the component (A-1) described later to form a resin mixture. When the component -1) is used alone, it is preferable to use one in the range of 17,000 to 23,000 from the viewpoint of formability. The viscosity average molecular weight (Mv) is a value calculated by measuring the intrinsic viscosity [η] of a methylene chloride solution at 20 ° C. and using Schnell's formula ([η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 ). It is.

ここで、一般式（１）中、Ｒ^１及びＲ^２、Ｘ、ａ及びｂは、上記一般式（Ｉ）と同じであり、一般式（２）中、Ｒ^３〜Ｒ^６、Ｙは、上記一般式（II）と同じであり、ｎは５０〜５００であり、ｍは０又は１を示し、Ｚはハロゲン、−Ｒ^７ＯＨ、−Ｒ^７ＣＯＯＨ、−Ｒ^７ＮＨ_２、−ＣＯＯＨ又は−ＳＨを示し、Ｒ^７は直鎖、分岐鎖もしくは環状アルキレン基、アリール置換アルキレン基、環上にアルコキシ基を有してもよいアリール置換アルキレン基、アリーレン基を示す。 The PC-POS copolymer of the component (A-1) comprises a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), phosgene, carbonate ester, Or it is obtained by copolymerizing chloroformate.

Here, in the general formula (1), R ¹ and R ² , X, a and b are the same as the above general formula (I), and in the general formula (2), R ^{3 to} R ⁶ and Y are are as defined for general formula (II), n is 50 to 500, m is 0 or 1, Z is ^{halogen, -R 7 OH, -R 7 COOH} , -R 7 NH 2, -COOH or R 4 represents —SH, and R 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), which is used as a raw material of the PC-POS copolymer of the component (A-1), is not particularly limited. 2-bis (4-hydroxyphenyl) propane (generally called bisphenol A) is preferred. When bisphenol A is used as the dihydric phenol, in the general formula (I), it is a PC-POS copolymer in which X is an isopropylidene group and a = b = 0.
Examples of dihydric phenols other than bisphenol A include, for example, 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- (4-hydroxyphenyl) propane) 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 and 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 (hydroxyaryl) cycloalkanes such as 2-bis (4-hydroxyphenyl) norbornane, 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 Dihydroxydiaryl sulfides such as doloxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Dihydroxydiarylsulfoxides such as sulfoxide, 4,4'-dihydroxydiphenylsulfone, dihydroxydiarylsulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone, dihydroxys such as 4,4'-dihydroxydiphenyl Dihydroxy diaryl fluorenes such as diphenyls, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenyl Dihydroxydiaryls such as 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, etc. 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.
You may use these dihydric phenol individually or in mixture of 2 or more types.

  The polyorganosiloxane represented by the general formula (2) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol, allylphenol, eugenol, isopropenylphenol, etc., with a predetermined degree of polymerization n It can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain having. 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.

上記一般式（３）〜（１１）中、Ｒ^３〜Ｒ^６は一般式（II）と同様に、それぞれ独立に、水素原子、ハロゲン原子又は炭素数１〜６のアルキル基、炭素数１〜６のアルコキシ基もしくは炭素数６〜１２のアリール基を示し、ｎはオルガノシロキサン構成単位の平均繰り返し数であって５０〜５００の数を示す。また、Ｒ^８はアルキル、アルケニル、アリール又はアラルキル基を示し、ｃは正の整数を示し、通常１〜６の整数である。
これらの中でも、重合の容易さの観点においては、一般式（３）に示すフェノール変性ポリオルガノシロキサンが好ましい。また、入手の容易さの観点においては、一般式（４）に示す化合物中の一種であるα，ω−ビス［３−（ｏ−ヒドロキシフェニル）プロピル］ポリジメチルシロキサン、一般式（５）に示す化合物中の一種であるα，ω−ビス［３−（４−ヒドロキシ−２−メトキシフェニル）プロピル］ポリジメチルシロキサンが好ましい。 As a polyorganosiloxane represented by General formula (2), the compound of the following general formula (3)-(11) is mentioned, for example.

In the above general formulas (3) to (11), R ^{3 to} R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, and have 1 to 1 carbon atoms, similarly to the general formula (II) 6 represents an alkoxy group of 6 or an aryl group having a carbon number of 6 to 12, and n is an average repeating number of an organosiloxane constitutional unit and represents a number of 50 to 500. R ⁸ represents an alkyl, alkenyl, aryl or aralkyl group, c represents a positive integer, and is usually an integer of 1 to 6.
Among these, phenol-modified polyorganosiloxanes represented by the general formula (3) are preferable in view of the easiness of polymerization. Further, in view of the availability, it is preferable to use α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is a kind of the compound represented by the general formula (4), to the general formula (5) Among the compounds shown, α, ω-bis [3- (4-hydroxy-2-methoxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds, is preferred.

The said phenol modified polyorganosiloxane can be manufactured by a well-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 .alpha.,. Omega.-dihydrogenorganopolysiloxane. At this time, it is possible to synthesize an α, ω-dihydrogenorganopolysiloxane having a desired average repeating unit by changing the feed ratio of cyclotrisiloxane to disiloxane. Next, in the presence of a catalyst for hydrosilylation reaction, the desired reaction is carried out by subjecting this α, ω-dihydrogenorganopolysiloxane to an addition reaction with a phenolic compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol. Phenol-modified polyorganosiloxanes having average repeating units can be prepared.
Further, at this stage, it is preferable to heat under reduced pressure to distill off these low molecular weight compounds, since the low molecular weight cyclic polyorganosiloxane and the excess amount of the above-mentioned phenol compound remain as impurities.

[Aromatic polycarbonate resins other than (A-2) (A-1)]
In the polycarbonate resin composition of the present invention, the component (A-2) which is an aromatic polycarbonate other than the component (A-1) is an organic solvent inert to the reaction, a dihydric phenol compound in the presence of an alkaline aqueous solution, and An interfacial polymerization method in which phosgene is reacted and then a polymerization catalyst such as tertiary amine or quaternary ammonium salt is added to carry out polymerization, or dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent Those obtained by conventional aromatic polycarbonate production methods such as the pyridine method in which phosgene is introduced and directly produced can be used.

