JP6426372B2 - Polycarbonate resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a polycarbonate resin composition with improved chemical resistance. More specifically, the present invention is excellent in flowability and chemical resistance, comprising a polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a polyolefin resin and a core-shell type acrylic polymer which does not contain a styrene component. In addition, the present invention relates to a polycarbonate resin composition in which a decrease in mechanical strength is small before and after coating, and an injection-molded article comprising the same.

  Thermoplastic resins reinforced with impact modifiers for the purpose of improving impact properties are widely used because of their excellent mechanical strength and processability. In particular, polycarbonate resins are used in many applications such as machine parts, automobile parts, electric and electronic parts, office equipment parts, etc. because of their excellent properties such as mechanical strength, dimensional stability and flame retardancy. In recent years, with the widespread use of portable information terminals such as smartphones and tablets, mechanical strength, in particular impact resistance, under various environments has been required compared to conventional stationary type information terminals. Moreover, in the case of an exterior material, it is mostly painted from a viewpoint of high design nature and a high appearance. Therefore, as a resin for a portable information terminal case, impact resistance in a coated state has been required, and a further improvement in mechanical strength is required as compared with a conventional polycarbonate resin.

  Patent Document 1 reports an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin, a polyolefin resin and an acrylic elastic polymer and having improved low-temperature impact resistance properties. However, in such a polycarbonate resin composition, although mechanical strength is satisfactory, a large problem occurs in chemical resistance. Patent documents 2 and 3 report a polycarbonate resin composition in which an acrylic elastic polymer is specified among the above compositions. However, even such polycarbonate resin compositions are insufficient for flowability and chemical resistance.

  On the other hand, polycarbonate-polydiorganosiloxane copolymer resins are known as polycarbonates exhibiting good low-temperature impact resistance (for example, Patent Document 4). Further, Patent Document 5 reports a thermoplastic resin composition in which polysiloxane domains having an average domain size of 20 to 45 nm or 20 to 40 nm are embedded in a matrix of a polycarbonate polymer. This report states that the low temperature impact properties will be better if the polysiloxane domains have a certain size. However, with these polycarbonate-polydiorganosiloxane copolymer resins, coating defects may occur, and the impact resistance properties after coating are not sufficient. Although the polycarbonate resin composition which mix | blended the rubber-like elastic body with the polycarbonate polydiorganosiloxane copolymer resin as a polycarbonate resin composition excellent in the further impact resistance is reported by patent document 6, chemical resistance is carried out. Is not mentioned.

  As a polycarbonate composition having both impact resistance and organic solvent resistance, Patent Document 7 discloses graft modification with an aromatic polycarbonate, a polycarbonate-polydiorganosiloxane copolymer resin and an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride. Polycarbonate resin compositions comprising hydrogenated aliphatic diene-vinyl aromatic block copolymers have been reported. This report evaluates impact resistance measured according to ASTM method D256 on 1/4 inch and 1/8 inch thick test pieces. However, not only portable information terminals but also thinning of electrical and electronic equipment cases has progressed, and there is no correlation between the strength of the actual molded product and the impact resistance according to the standard, and further improvement is required. Patent Document 8 reports a polycarbonate resin composition comprising an aromatic polycarbonate resin and a polyolefin resin and an acrylic elastic polymer. This report describes the improvement of low temperature impact resistance and chemical resistance. However, the characteristics in the case of a thin and complex shape close to the case of an actual portable information terminal are not sufficient. Patent Document 9 reports a portable electronic device case made of a polycarbonate-polydiorganosiloxane copolymer resin having a specific siloxane chain length and an aromatic polycarbonate other than that. However, chemical resistance needs to be further improved.

Japanese Examined Patent Publication No. 2-27380 JP-A-56-76449 JP-A-4-249576 JP-A-5-247195 Japanese Patent Application Publication No. 2006-523243 Japanese Patent Application Laid-Open No. 4-225060 Japanese Patent Laid-Open No. 3-229755 JP, 2010-222480, A JP, 2011-21127, A

  An object of the present invention is to provide a polycarbonate resin composition having the properties required for a portable electronic device casing, that is, good low temperature impact resistance and chemical resistance, and further having fluidity sufficient to correspond to thin-wall molding and It is in providing an article.

  As a result of intensive studies to achieve the above object, the present inventors have a fluidity suitable for thin-wall molding by blending a polycarbonate-polydiorganosiloxane copolymer resin, a specific elastic polymer and a polyolefin resin. The present invention has been also achieved by finding that a polycarbonate resin composition having both low temperature impact resistance and chemical resistance sufficient as a portable electronic device case can be obtained. That is, according to the present invention, (C) polyolefin is used per 100 parts by weight of the resin component consisting of (1) (A) polycarbonate resin (component A) and (B) polycarbonate-polydiorganosiloxane copolymer resin (component B). Polycarbonate resin composition containing 0.1 to 5 parts by weight of a resin (C component) and 1 to 15 parts by weight of an acrylic elastic polymer (D component) which is (D) a core-shell type and does not contain a styrene component Is provided.