As a dihydric phenol type compound used for manufacture of the aromatic polycarbonate of a component (A-2), 2, 2-bis (4-hydroxyphenyl) propane [general 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, 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′-dihydroxyphenyl ether Dihydroxy aryl ethers such as 4,4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and the like Dihydroxy diaryl sulfides, 4,4'-dihydroxy diphenyl sulfoxide, 4,4'- dihydroxy 3,3'- dihydroxy di aryl sulfoxides such as 3,3'- dimethyl diphenyl sulfoxide, 4,4'- dihydroxy diphenyl sulfone, 4,4'- Dihydroxydiaryl sulfones such as dihydroxy-3,3'-dimethyldiphenyl sulfone dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis ( 4-hydroxy-3-me Dihydroxy diaryl fluorenes such as lphenyl) fluorene, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis Dihydroxydiaryladamantanes such as (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxy) Examples include phenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-dioxapentaene and the like.
You may use these dihydric phenol individually or in mixture of 2 or more types.

  In the production of the aromatic polycarbonate of the component (A-2), a molecular weight modifier, an end terminator and the like may be used, if necessary. As these, various types can be used as long as they are generally used for polymerization of polycarbonate resins.

Specific molecular weight modifiers include monohydric phenol such as phenol, on-butylphenol, m-n-butylphenol, p-n-butylphenol, o-isobutylphenol, m-isobutylphenol and p-isobutylphenol O-t-butylphenol, m-t-butylphenol, p-t-butylphenol, o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol, o-n-hexylphenol, m-n -Hexylphenol, p-n-hexylphenol, p-t-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, o n-nonylphenol, m-nonylphenol, p-n-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5 -Di-tert-butylphenol, 2,4-di-tert-butylphenol, 3,5-di-tert-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 position, meta position 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, p-t-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 of compounds.

  As the terminal stopper, a monovalent carboxylic acid and its derivative, and a monovalent phenol can be used. For example, p-tert-butyl-phenol, p-phenylphenol, p-cumylphenol, p-perfluorononylphenol, p- (perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert -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-tetraflo 2-propanol.

Furthermore, it can also be made into a branched polycarbonate with respect to said dihydric phenol type compound using a branching agent. The amount of the branching agent added is preferably 0.01 to 3 mol%, more preferably 0.1 to 1.0 mol%, based on the above-mentioned dihydric phenol compound.
As a branching agent, for example, 1,1,1-tris (4-hydroxyphenyl) ethane, 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]- Compounds having three or more functional groups such as 4- [α ′, α′-bis (4 ′ ′-hydroxyphenyl) ethyl] benzene, fluoroglycine, trimellitic acid and isatin bis (o-cresol) can be mentioned.

In the resin mixture (A) consisting of the component (A-1) and the component (A-2), the content of (A-1) is 30 to 100% by mass, preferably 45 to 100% by mass, more preferably Is 60 to 100% by mass, and the content of (A-2) is 70 to 0% by mass, preferably 55 to 0% by mass, more preferably 40 to 0% by mass.
When the content of (A-1) is less than 30% by mass or the content of (A-2) exceeds 70% by mass, the content of the polyorganosiloxane block portion in the resin mixture (A) is increased In order to improve the low temperature impact strength, it is necessary to increase the content of the polyorganosiloxane block portion including the structural unit represented by the general formula (II) when producing the component (A-1). However, if the content is increased during the production of the component (A-1), the uniformity of the reaction in the polymerization step may decrease, and the separation between the polymer and the washing water in the washing step of the polymer is deteriorated. As a result, the productivity of the component (A-1) is greatly reduced.

  The content of the polyorganosiloxane block moiety having a structural unit of the general formula (II) is preferably 2 to 30% by mass in the resin mixture (A) comprising the components (A-1) and (A-2), More preferably, it is 2.5-15 mass%, More preferably, it is 3-10 mass%. If it is 2 mass% or more, the effect of an impact-resistant strength improvement will be enough, and if it is 30 mass% or less, it will have sufficient heat resistance.

[(B) polyorganosiloxane-acrylic composite rubber]
The polyorganosiloxane-acrylic composite rubber used in the polycarbonate resin composition of the present invention has a core structure of a rubber component in which acrylic components such as polyorganosiloxane and polyalkyl (meth) acrylate can not be separated from each other It is. The polyorganosiloxane used for the polyorganosiloxane-acrylic composite rubber is not particularly limited, but is preferably a polyorganosiloxane containing a vinyl polymerizable functional group. Such polyorganosiloxane can be obtained, for example, by polymerizing a mixture of a diorganosiloxane and a vinyl polymerizable functional group-containing siloxane or, if necessary, a latex containing a siloxane crosslinking agent under high temperature using an acid catalyst, It can be manufactured.

  As a diorganosiloxane used for manufacture of polyorganosiloxane, the 3 or more membered ring diorganosiloxane cyclic body is mentioned, The thing of a 3-7 membered ring is preferable. Specifically, hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane and the like can be mentioned, but these can be used alone or in combination of two or more.

  In addition, the vinyl polymerizable functional group-containing siloxane may contain a vinyl polymerizable functional group and may be capable of bonding with a diorganosiloxane via a siloxane bond, taking into consideration the reactivity with the diorganosiloxane. Then, various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, Methacryloyloxysilanes such as γ-methacryloyloxypropylethoxydiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane, vinylsiloxanes such as tetramethyltetravinylcyclotetrasiloxane, and vinylphenylsilanes such as p-vinylphenyldimethoxymethylsilane , And further, for example, a mel- or y-mercaptopropyldimethoxymethylsilane, a γ-mercaptopropyltrimethoxysilane or the like Script siloxanes. These vinyl polymerizable functional group-containing siloxanes can be used alone or as a mixture of two or more.

  As a siloxane type crosslinking agent, trifunctional or tetrafunctional silane type crosslinking agents, for example, trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, etc. can be used. Specifically, for example, a mixture of a diorganosiloxane and a vinyl polymerizable functional group-containing siloxane or, if necessary, a mixture containing a siloxane-based crosslinking agent is emulsified with an emulsifier and water. The latex is micronized using a homomixer to micronize with high-speed rotation shear force, a homogenizer to micronize with high pressure generator, etc., and then polymerized under high temperature using acid catalyst, then alkaline It can be carried out by neutralizing the acid with the substance.