  One of the more preferable embodiments of the present invention is a polycarbonate-polydicarbonate comprising (2) a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3] It is an organosiloxane copolymer resin, It is a polycarbonate resin composition as described in said structure (1) characterized by the above-mentioned.

[In the above general formula [1], R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different And a and b each represent an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. .

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to ²⁰ carbon atoms. Alkyl group, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms To 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7)]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms And R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms .)

  One of the more preferable embodiments of the present invention is (3) the polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] based on the total weight of the polycarbonate resin composition It is a polycarbonate resin composition as described in said structure (1) or (2) characterized by content being 1.0 to 10.0 weight%.

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms Or p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.

One of the more preferable embodiments of the present invention is that (4) the component B is a polycarbonate-polydiorganosiloxane copolymer resin in which polydiorganosiloxane domains having an average size of 0.5 to 18 nm are present in a matrix of polycarbonate polymer The polycarbonate resin composition according to any one of the above configurations (1) to (3), characterized in that
One of the more preferable embodiments of the present invention is the polycarbonate resin composition according to any one of the above-mentioned constitutions (1) to (4), wherein the component (5) C is polyethylene.
One of the more preferable embodiments of the present invention is that the component (6) D is an acrylic elastic polymer in which the compound to be grafted is at least one monomer selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is a polycarbonate resin composition in any one of the said structures (1)-(5) characterized by being.
One of the more preferable embodiments of the present invention is that the component (7) D is an acrylic elastic polymer characterized in that the rubber content is 60% by weight or more. It is a polycarbonate resin composition in any one.
One of the more preferable embodiments of the present invention is that the component (8) A contains (A-1) 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and a divalent phenol and a carbonate precursor. It is a polycarbonate resin composed of an aromatic polycarbonate resin (component A-1) obtained by reaction and an aromatic polycarbonate resin (component A-2) other than the component (A-2) A-1. It is a polycarbonate resin composition in any one of (1)-(7).
One of the more preferable embodiments of the present invention is any one of the above constitutions (1) to (8) characterized in that the viscosity average molecular weight of the (9) component A is in the range of 13,000 to 25,000. It is a polycarbonate resin composition of a statement.
One of the more preferable embodiments of the present invention is (10) an injection-molded article formed from the polycarbonate resin composition according to any one of the above-mentioned constitutions (1) to (9).
One of the more preferable embodiments of the present invention is (11) the injection-molded article according to the above configuration (10), wherein the injection-molded article is a portable information terminal exterior member.
One of the more preferable embodiments of the present invention is (12) the injection molded article according to the above configuration (10), which is a portable information terminal exterior member formed by coating the injection molded article.

Hereinafter, the present invention will be specifically described.
(A component: polycarbonate resin)
The polycarbonate resin to be used as component A of the present invention is usually obtained by reacting a dihydroxy compound with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, as well as a solid phase transesterification method using a carbonate prepolymer. Or a polymer obtained by polymerization according to a ring-opening polymerization method of a cyclic carbonate compound. As a dihydroxy component used here, what is normally used as a dihydroxy component of aromatic polycarbonate may be sufficient, and bisphenol and aliphatic diols may be sufficient. As bisphenols, for example, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- Phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5 -Trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-) Butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) ) Octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4) -Hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 4,4′-dihydroxydiphenyl ether, 4,4'-Dihydroxy-3,3'-dimethyl diphenyl ether, 4,4'-sulfone Diphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyl Diphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide 4,4'-Dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl } Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydro) Xyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 '-(1,3-adamantandiyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