Methods of adding the acid catalyst used for polymerization include a method of mixing with a siloxane mixture, an emulsifying agent and water, and a method of dropping a latex formed by micronizing a siloxane mixture into a high temperature aqueous acid solution at a constant speed. In view of the ease of controlling the particle diameter of the organosiloxane, a method in which the latex in which the siloxane mixture is micronized is dropped at a constant rate into a high temperature aqueous acid solution is preferably used.
Moreover, as an emulsifier used in the production of polyorganosiloxane, an anionic emulsifier is preferable, and an emulsifier selected from sodium alkylbenzene sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like is used. In particular, sodium alkylbenzene sulfonate, sodium lauryl sulfate and the like are preferable.

  As a method of mixing a siloxane mixture, an emulsifier, water and / or an acid catalyst, there are mixing by high speed stirring, mixing by a high pressure emulsification device such as a homogenizer, etc., the particle diameter of polyorganosiloxane latex is the method of using a homogenizer Is a preferred method because the distribution of Examples of acid catalysts used for polymerization of polyorganosiloxanes include sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzene sulfonic acids and aliphatic substituted naphthalene sulfonic acids, and mineral acids such as sulfuric acid, hydrochloric acid and nitric acid. These acid catalysts can be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable in that it is also excellent in the stabilizing action of the polyorganosiloxane latex. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, appearance defects of the thermoplastic resin composition caused by the emulsifier component of the polyorganosiloxane latex can be reduced.

50 degreeC or more is preferable and, as for the polymerization temperature of polyorganosiloxane, 80 degreeC or more is more preferable. The polymerization time of the polyorganosiloxane is preferably 2 hours or more, more preferably 5 hours or more, in the case where the acid catalyst is mixed with the siloxane mixture, the emulsifying agent and water and made into fine particles for polymerization. In the method of dropping the latex in which the siloxane mixture is micronized into the aqueous solution, it is preferable to hold for about one hour after the end of the dropping of the latex.
The termination of the polymerization can be carried out by cooling the reaction solution and further neutralizing the latex with an alkaline substance such as sodium hydroxide, potassium hydroxide or sodium carbonate.

  The rubber component to be the core of the polyorganosiloxane-acrylic composite rubber used in the present invention is a polyorganosiloxane latex impregnated with a (meth) acrylate component consisting of an alkyl (meth) acrylate and a multifunctional (meth) acrylate. It can be produced by polymerization after polymerization.

  Examples of alkyl (meth) acrylates include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, etc. Methacrylates may be mentioned, and these can be used alone or in combination of two or more. Also, in view of the impact resistance and molding gloss of the resin composition containing a graft copolymer, the use of n-butyl acrylate is particularly preferred.

  Examples of polyfunctional (meth) acrylates include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. It can be used alone or in combination of two or more. As an example of a preferable polyfunctional (meth) acrylate, in consideration of the graft structure of the graft copolymer (the amount of insoluble matter in acetone and the solution viscosity of an acetone soluble component), it is possible to use allyl methacrylate and 1,3-butylene glycol dimethacrylate. A combination is mentioned.

  The rubber component (core) of the polyorganosiloxane-acrylic composite rubber comprising the polyorganosiloxane and the alkyl (meth) acrylate used in the present invention is an acrylic component such as the above alkyl (meth) acrylate in the latex of the polyorganosiloxane component. Can be prepared by the addition and polymerization under the action of a conventional radical polymerization initiator. As a method of adding an acrylic compound such as alkyl (meth) acrylate, there are a method of mixing with a latex of a polyorganosiloxane component at once and a method of dropping it into a latex of a polyorganosiloxane component at a constant speed. In addition, in consideration of the impact resistance of the resin composition containing the polyorganosiloxane-acrylic composite rubber to be obtained, a method in which latexes of polyorganosiloxane components are mixed at once is preferable. Moreover, as a radical polymerization initiator used for superposition | polymerization, the redox system initiator which combined the peroxide, the azo system initiator, or the oxidizing agent and the reducing agent is used. Among these, redox initiators are preferred, and in particular, a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite hydroperoxide is preferred.

  Then, in the presence of the rubber component (core) obtained as described above, one or more vinyl monomers are graft-polymerized to form a shell, thereby forming a polyorganosiloxane-acrylic composite rubber ( B) is obtained. The vinyl monomer is not particularly limited, and examples thereof include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, methacrylic esters such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate, and methyl acrylate. And acrylic acid esters such as ethyl acrylate and butyl acrylate; and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. These can be used alone or in combination of two or more. Also, in view of the impact resistance of the resin composition containing the polyorganosiloxane-acrylic composite rubber and the appearance of the molded product, the use of methyl methacrylate or acrylonitrile is preferable.

  The graft polymerization can be carried out by adding a vinyl monomer to the latex of the rubber component and performing radical polymerization in one or more stages. As a radical polymerization initiator to be used for the polymerization, a redox initiator in which a peroxide, an azo initiator, or an oxidizing agent and a reducing agent are combined is used. Among them, redox initiators are preferred, and in particular, a combination of ferrous sulfate, ethylenediaminetetraacetic acid disodium salt and Rongalite hydroperoxide is preferred.

  Various chain transfer agents for adjusting the molecular weight and grafting ratio of the graft polymer can be added to the vinyl monomer used in the graft polymerization. Moreover, in the case of graft polymerization, in order to stabilize polymerization latex and to control the average particle diameter of a graft copolymer, an emulsifier can be added. The emulsifier to be used is not particularly limited, but preferred examples thereof are cationic emulsifiers, anionic emulsifiers and nonionic emulsifiers, and more preferred examples are sulfonate emulsifiers or sulfate emulsifiers and carboxylates. There is a combination with an emulsifier.

  Further, the particle diameter of the polyorganosiloxane-acrylic composite rubber prepared as described above is not particularly limited, but the polycarbonate resin composition including the obtained polyorganosiloxane-acrylic composite rubber In consideration of the impact resistance and the surface appearance of the molded product, the average particle diameter of the polyorganosiloxane-acrylic composite rubber is preferably in the range of 0.01 to 2 μm. While the impact resistance of the molded object obtained from a thermoplastic polycarbonate-type resin composition being an average particle diameter of 0.01 micrometer or more and 2 micrometers or less is favorable, the molded object surface external appearance is favorable.

In the present invention, the polyorganosiloxane-acrylic composite rubber is a salt in which the graft copolymer latex produced as described above is introduced into hot water in which a metal salt such as calcium chloride, calcium acetate or aluminum sulfate is dissolved. By separating out and solidifying, the graft copolymer is separated and manufactured by recovering in powder form.
As such polyorganosiloxane-acrylic composite rubber, for example, commercially available products such as methabrene SX005, methabrene SRK-200, methabrene S-2030, methabrene S-2006, etc. manufactured by Mitsubishi Rayon Co., can be used.

  The content of the (B) polyorganosiloxane-acrylic composite rubber is 1.0 to 5.5 parts by mass, preferably 1.5 to 5.0 parts by mass with respect to 100 parts by mass of the (A) resin mixture. It is a part, more preferably 2.0-5.0, still more preferably 2.0-4.5 mass parts. If the amount is less than 1.0 part by mass, the effect of the low temperature impact characteristics after long-term high temperature aging is insufficient. If it exceeds 5.5 parts by mass, the rigidity inherent to polycarbonate tends to decrease, that is, the balance of physical properties tends to deteriorate.

[(C) Alkali metal salt and alkaline earth metal salt of organic sulfonic acid]
In the present invention, in order to improve the flame retardancy, as component (C), alkali metal salts and / or alkaline earth metal salts of organic sulfonic acids (hereinafter also referred to as organic sulfonic acid alkali (earth) metal salts) Can be blended.
Examples of the organic sulfonic acid include perfluoroalkanesulfonic acid and polystyrenesulfonic acid.
Although various things are mentioned as an organic sulfonic acid alkali (earth) metal salt, It is an organic sulfonic acid alkali metal salt and alkaline-earth metal salt which have an at least 1 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. Among these, sodium, potassium and cesium salts are preferred.

As the component (C), alkali metal salts and / or alkaline earth metal salts of perfluoroalkanesulfonic acid or polystyrenesulfonic acid are preferable.
Examples of alkali (earth) metal salts of perfluoroalkanesulfonic acid include those represented by the following general formula (12).
[Formula 4]
_{(C d F 2d + 1 SO} 3) e M ··· (12)

In the 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 Indicates the valence of
As these metal salts, for example, those described in Japanese Patent Publication No. 47-40445 correspond.

  As the perfluoroalkanesulfonic acid in the general formula (12), for example, perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluoro Hexane sulfonic acid, perfluoroheptane sulfonic acid, perfluorooctane sulfonic acid and the like can be mentioned. In particular, these potassium salts are preferably used.

  In the polycarbonate resin composition of the present invention, organic sulfonic acid alkali (earth) metal salts other than the above-mentioned perfluoroalkanesulfonic acid alkali (earth) metal salts can also be used, and these organic sulfones can be used. As an acid alkali (earth) metal salt, for example, alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzene Alkali (earth) metal salts of organic sulfonic acids such as sulfonic acid, diphenyl sulfone-3-sulfonic acid, diphenyl sulfone-3,3'-disulfonic acid, naphthalene trisulfonic acid and their fluorine-substituted compounds can be mentioned. Among them, alkali (earth) of diphenyl sulfonic acid Shokushio is one of those preferred with alkali metal or alkaline earth metal salt of perfluoroalkane sulfonic acid.

式（１３）中、Ｑはスルホン酸塩基を示し、Ｒ^９は水素原子又は炭素数１〜１０の炭化水素基を示す。ｓは１〜５の整数を示し、ｔはモル分率を示し、０＜ｔ≦１である。
ここで、Ｑのスルホン酸塩基は、スルホン酸のアルカリ金属塩及び／又はアルカリ土類金属塩であり、金属としては、ナトリウム、カリウム、リチウム、ルビジウム、セシウム、ベリリウム、マグネシウム、カルシウム、ストロンチウム及びバリウム等が挙げられる。
また、Ｒ^９は、水素原子又は炭素数１〜１０の炭化水素基であるが、好ましくは水素原子又はメチル基である。
ｓは１〜５の整数であり、ｔは、０＜ｔ≦１の関係である。そのため、スルホン酸塩基Ｑは、芳香環に対して、全置換したもの、部分置換したものを含んでもよい。 Moreover, as an alkali (earth) metal salt of polystyrene sulfonic acid, an alkali (earth) metal salt of a sulfonate group-containing aromatic vinyl resin represented by the following general formula (13) can be mentioned.

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 an alkaline earth metal salt of sulfonic acid, and as metals, 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 groups Q may include those completely substituted or partially substituted on the aromatic ring.

  The content of the alkali (earth) metal salt of the organic sulfonic acid is 0.01 to 0.10 parts by mass, preferably 0.02 to 0.09 parts by mass with respect to 100 parts by mass of the (A) resin mixture. Part, more preferably 0.03 to 0.08 parts by mass. It is preferable that it is in this range because the flame retardancy can be sufficiently improved.

[(D) polytetrafluoroethylene based anti-dripping agent having fibril forming ability]
In the present invention, a polytetrafluoroethylene-based anti-dripping agent having fibril-forming ability is compounded as the component (D) in order to impart a melt dripping prevention effect to the polycarbonate resin composition and to improve the flame retardancy. It can also be done.
As the anti-drip agent, polytetrafluoroethylene having a fibril-forming ability can be used. Here, “fibril-forming ability” means that the resins are bound together by an external action such as shear force to form fibers. To show a tendency to

Polytetrafluoroethylene having a fibril-forming ability (hereinafter, also referred to as PTFE) has a very high molecular weight, and usually has a number average molecular weight determined from a standard specific gravity of 500,000 or more, preferably 500,000 to 15,000,000, more preferably One million to ten million. Such PTFE is preferably, for example, tetrafluoroethylene in an aqueous solvent, in the presence of sodium, potassium or ammonium peroxydisulfide, at a pressure of 6.9 to 690 kPa (1 to 100 psi), at a temperature of 0 to 200 ° C., preferably It can be obtained by polymerization at 20 to 100 ° C.
In the polymerization, fluorine-containing olefin such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkylvinylether as a copolymerizable component, perfluoroalkyl (meth) as long as the properties of polytetrafluoroethylene are not impaired Fluorine-containing alkyl (meth) acrylates, such as an acrylate, can be used. The content of such a copolymerization component is preferably 10% by mass or less based on tetrafluoroethylene in polytetrafluoroethylene.