  Examples of aliphatic diols include 2,2-bis- (4-hydroxycyclohexyl) -propane, 1,14-tetradecanediol, octaethylene glycol, 1,16-hexadecanediol, 4,4'-bis (2- Hydroxyethoxy) biphenyl, bis {(2-hydroxyethoxy) phenyl} methane, 1,1-bis {(2-hydroxyethoxy) phenyl} ethane, 1,1-bis {(2-hydroxyethoxy) phenyl} -1- Phenylethane, 2,2-bis {(2-hydroxyethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-methylphenyl} propane, 1,1-bis {(2-hydroxyethoxy) ) Phenyl} -3,3,5-trimethylcyclohexane, 2,2-bis {4- (2-hydroxy) Ethoxy) -3,3'-biphenyl} propane, 2,2-bis {(2-hydroxyethoxy) -3-isopropylphenyl} propane, 2,2-bis {3-t-butyl-4- (2-hydroxy) Ethoxy) phenyl} propane, 2,2-bis {(2-hydroxyethoxy) phenyl} butane, 2,2-bis {(2-hydroxyethoxy) phenyl} -4-methylpentane, 2,2-bis {(2 -Hydroxyethoxy) phenyl} octane, 1,1-bis {(2-hydroxyethoxy) phenyl} decane, 2,2-bis {3-bromo-4- (2-hydroxyethoxy) phenyl} propane, 2,2- Bis {3,5-dimethyl-4- (2-hydroxyethoxy) phenyl} propane, 2,2-bis {3-cyclohexyl-4- (2-hydroxy) X) phenyl} propane, 1, 1-bis {3-cyclohexyl 4- (2-hydroxy ethoxy) phenyl} cyclohexane, bis {(2-hydroxy ethoxy) phenyl} diphenyl methane, 9, 9- bis {(2-hydroxy Ethoxy) phenyl} fluorene, 9,9-bis {4- (2-hydroxyethoxy) -3-methylphenyl} fluorene, 1,1-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,1-bis { (2-hydroxyethoxy) phenyl} cyclopentane, 4,4′-bis (2-hydroxyethoxy) diphenyl ether, 4,4′-bis (2-hydroxyethoxy) -3,3′-dimethyldiphenyl ether Ter, 1,3-bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1 , 4-Bis [2-{(2-hydroxyethoxy) phenyl} propyl] benzene, 1,4-bis {(2-hydroxyethoxy) phenyl} cyclohexane, 1,3-bis {(2-hydroxyethoxy) phenyl} Cyclohexane, 4,8-bis {(2-hydroxyethoxy) phenyl} tricyclo [5.2.1.02,6] decane, 1,3-bis {(2-hydroxyethoxy) phenyl} -5,7-dimethyl Adamantane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 1,4: 3,6-dianhydro-D-sorbitol (Isosorbide), 1,4: 3,6-dianhydro-D-mannitol (isomannide), 1,4: 3,6-dianhydro-L-iditol Isoidide), and the like.

  Among these, aromatic bisphenols are preferred, and among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4). -Hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyl Diphenol, 2,2′-dimethyl-4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene are preferred, in particular 2,2-bis. 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

  The polycarbonate resin used as the component A of the present invention may be a branched polycarbonate resin by using a branching agent in combination with the above dihydroxy compound. Examples of trifunctional or higher polyfunctional aromatic compounds used for the branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2 , 4,6-Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [4 Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol Roxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acids thereof And the like, and among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and in particular 1-tris (4-hydroxyphenyl) ethane is preferred.

  These polycarbonate resins are produced by a reaction means known per se which produces ordinary aromatic polycarbonate resins, for example, a method of reacting an aromatic dihydroxy component with a carbonate precursor such as phosgene or carbonic acid diester. The basic means of the manufacturing method will be briefly described.

  In reactions using, for example, phosgene as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Also, catalysts such as tertiary amines or quaternary ammonium salts can be used to accelerate the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours. Transesterification using a carbonic acid diester as a carbonate precursor is carried out by a method in which a predetermined proportion of an aromatic dihydroxy component is heated and stirred with a carbonic acid diester in an inert gas atmosphere to distill off the alcohol or phenol formed. . The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced and the like, but is usually in the range of 120 to 300 ° C. The reaction is initially completed under reduced pressure to complete the reaction while distilling off the alcohol or phenol formed. It is also possible to use catalysts which are usually used in transesterification reactions to accelerate the reaction. As a carbonic diester used for the said transesterification, a diphenyl carbonate, a dinaphthyl carbonate, a bis (diphenyl) carbonate, a dimethyl carbonate, a diethyl carbonate, a dibutyl carbonate etc. are mentioned, for example. Among these, diphenyl carbonate is particularly preferred.

  In the present invention, an end terminator is used in the polymerization reaction. End terminators are used for molecular weight control, and the polycarbonate resins obtained are superior in thermal stability compared to those which are not because they are end-capped. As such an end terminator, monofunctional phenols represented by the following general formulas [5] to [7] can be shown.

[Wherein, A represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkylphenyl group (having 1 to 9 carbon atoms in the alkyl portion), a phenyl group, or a phenylalkyl group (1 to 9 carbon atoms in the alkyl portion)] And r is an integer of 1 to 5, preferably 1 to 3].