The polytetrafluoroethylene is preferably PTFE particles from the viewpoint of uniformly dispersing in polycarbonate. The particle diameter of the PTFE particles is usually 10 μm or less, preferably 0.05 to 1.0 μm.
As commercially available products of PTFE having fibril forming ability, for example, Teflon (registered trademark) 6-J (trade name, manufactured by Mitsui / Dupont Fluorochemicals Co., Ltd.), Polyflon D-1 and Polyflon F-103 (trade name, Daikin) Manufactured by Kogyo Co., Ltd., CD-076 and CD- 097 (trade name, manufactured by Asahi Glass Co., Ltd.), Algoflon F5 (trade name, manufactured by Montefluos Co., Ltd.) and Polyflon MPA, Polyflon FA- 100 (trade name, Daikin Industries, Ltd.) And the like.
These PTFEs can be used alone or in combination of two or more.

  The content of the anti-drip agent is 0.1 to 1.0 parts by mass, preferably 0.2 to 0.9 parts by mass, more preferably 0.3 based on 100 parts by mass of the (A) resin mixture. It is -0.8 mass parts. If the amount is less than 0.1 parts by mass, the flame retardancy can not be sufficiently improved. If the amount is more than 1.0 part by mass, the low temperature impact characteristics may be a factor to deteriorate.

[Mixed powder composed of polytetrafluoroethylene particles and organic polymer particles]
Such a polytetrafluoroethylene-based anti-drip agent used as the component (D) is a mixed powder composed of polytetrafluoroethylene particles and organic polymer particles from the viewpoint of appearance and physical properties of a molded article This mixed powder is preferably described below.

The polytetrafluoroethylene particles in the mixed powder comprising polytetrafluoroethylene particles and organic polymer particles generally have a particle size of 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. The aqueous dispersion of polytetrafluoroethylene particles can be obtained by emulsion polymerization of tetrafluoroethylene monomers using a fluorine-containing surfactant.
In emulsion polymerization of polytetrafluoroethylene particles, fluorine-containing olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkylvinylether as copolymerizable components, as long as the characteristics of polytetrafluoroethylene are not impaired. Fluorine-containing alkyl (meth) acrylates, such as perfluoroalkyl (meth) acrylate, can be used.

The content of the copolymerization component is preferably 10% by mass or less based on tetrafluoroethylene in the polytetrafluoroethylene particles.
The organic polymer particles used in combination with the polytetrafluoroethylene particles are not particularly limited, but from the viewpoint of the dispersibility of the polytetrafluoroethylene particles when compounded into the (A) resin mixture And polycarbonate resins are preferred.

Specific examples of monomers for producing organic polymer particles include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene Styrene-based monomers such as 2,4-dimethylstyrene and α-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate Alkyl such as dodecyl methacrylate, tridecyl acrylate, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate Meta) acrylate monomers; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate Examples of the monomer include olefin monomers such as ethylene, propylene and isobutylene, and diene monomers such as butadiene, isoprene and dimethyl butadiene. In particular, the use of an alkyl (meth) acrylate monomer is preferred.
By polymerizing these monomers, organic polymer particles are obtained. The said monomer can be used 1 type or in mixture of 2 or more types. As the organic polymer particles, particles of an alkyl (meth) acrylate copolymer are preferable.

The organic polymer particles are prepared, for example, as an aqueous dispersion of organic polymer particles. The method for producing the aqueous dispersion of organic polymer particles is not particularly limited, and examples thereof include an emulsion polymerization method using an ionic emulsifier and a soap-free emulsion polymerization method using an ionic polymerization initiator.
As an ionic emulsifier, any of an anionic emulsifier, a cationic emulsifier and a zwitterionic emulsifier can be used. Moreover, a nonionic emulsifier can also be used together with these ionic emulsifiers.
As an anionic emulsifier, fatty acid salts, higher alcohol sulfuric acid ester salts, liquid fatty acid sulfuric acid ester salts, fatty amines and sulfuric acid sulfates of aliphatic amides, fatty alcohol phosphoric acid ester salts, sulfonic acid salts of dibasic fatty acid esters And fatty acid amido sulfonates, alkyl allyl sulfonates and naphthalene sulfonates of formalin condensates.
Examples of cationic emulsifiers include aliphatic amine salts, quaternary ammonium salts, and alkyl pyridinium salts.
As an amphoteric emulsifier, alkyl betaine etc. can be mentioned.
Examples of ionic polymerization initiators include anionic persulfates (eg, potassium persulfate and ammonium persulfate), azobis (isobutyronitrile sulfonate), 4,4'-azobis (4-cyanovaleric acid) and the like Polymerization initiator, 2,2′-azobis (amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2 ′ Mention may be made of cationic polymerization initiators such as -azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobisisobutyramide dihydrate and the like.

The particle diameter d of the organic polymer particles of the present invention is not particularly limited, but from the viewpoint of the stability of the aggregation state with the polytetrafluoroethylene particles, the particle diameter d of the polytetrafluoroethylene particles is next to the particle diameter D A range of formulas is preferred.
[Equation 1]
0.1D <d <10D

The mixed powder consisting of polytetrafluoroethylene particles and organic polymer particles is prepared, for example, by mixing the aqueous dispersion of the polytetrafluoroethylene particles and the aqueous dispersion of organic polymer particles, and then the method described later. Obtained by powderization. This mixed powder contains aggregated particles in which polytetrafluoroethylene particles and organic polymer particles are aggregated due to the difference in surface charge, and individual particles which remain without aggregation.
The aggregated particles have a structure in which the polytetrafluoroethylene particles and the organic polymer particles are integrated, but the morphology may vary depending on the mixing ratio of the two particles and the particle diameter. That is, a form in which the organic polymer surrounds the polytetrafluoroethylene particles, a form in which the polytetrafluoroethylene particles surround the organic polymer particles, and several particles per particle. There is a form of aggregation of

In order to reduce the aggregation speed during the mixing of the aqueous dispersion, the nonionic emulsifier may be adsorbed on the surface of the polytetrafluoroethylene particles and / or the organic polymer particles before the mixing.
The nonionic emulsifier is not particularly limited, and examples thereof include polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, dialkyl phenoxy poly (ethylene oxy) ethanol, polyvinyl alcohol, polyacrylic acid and alkyl cellulose.

Then, the aqueous dispersion mixed as described above is introduced into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out, coagulation followed by drying or powder drying by spray drying can do.
In the above aqueous dispersion of polytetrafluoroethylene particles, a monomer having an ethylenically unsaturated bond may be emulsion-polymerized and coagulated or powder-dried by spray drying.