[Wherein, X is -R-O-, -R-CO-O- or -R-O-CO-, wherein R is a single bond or a C1-C10, preferably 1-5, Is a monovalent aliphatic hydrocarbon group, and n is an integer of 10 to 50. ]

  Specific examples of monofunctional phenols represented by the above general formula [5] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl And phenol and isooctylphenol. The monofunctional phenols represented by the above general formulas [6] to [7] are phenols having a long chain alkyl group or aliphatic ester group as a substituent, and using these, the terminal of polycarbonate resin Not only functions as a termination agent or a molecular weight modifier, but also improves the melt flowability of the resin, facilitates molding and processing, and has the effect of reducing the water absorption of the resin, used. The substituted phenols of the above general formula [7] preferably have n of 10 to 30, more preferably 10 to 26, and specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol and octadecylphenol. Eicosylphenol, docosylphenol and triacontylphenol can be mentioned. Further, as substituted phenols of the above general formula [7], compounds in which X is -R-CO-O- and R is a single bond are suitable, and those in which n is 10 to 30, particularly 10 to 26 Are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Among these monofunctional phenols, monofunctional phenols represented by the above general formula [5] are preferable, more preferable are alkyl substituted or phenyl alkyl substituted phenols, and particularly preferable is p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenols be terminated at least 5 mol%, preferably at least 10 mol%, with respect to all the ends of the obtained polycarbonate resin, and the termination agent alone be used. Or two or more of them may be used in combination.

  The polycarbonate resin used as the component A of the present invention is a polyester carbonate obtained by copolymerizing an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the purpose of the present invention is not impaired. Good.

The range of 13,000-25,000 is preferable, as for the viscosity average molecular weight of polycarbonate resin used as A component of this invention, 13,000-21,000 are more preferable, and the range of 16,000-21,000 is preferable. Even more preferred, the range of 16,000 to 20,000 is most preferred. If the molecular weight exceeds 25,000, the melt viscosity may be too high and formability may be poor, and if the molecular weight is less than 13,000, mechanical strength may be a problem. The viscosity average molecular weight as referred to in the present invention is determined by using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20 ° C. The specific viscosity is inserted according to the following equation to determine the viscosity average molecular weight M.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the second drop of methylene chloride, t is the second drop of the sample solution]
η _SP /c=[η]+0.45×[η] ² c (where [[] is the limiting viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The polycarbonate resin used as the component A of the present invention preferably has a total Cl (chlorine) content in the resin of 0 to 200 ppm, more preferably 0 to 150 ppm. When the total amount of Cl in the polycarbonate resin exceeds 200 ppm, the hue and the thermal stability deteriorate, which is not preferable.

  The polycarbonate resin used as A component of this invention can be used 1 type or in combination of 2 or more types. As an example of combining two or more polycarbonate resins, (A-1) obtained by reacting a dihydric phenol containing 9,9-bis (4-hydroxy-3-methylphenyl) fluorene with a carbonate precursor Polycarbonate resin which consists of aromatic polycarbonate resin (A-2 component) other than aromatic polycarbonate resin (A-1 component) and (A-2) A-1 component is mentioned. Although the component A-1 alone has little effect on the low-temperature impact resistance, it is preferable in the polycarbonate resin composition of the present invention because the low-temperature impact resistance is further improved as compared with the case where the component A-1 is not added. The ratio (A-1 / A-2) of the A-1 component to the A-2 component is not particularly limited, but is preferably 0.1 / 99.9 to 50/50, more preferably 0.1. /99.9 to 20/80, still more preferably 0.1 / 99.9 to 10/90, and most preferably 0.1 / 99.9 to 5/95. 9,70-bis (4-hydroxy-3-methylphenyl) fluorene constituting the component A-1 is preferably 10 to 70% by weight with respect to 100% by weight of all dihydroxy compounds constituting the component A-1, more preferably It is 10 to 50% by weight, still more preferably 20 to 50% by weight, and most preferably 30 to 50% by weight.

<Component B: Polycarbonate-polydiorganosiloxane copolymer resin>
As polycarbonate-polydiorganosiloxane copolymer resin used as B component of this invention, the polycarbonate-polydiorganosiloxane copolymer which the polydiorganosiloxane domain whose average size is 0.5-18 nm exists in the matrix of a polycarbonate polymer It is preferably a resin. The average size of the polydiorganosiloxane domain is more preferably 2.0 to 18 nm, still more preferably 5.0 to 18 nm, and most preferably 5.0 to 15 nm. If the average size is less than 0.5 nm, the low temperature impact resistance is not sufficient, and if it exceeds 18 nm, problems may occur in the appearance of the molded article and the paintability, which is not preferable. The average size of this polydiorganosiloxane domain was measured by Small Angel X-ray Scattering (SAXS). The small-angle X-ray scattering method is a method of measuring diffuse scattering diffraction that occurs in a small-angle region in which the scattering angle (2θ) is less than 10 °. In this small-angle X-ray scattering method, if there is a region of about 1 to 100 nm in size with different electron density in the substance, diffuse scattering of X-rays is measured by the difference in electron density. The particle diameter of the object to be measured is determined based on the scattering angle and the scattering intensity. In the case of a polycarbonate-polydiorganosiloxane copolymer resin in which a polydiorganosiloxane domain is dispersed in a matrix of a polycarbonate polymer, the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domain causes diffuse scattering of X-rays. Small-angle X-ray scattering profile is measured by measuring the scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 °, the polydiorganosiloxane domain is a spherical domain, and the dispersion of particle size distribution The virtual particle size and the temporary particle size distribution model are simulated using commercially available analysis software, assuming the existence of and the average size of the polydiorganosiloxane domain is determined. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a matrix of polycarbonate polymer, which can not be accurately measured by observation with a transmission electron microscope, can be measured accurately, simply and reproducibly. Can.

  Component B is preferably a polycarbonate-polydiorganosiloxane copolymer resin comprising a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3].

[In the above general formula [1], R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different And a and b each represent an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. .

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to ²⁰ carbon atoms. Alkyl group, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms To 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7)]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms And R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 to 150. X is a divalent aliphatic group having 2 to 8 carbon atoms .)

  As dihydric phenol (I) which derives the carbonate structural unit represented by the above general formula [1], for example, 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (1) 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3'-biphenyl) propane, 2,2-bis ( 4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4 Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9 -Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'- Hydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4 '-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'- Sulfonyl diphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6 Decane, 4,4 '-(1,3-adamantanediyl) diphenol, and 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl- 4,4'-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, in particular 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane, 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

In the carbonate structural unit represented by the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or carbon A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a hydrogen atom or carbon Particularly preferred is an alkyl group of 1 to 6 or a phenyl group. R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms It is an alkyl group, and a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are particularly preferable. As a dihydroxy aryl terminal polydiorganosiloxane (II) which derives the carbonate structural unit represented by said Formula [3], a compound as shown to the following general formula (I) is used suitably, for example.

  Each of p and q representing the degree of polymerization of diorganosiloxane is a natural number, and p + q is a natural number of 4 or more and 150 or less, preferably 4 to 120, more preferably 30 to 120, still more preferably 30 to 100, and 30 -60 are most preferred.

The content of the polydiorganosiloxane component in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is preferably 1.0 to 20.0% by weight, more preferably 2.0 to 20.0. % By weight, more preferably 2.0 to 10.0% by weight, still more preferably 3.0 to 10.0% by weight, and most preferably 3.0 to 8.0% by weight is there. If the polydiorganosiloxane component content is less than 1.0% by weight, the low-temperature impact resistance is not sufficient, and if it exceeds 20.0% by weight, problems may occur in the appearance of the molded article and the paintability. The diorganosiloxane polymerization degree and the polydiorganosiloxane component content can be calculated by ¹ H-NMR measurement.

  Next, the method for producing the above preferable polycarbonate-polydiorganosiloxane copolymer resin will be described below. By reaction of dihydric phenol (I) with a chloroformate-forming compound such as phosgene or chloroformate of dihydric phenol (I) in advance in a mixture of an organic solvent insoluble in water and an aqueous alkali solution, A mixed solution of a chloroformate compound containing a carbonate oligomer of dihydric phenol (I) having a chloroformate of dihydric phenol (I) and / or a terminal chloroformate group is prepared. As a chloroformate-forming compound, phosgene is preferred.

  When producing a chloroformate compound from dihydric phenol (I), the entire amount of dihydric phenol (I) from which the carbonate structural unit represented by the above general formula [1] is derived can also be used as a chloroformate compound at one time. Alternatively, a part of it may be added as a post-addition monomer as a reaction raw material to the subsequent interfacial polycondensation reaction. The post-addition monomer is added to accelerate the subsequent polycondensation reaction, and it is not necessary to add it if not necessary.

Although the method of this chloroformate compound formation reaction is not specifically limited, Usually, the system of performing in a solvent in the presence of an acid binder is preferable. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add.
The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. When phosgene, which is a suitable chloroformate-forming compound, is used, a method of blowing gasified phosgene into the reaction system can be suitably employed.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and organic bases such as pyridine, or mixtures thereof Is used.
Similarly to the above, the use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction. Specifically, per equivalent (usually 1 mole corresponds to 2 equivalents), 2 equivalents or a slight excess thereof per mole of dihydric phenol (I) used to form a chloroformate compound of dihydric phenol (I) It is preferred to use an acid binder.

  As the solvent, solvents inert to various reactions such as those used for producing a known polycarbonate may be used alone or as a mixed solvent. Representative examples include hydrocarbon solvents such as, for example, xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

The pressure in the reaction for producing a chloroformate compound is not particularly limited, and may be normal pressure, elevated pressure or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, the reaction is accompanied by heat generation, so it is desirable to use water cooling or ice cooling. The reaction time depends on other conditions and can not be generally defined, but is usually 0.2 to 10 hours.
Known interfacial reaction conditions can be used for the pH range in the reaction for producing a chloroformate compound, and the pH is usually adjusted to 10 or more.