  Ethylenically unsaturated monomers to be emulsion-polymerized in an aqueous dispersion include styrene, p-methylstyrene, o-methylstyrene, p-chlorostyrene, o-chlorostyrene, p-methoxystyrene, o-methoxystyrene, Styrenic monomers such as 2,4-dimethylstyrene and α-methylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, Alkyl (meth) acrylate monomers such as dodecyl methacrylate, cyclohexyl acrylate and cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Vinyl ether monomers such as methyl ether and vinyl ethyl ether; Vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate; olefin monomers such as ethylene, propylene and isobutylene; butadiene, isoprene, prene, dimethyl butadiene and the like And diene monomers and the like. These monomers can be used alone or in combination of two or more.

  As a commercial product of mixed powder consisting of polytetrafluoroethylene particles and organic polymer particles, for example, A-3750 and A-3800 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.), SN 3300 B7 (trade name, manufactured by Shinepolymer Co., Ltd.) Etc.).

[(E) polyorganosiloxane]
In the present invention, in order to prevent the deterioration of the resin composition and maintain the properties such as mechanical strength, stability and heat resistance, it is preferable to further contain polyorganosiloxane as the component (E).
Such polyorganosiloxane is not particularly limited, and examples thereof include alkyl hydrogen silicone, alkoxy silicone and the like.
Examples of the alkyl hydrogen silicone include methyl hydrogen silicone and ethyl hydrogen silicone. On the other hand, as an alkoxy silicone, a methoxy silicone, an ethoxy silicone etc. are mentioned, for example.

Among these, particularly preferred are alkoxysilicones, specifically, silicone compounds containing an alkoxysilyl group in which an alkoxy group is bonded to a silicon atom directly or via a divalent hydrocarbon group, for example, a straight chain And cyclic, reticulated and partially branched linear polyorganosiloxanes, and linear polyorganosiloxanes are particularly preferable. Specifically, polyorganosiloxanes having a molecular structure in which an alkoxy group is bonded to a silicone main chain via a methylene chain are preferred.
As such a component (E), for example, SH1107, SR2402, BY16-160, BY16-161, BY16-160E, BY16-161E, etc., which are commercially available from Toray Dow Corning, are preferably used. it can.

  The content of the (E) polyorganosiloxane is preferably 0.05 to 0.30 parts by mass, more preferably 0.05 to 0.20 parts by mass, still more preferably 100 parts by mass of the (A) resin mixture. Is 0.07 to 0.15 parts by mass. If it is 0.05 mass part or more, deterioration of polycarbonate resin does not occur easily, and the fall of the molecular weight of resin can be controlled. If the amount is 0.30 parts by mass or less, the balance of economy is good, and moreover, since silver does not occur on the surface of the molded product, the appearance of the molded product is improved.

[Other additives]
In addition to the components (A) to (E) described above, the polycarbonate resin composition of the present invention is conventionally added to the polycarbonate resin composition as needed, as long as the effects of the present invention are not impaired. Various known additives can be blended. As these additives, antioxidants, reinforcing materials, fillers, stabilizers, UV absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, elastomers for improving flame resistance and impact resistance, etc. Can be mentioned.
The content of these additives is usually about 0 to 1 part by mass, preferably about 0.01 to 0.5 parts by mass, with respect to 100 parts by mass of the (A) resin mixture.

In particular, when an antioxidant is used, a phosphorus-based antioxidant and / or a phenol-based antioxidant and the like are suitably used. Furthermore, among the above-mentioned antioxidants, phosphite-based antioxidants such as tris (2,4-di-t-butylphenyl) phosphite, etc. are the heat stability during high temperature molding, and the long-term heat stability of molded articles From the point of improvement of
One of these antioxidants may be used alone, or two or more of these antioxidants may be used in combination. The compounding amount thereof is 0.01 with respect to 100 parts by mass of the resin mixture of component (A). The amount is about 1 part by mass, preferably 0.1 to 0.3 parts by mass, and more preferably 0.05 to 0.3 parts by mass.
When the compounding amount is within this range, the thermal stability in the molding step and the long-term thermal stability of the molded article can be maintained, and molecular weight reduction is unlikely to occur, and when the compounding amount exceeds 1 part by mass, the antioxidant There is a tendency that the adverse effect of decomposition products generated due to heat, moisture, etc. on polycarbonate increases.

[Molding]
The molded product which consists of a polycarbonate-type resin composition of this invention mix | blends each above-mentioned component, and is obtained by shape | molding what knead | mixed.
When producing the polycarbonate-based resin composition of the present invention, each of the obtained polycarbonate-based resin composition has a viscosity average molecular weight of 17,000 to 23,000, preferably 18,000 to 22,000. Considering the blend ratio of the components, especially the viscosity average molecular weight possessed by the components (A-1) and (A-1) other than the component (A-1) of the polycarbonate-polyorganosiloxane copolymer, It is necessary to adjust the blending ratio of By setting the viscosity average molecular weight of the polycarbonate resin composition within this range, the flowability at the time of melting can be secured, and a polycarbonate resin composition excellent in moldability can be obtained.

  The kneading method is not particularly limited, and examples thereof include methods using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneider, a multiscrew extruder, etc. . Moreover, the heating temperature at the time of kneading | mixing is normally selected in the range of 240-330 degreeC, Preferably 250-320 degreeC.

  As the molding method, various known molding methods can be used, and examples thereof include injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and foam molding. Be

  The components other than the polycarbonate resin may be previously melt-kneaded with the polycarbonate resin or another thermoplastic resin, that is, added as a master batch.

In addition, pelletization and injection molding are preferable, and general molding methods such as general injection molding method, injection compression molding method and gas assist molding method can be used, and various molded articles can be manufactured. .
Moreover, when using the molded object of this invention as an external appearance member, it is preferable to use the molding technology which improves the external appearance of a heat cycle molding method, a high temperature metal mold | die, a heat insulation metal mold | die etc.
Moreover, when parts are required to be flame retardant, it is preferable to use a molding technique such as lamination molding with a resin material having flame resistance, or two-color molding.
Since the heat transfer efficiency from the heat source can be enhanced by performing insert molding and outsert molding of the metal parts, it becomes an effective method when having a high heat source.
In order to obtain a large thin-walled injection-molded article, it is preferable to use injection compression molding or high-pressure or ultra-high pressure injection molding, and use partial compression molding or the like for molding of a molded article having a partially thin-walled portion. You can also.

  The polycarbonate-based resin composition of the present invention is excellent in impact resistance at low temperatures and can be molded into a molded article having excellent impact resistance even after high-temperature aging, so it is used as a component member of current breakers used in automobiles and the like. be able to.