  Thus, in the preparation of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention, the dihydric phenol (I) having a chloroformate of the dihydric phenol (I) and a terminal chloroformate group After preparing a mixed solution of a chloroformate compound containing a carbonate oligomer of formula (I), the dihydroxyaryl-terminated polydiorganosiloxane (II) is derived from a carbonate constitutional unit represented by the general formula [3] while stirring the mixed solution; The dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound are added at a rate of 0.01 mol / min or less per 1 mol of the amount of dihydric phenol (I) charged in preparation of the mixed solution. Polycarbonate by interfacial polycondensation Obtaining a lysine organosiloxane copolymer resin.

  The polycarbonate-polydiorganosiloxane copolymer resin used as B component of this invention can be used as a branched polycarbonate polydiorganosiloxane copolymer resin, using a branching agent together with a dihydric phenol type compound. Examples of trifunctional or higher polyfunctional aromatic compounds used for the branched polycarbonate resin include phloroglucin, phloroglucide, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2 , 4,6-Trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [4 Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol Roxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and acids thereof And the like, and among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and in particular 1-tris (4-hydroxyphenyl) ethane is preferred.

The method for producing such a branched polycarbonate-polydiorganosiloxane copolymer resin is an interfacial polycondensation after the completion of the reaction even if a branching agent is contained in the mixed solution at the time of the reaction for forming a chloroformate compound. It may be a method in which a branching agent is added at the time of reaction. The proportion of the carbonate structural unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, of the total amount of carbonate structural units constituting the copolymer resin. Particularly preferably, it is 0.05 to 1.0 mol%. The branched structure amount can be calculated by ¹ H-NMR measurement.

The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but usually, it can be suitably carried out at normal pressure or about the autogenous pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, it is desirable to be cooled with water or ice because it generates heat during the polymerization. Although the reaction time varies depending on other conditions such as the reaction temperature, it can not be generally specified, but it is usually performed in 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of viscosity [η _SP / c]. The resulting reaction product (crude product) can be subjected to various post treatments such as known separation and purification methods, and recovered as a polycarbonate-polydiorganosiloxane copolymer resin of desired purity (purification degree).

  The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and 16,000 to A range of 21,000 is even more preferred, and a range of 16,000 to 20,000 is most preferred. If the molecular weight exceeds 25,000, the melt viscosity may be too high and formability may be poor, and if the molecular weight is less than 13,000, mechanical strength may be a problem.

In addition, calculation of the viscosity average molecular weight of polycarbonate polydiorganosiloxane copolymer resin used as B component of this invention is performed in the following way. First, the specific viscosity (η _SP ) calculated by the following formula is determined using a Ostwald viscometer from a solution of 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin dissolved in 100 ml of methylene chloride at 20 ° C.
Specific viscosity (η _SP ) = (t−t ⁰ ) / t ⁰
[T ⁰ is the second drop of methylene chloride, t is the second drop of the sample solution]
The viscosity average molecular weight Mv is calculated by the following formula from the determined specific viscosity (( _SP ).
η _SP /c=[η]+0.45×[η] ^{2 c} (where []] is the limiting viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  The content of the polydiorganosiloxane block represented by the following general formula [4] contained in the above general formula [3] contained in the component B is 1.0 based on the total weight of the polycarbonate resin composition of the present invention It is preferable that it is -10.0 wt%, more preferably 1.0-8.0 wt%, still more preferably 1.0-5.0 wt%, and most preferably 1.0-3.0 wt%. . If this proportion is less than 1.0% by weight, the low-temperature impact resistance after coating of molded articles is not sufficient, and if it exceeds 10.0% by weight, problems may occur in heat resistance and surface appearance, which is not preferable.

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms Or p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 or more and 150 or less.

  The content of the component B is adjusted so that the content of the polydiorganosiloxane component contained in the component B falls within the above-mentioned preferable range, but preferably 1 to 90 parts by weight in 100 parts by weight of the resin component, 80 parts by weight is more preferable, 5 to 50 parts by weight is further preferable, 5 to 30 parts by weight is particularly preferable, and 10 to 30 parts by weight is most preferable. If the B component is less than 1 part by weight, the low-temperature impact resistance after coating of the molded product is not sufficient, and if it exceeds 90 parts by weight, problems may occur in heat resistance and surface appearance, which is not preferable.

(Component C: polyolefin resin)
The polyolefin resin of component C in the present invention is known per se, for example, polyethylene, polypropylene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, ethylene- Acrylic acid copolymer, ethylene-carbon monoxide-ethyl acrylate copolymer, olefin copolymer of ethylene and / or α-olefin having 3 or more carbon atoms and unsaturated carboxylic acid ester, ethylene-propylene copolymer And ethylene-glycidyl (meth) acrylate copolymer, propylene-vinyl acetate copolymer, and 1-alkene polymer.

  Among the olefin polymers of component C, among them, polyethylene, polypropylene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer A combined use, an olefin-based copolymer of ethylene and / or an α-olefin having 3 or more carbon atoms and an unsaturated carboxylic acid ester, and a 1-alkene polymer can be preferably used. These polyolefins and their copolymers are available by commercial routes. These polyolefin resins may be modified polyolefin resins having functional groups such as carboxylic acid groups, acid anhydride groups and epoxy groups.

  In component C, it is particularly preferable to use polyethylene. Examples of polyethylene in the present invention include high density polyethylene, low density polyethylene, linear low density polyethylene and the like, and the production method is not particularly limited. For example, Ziegler-based catalysts are also used for linear low density polyethylene, It is possible to use various currently known catalysts such as metallocene based catalysts. Further, the amount of the catalyst contained in the polyethylene and the amount of unreacted unsaturated bond are not limited. Furthermore, polyethylene which has been prepared once may be reduced in molecular weight by thermal decomposition or the like. The viscosity average molecular weight of polyethylene is preferably 1,000 to 1,000,000, and particularly preferably 3,000 to 300,000. As this polyethylene, commercially available products include, for example, Hy-Zex 2100 JP, 3300 F (all trade names of Mitsui Chemical Co., Ltd.), GML 2420 (trade names of Nippon Unica Co., Ltd.), and the like.

  The content of the component C is 0.1 to 5 parts by weight, preferably 0.3 to 5 parts by weight, and more preferably 0.3 to 3.5 parts by weight with respect to 100 parts by weight of the resin component. If the amount is less than 0.1 parts by weight, the effect of improving the chemical resistance and the low temperature impact resistance can not be observed. If the amount is more than 5 parts by weight, the appearance may be deteriorated.

(Component D: acrylic elastic polymer)
The acrylic elastic polymer of component D in the present invention is preferably a rubbery polymer having a glass transition temperature of 0 ° C. or less, more preferably −20 ° C. or less, and a monomer component copolymerizable therewith. The copolymer is a copolymer, which contains an acrylic component in either of a rubber elastic body and a monomer. The acrylic elastic polymer used in the present invention is a core / shell type acrylic elastic polymer substantially free of a styrene component. As a result of intensive investigations by the inventors, in the polycarbonate resin composition using an acrylic elastic polymer containing a styrene component, the low temperature impact characteristics and chemical resistance of the styrene component itself are affected, and the required low temperature impact characteristics and It has been found that chemical resistance can not be achieved. Thus, methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), acrylonitrile-styrene-acrylic rubber copolymer (ASA), methyl methacrylate-acrylic rubber An acrylic elastic polymer containing a styrene component such as a styrene copolymer (MAS) can not be used for the polycarbonate resin composition of the present invention.

  Specific examples of the rubbery polymer used in the present invention include polyalkyl acrylates such as polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), and butyl acrylate / 2-ethylhexyl acrylate copolymer. Rubber; silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN type composite rubber comprising polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene-α-olefin rubber (ethylene-propylene rubber, ethylene -Butene rubber, ethylene-octene rubber and the like), ethylene-acrylic rubber, fluororubber and the like. Two or more of these may be used in combination. Among these, any of the group selected from the group of IPN type composite rubbers consisting of polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber and polyalkyl acrylate rubber from the viewpoint of chemical resistance in addition to impact resistance. One is preferred.

  Specific examples of monomer components copolymerizable with the rubbery polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, etc. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methyl maleimide, N-phenyl maleimide, etc .; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, itaconic acid and the like Anhydrides (for example, maleic anhydride etc.) etc. are mentioned. Two or more of these monomer components may be used in combination. Among these, from the viewpoint of impact resistance, preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds and (meth) acrylic acid compounds And more preferably (meth) acrylic acid ester compounds. Specific examples of (meth) acrylic acid ester compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate and the like Be

  As the acrylic elastic polymer of the present invention, a core-shell type graft copolymer type is used from the viewpoint of impact resistance. In this case, the core layer is at least one rubber component selected from the group consisting of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, and IPN (interpenetrating polymer network) type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber. Preferably, the shell layer is formed of (meth) acrylic acid ester.