  EXAMPLES Hereinafter, the present invention will be more specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

First, a polycarbonate-polyorganosiloxane copolymer of component (A-1) was produced as follows.
Production Example 1
[Production of Polycarbonate-Polydimethylsiloxane Copolymer (Si-PC-1)]
(1) Synthesis of Polycarbonate Oligomer To a 5.6 mass% aqueous sodium hydroxide solution, 2000 mass ppm of sodium dithionite was added with respect to bisphenol A (BPA) to be dissolved later, to which a bisphenol A concentration of 13.4 was added. Bisphenol A was dissolved to 5% by mass to prepare an aqueous sodium hydroxide solution of bisphenol A.
The aqueous solution of sodium hydroxide of bisphenol A was fed at a flow rate of 40 L / hr, methylene chloride at a flow rate of 15 L / hr, and phosgene at a flow rate of 4.0 kg / hr continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m. The tubular reactor had a jacket portion, and cooling water was passed through the jacket to keep the temperature of the reaction solution below 40 ° C.
The reaction solution leaving the tubular reactor is continuously introduced into a baffled tank reactor with an internal volume of 40 L equipped with a receding wing, and further an aqueous solution of sodium hydroxide of bisphenol A at 2.8 L / hr, 25 The reaction was carried out by adding a mass% sodium hydroxide aqueous solution at 0.07 L / hr, water at 17 L / hr, and a 1 mass% triethylamine aqueous solution at a flow rate of 0.64 L / hr. The reaction liquid which overflowed from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by leaving to stand, and the methylene chloride phase was collected.
The concentration of the polycarbonate oligomer thus obtained was 329 g / L, and the concentration of chloroformate group was 0.74 mol / L.

(2) Production of polycarbonate-polydimethylsiloxane copolymer (Si-PC-1) 15 L of the polycarbonate oligomer solution produced above in a 50 L tank reactor equipped with a baffle plate, paddle type stirring blade and cooling jacket, 9.0 L of methylene, 393 g of allylphenol end-modified polydimethylsiloxane (PDMS) having a repeating number of dimethylsiloxane units of 90, and 8.8 mL of triethylamine are charged, and 1389 g of a 6.4 mass% aqueous solution of sodium hydroxide is added thereto under stirring. In addition, the reaction between the polycarbonate oligomer and allylphenol end-modified PDMS was carried out for 10 minutes.
In this polymerization solution, a methylene chloride solution of p-t-butylphenol (PTBP) (138 g of PTBP dissolved in 2.0 L of methylene chloride), an aqueous sodium hydroxide solution of BPA (577 g of NaOH and 2.0 g of sodium dithionite) A solution obtained by dissolving 10 12 g of BPA in an aqueous solution dissolved in 4 L was added, and a polymerization reaction was performed for 50 minutes.
After adding 10 L of methylene chloride for dilution and stirring for 10 minutes, the mixture was separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained is sequentially washed with 15% by volume of 0.03 mol / L aqueous NaOH solution, 0.2 mol / L hydrochloric acid, and then after washing with respect to the solution Washing with pure water was repeated until the electric conductivity in the aqueous phase of the aqueous solution became 0.01 μS / m or less.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
The PDMS residue amount (PDMS copolymerization amount) determined by nuclear magnetic resonance (NMR) of the obtained polycarbonate-polydimethylsiloxane copolymer was measured according to ISO 1628-4 (1999) at 6.0 mass%. The viscosity number was 47.5 and the viscosity average molecular weight Mv = 17,700.

Production Examples 2 and 3
[Production of Polycarbonate-Polydimethylsiloxane Copolymer (Si-PC-2) and (Si-PC-3)]
Table 1 shows the type of polydimethylsiloxane (with the average repetition number n of siloxane groups in the constituent units represented by formula (II) changed), the amount of polydimethylsiloxane used, and the amount of p-t-butylphenol used. (Si-PC-2) and (Si-PC-3) were synthesized in the same manner as in Production Example 1, changing as described.

The composition, viscosity number and viscosity average molecular weight Mv of the obtained polycarbonate-polydimethylsiloxane copolymer are shown in Table 1.

Examples 1 to 6 and Comparative Examples 1 to 6
Each component was mix | blended in the ratio shown in Table 2, and the polycarbonate-type resin composition was prepared. In preparation, tris (2,4-di-tert-butylphenyl) phosphite (manufactured by BASF, trade name “Irgafos 168”) is used as an antioxidant in an amount of 0 parts by weight based on 100 parts by weight of the component (A). 10 parts by mass were mixed and melt-kneaded at a resin temperature of 280 ° C. by a vented twin screw extruder (manufactured by Toshiba Machine Co., Ltd., model name “TEM-35B”) to obtain pellets of each polycarbonate resin composition .
The polycarbonate-based resin composition pellets were injection molded using an injection molding machine under molding conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.
The impact resistance at 23 ° C. and −40 ° C., the flammability, and the elastic modulus were measured by the following method using the obtained test pieces. The results are shown in Table 2.

Each component shown in Table 2 used when preparing a polycarbonate-type resin composition is as follows.
(A-1) Polycarbonate-polyorganosiloxane copolymer The polycarbonate-polydimethylsiloxane copolymer produced in Production Examples 1 to 3 (Si-PC-1 to 3)
(A-2) Aromatic polycarbonate resins other than (A-1) 1) TAFLON FN 2200A (trade name, manufactured by Idemitsu Kosan Co., Ltd., BPA polycarbonate having a terminal of p-t-butylphenol, viscosity average molecular weight Mv = 21500 )
2) TAFLON FN 2600 A (trade name, manufactured by Idemitsu Kosan Co., Ltd., BPA polycarbonate having p-t-butylphenol as an end group, viscosity average molecular weight Mv = 25500)
3) Novarex 7030PJ (trade name, manufactured by Mitsubishi Engineering Plastics Co., Ltd., BPA polycarbonate having p-t-butylphenol as an end group, viscosity average molecular weight Mv = 29000)
(B) Polyorganosiloxane-acrylic composite rubber B-1) Metabrene SX-005 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., a polyorganosiloxane having a core of polyorganosiloxane and n-butyl acrylate, and a shell of methyl methacrylate) -Acrylic composite rubber)
B-2) Metabrene SRK-200 (trade name, manufactured by Mitsubishi Rayon Co., Ltd., a polyorganosiloxane-acrylic composite rubber in which the core comprises polyorganosiloxane and n-butyl acrylate, and the shell comprises styrene / acrylonitrile)
(C) F-top KFBS (trade name, Mitsubishi Materials Electronic Chemicals Co., Ltd., potassium perfluorobutane sulfonate)
(D) Metabrene A-3800 (trade name, a mixed powder made of Mitsubishi Rayon Co., Ltd., polytetrafluoroethylene particles and organic polymer particles)
(E) BY16-161 (trade name, manufactured by Toray Dow Corning Co., Ltd., a polysiloxane containing a methoxysilyl group in which a methoxy group is bonded to a silicon atom via a divalent hydrocarbon group).

Moreover, the physical-property evaluation in this invention evaluated each characteristic of resin by the following method using the granulated pellet obtained by the Example and the comparative example.
(Evaluation of the physical properties)
(1) Viscosity average molecular weight (Mv)
The intrinsic viscosity [η] of the methylene chloride solution at 20 ° C. was measured and calculated from the Schnell's equation ([η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 ).
(2) Fluidity (Q value) measurement After drying the obtained pellet at 120 degreeC for 5 hours, Q value (flow value) [unit; 10 ^<-2 > mL / sec] measurement was performed.
Using an elevated flow tester, the amount of molten resin (mL / sec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured under a pressure of 280 ° C. and 15.7 MPa according to JIS K 7210.
The Q value represents the outflow per unit time, and the larger the value, the higher the liquidity.
(3) Moldability Moldability was evaluated according to the following criteria, taking into consideration the Q value indicating fluidity.
○ (Good): Q value is 5 or more × (Defect): Q value is less than 5 (4) Izod impact test (without aging)
Notched Izod impact test was performed at 23 ° C. and −40 ° C. according to ASTM D256.
(5) Izod impact test (with aging)
After aging at 105 ° C. for 400 hours using a hot air circulating oven, the film was allowed to stand at 23 ° C. for 4 hours and then subjected to a notched Izod impact test at 23 ° C. and −40 ° C. according to ASTM D256. .
It is preferable that the Izod impact value at 23 ° C. and −40 ° C. is 400 J / m or more regardless of the presence or absence of aging.
(6) Flammability A vertical combustion test was conducted using a test piece of test piece (length 12.7 mm, width 12.7 mm, thickness 1.5 mm) prepared according to UL Standard 94, V-0, It classified and evaluated to V-1 and V-2.
(7) Flexural modulus According to ASTM D790, a flexural test was performed.

  According to Table 2, the polycarbonate resin compositions of Examples 1 to 6 comprising a polycarbonate-polyorganosiloxane copolymer having a repeating number of a specific organosiloxane constituent unit and a polyorganosiloxane-acrylic composite rubber are It can be seen that it is excellent in low-temperature impact resistance and excellent in impact resistance after high-temperature aging. On the other hand, Comparative Example 1 containing no polyorganosiloxane-acrylic composite rubber is inferior in impact resistance after high temperature aging, and Q value becomes small in Comparative Example 2 in which the viscosity average molecular weight of the resin mixture exceeds 23000. , The formability is worse. In Comparative Example 3 in which the number of repeating organosiloxane structural units in the polycarbonate-polyorganosiloxane copolymer is small, and in Comparative Examples 4 and 5 in which the aromatic polycarbonate is used without using the polycarbonate-polyorganosiloxane copolymer. It can be seen that both the low temperature impact resistance and the impact resistance after high temperature aging are reduced. Furthermore, when the compounding amount of the polyorganosiloxane-acrylic composite rubber compounded as the component (B) is large, as can be understood from Comparative Example 6, although the low temperature impact resistance and the impact resistance after high temperature aging are satisfactory, bending is possible. The elastic modulus is low, and it is not possible to obtain a polycarbonate resin composition satisfying all the properties.

Claims (9)

(A) A structural unit represented by the general formula (I) and a structural unit represented by the general formula (II), and an average repeating number n of the organosiloxane constituent unit in the general formula (II) is 50 to 50 30 to 100 mass% of polycarbonate-polyorganosiloxane copolymer (A-1) which is 500, and 100 mass of resin mixture which is 0 to 70 mass% of aromatic polycarbonate (A-2) other than (A-1) Halogen system containing 1 to 5.5 parts by mass of (B) polyorganosiloxane-acrylic composite rubber with respect to 1 part, and the halogen content in the whole composition corresponding to 0.1 to 6% by mass The polycarbonate-type resin composition which is a compound- free and whose viscosity average molecular weights are 1700-23000.

[Wherein, R ¹ and R ² each independently represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group, and X represents a single bond, an alkylene group having 1 to 8 carbon atoms, or an alkylidene group having 2 to 8 carbon atoms] And 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 a and b are each independently Represents an integer of 0-4. 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 Y is aliphatic Or an organic residue containing an aromatic group, and n represents an average number of repetitions. ]   The polycarbonate resin composition according to claim 1, wherein the structural unit represented by the general formula (I) is a structural unit derived from bisphenol A. Formula (II) polycarbonate resin composition according to claim 1 or 2 R ³ to R ⁶ in the structural unit represented are all methyl groups in.   The polyorganosiloxane-acrylic composite rubber (B) is a composite rubber in which the core is composed of polyorganosiloxane and polyalkyl (meth) acrylate, and the shell is graft-polymerized with one or more vinyl monomers. The polycarbonate resin composition according to any one of claims 1 to 3.   Furthermore, 0.01 to 0.10 parts by mass of (C) an alkali metal salt of an organic sulfonic acid and / or an alkaline earth metal salt with respect to 100 parts by mass of the component (A), and / or (D) fibril forming ability The polycarbonate resin composition according to any one of claims 1 to 4, which comprises 0.1 to 1.0 parts by mass of a polytetrafluoroethylene-based anti-dripping agent.   The polycarbonate resin composition according to claim 5, wherein the polytetrafluoroethylene drip inhibitor (D) having a fibril forming ability is a mixed powder composed of polytetrafluoroethylene particles and organic polymer particles.   The polycarbonate resin composition according to any one of claims 1 to 6, further comprising 0.05 to 0.30 parts by mass of the (E) polyorganosiloxane per 100 parts by mass of the component (A).   The molded article formed by shape | molding the polycarbonate-type resin composition in any one of Claims 1-7.   A current breaker structural member comprising the molded article according to claim 8.