Preferred specific examples of the above core-shell type graft copolymer include methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate- (acrylic silicone IPN rubber) A copolymer etc. are mentioned. Two or more of these may be used in combination.
Moreover, as a product of said core-shell type graft copolymer, EXL series, such as "Paraloid EXL2315" by "Rome and hearth Japan", "EXL2602,""EXL2603", etc. are mention | raise | lifted, for example.

The content of the component D is 1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 9 parts by weight, and most preferably 2 to 6 parts by weight with respect to 100 parts by weight of the resin component. If it is less than 1 part by weight, no improvement in low temperature impact properties is observed, and if it exceeds 15 parts by weight, in addition to the reduction in mechanical strength such as heat resistance and low temperature impact properties, the chemical resistance significantly decreases and appearance It is not preferable because it causes a decrease.
The rubber content of the acrylic elastic polymer is preferably 60% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more. If it is less than 60% by weight, improvement in low temperature impact properties may not be observed, which is not preferable.

(Other additives)
In order to improve the flame retardancy, light diffusion property, antioxidant property, light stability (ultraviolet light stability), stabilizer, fluorescent whitening property, mold releasability and mold corrosion of the resin composition of the present invention, The additives used for the improvement of are advantageously used. Hereinafter, these additives will be specifically described.

(I) Flame Retardant The resin composition of the present invention may contain various compounds known as flame retardants of polycarbonate resins. Although the compounding of such compounds brings about the improvement of the flame retardance, other than that, based on the properties of each compound, for example, the improvement of the antistatic property, the flowability, the rigidity and the thermal stability etc. are brought about. Such flame retardants include (i) organic metal salt based flame retardants (eg, organic sulfonic acid alkali (earth) metal salts, organic borate metal salt based flame retardants, organic stannate metal salt based flame retardants, etc.), ii) Silicone-based flame retardants comprising organophosphorus flame retardants (eg, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, etc.), (iii) silicone compounds And (iv) fibrillated PTFE, and among them, organic metal salt flame retardants and organophosphorus flame retardants are preferable.

(I) Organic Metal Salt-Based Flame Retardant The organic metal salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50, preferably 1 to 40 carbon atoms, preferably an alkali (earth) metal salt of an organic sulfonic acid Is preferred. The organic sulfonic acid alkali (earth) metal salt includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10, preferably 2 to 8 carbon atoms and an alkali metal or alkaline earth metal. Included are metal salts of acids as well as metal salts of aromatic sulfonic acids of 7 to 50, preferably 7 to 40, carbon atoms with alkali metals or alkaline earth metals. The alkali metals constituting the metal salts include lithium, sodium, potassium, rubidium and cesium, and the alkaline earth metals include beryllium, magnesium, calcium, strontium and barium. More preferably, it is an alkali metal. Among such alkali metals, rubidium and cesium having larger ion radii are preferable when transparency is required at a higher level, while they are not versatile and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals of smaller ionic radius such as lithium and sodium may be disadvantageous in terms of flame retardancy. Although the alkali metal in the sulfonic acid alkali metal salt can be used properly in consideration of the above, the potassium salt of sulfonic acid having the excellent balance of characteristics is most preferable in any point. It is also possible to use such a potassium salt in combination with a sulfonic acid alkali metal salt comprising another alkali metal.

Specific examples of the perfluoroalkyl sulfonic acid alkali metal salt include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, and perfluoro Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, perfluorooctane sulfonate Cesium, cesium cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and still more preferably in the range of 1 to 8. Among these, potassium perfluorobutane sulfonate is particularly preferable. In the alkali metal (perfluoroalkyl sulfonic acid) alkali metal salt composed of an alkali metal, fluoride ion (F ⁻ ) is usually mixed. Since the presence of such fluoride ions can be a factor to reduce the flame retardancy, it is preferably reduced as much as possible. The proportion of such fluoride ions can be measured by ion chromatography. The content of the fluoride ion is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. In addition, it is preferable that the production efficiency be 0.2 ppm or more. The perfluoroalkylsulfonic acid alkali (earth) metal salt having a reduced amount of fluoride ion is contained in the raw material for producing the fluorine-containing organic metal salt, using a known production method. Method for reducing the amount of fluoride ion, method for removing hydrogen fluoride and the like obtained by the reaction by gas generated during reaction and heating, and purification method such as recrystallization and reprecipitation for manufacturing fluorine-containing organic metal salt And the like to reduce the amount of fluoride ion. In particular, since the organic metal salt flame retardant is relatively soluble in water, ion exchange water, particularly water having an electric resistance value of 18 MΩ · cm or more, ie, an electric conductivity of about 0.55 μS / cm or less, is used. And it is preferable to manufacture by the process of making it melt | dissolve and wash | clean at temperature higher than normal temperature, and then cooling and recrystallizing. Specific examples of the aromatic sulfonic acid alkali (earth) metal salt include, for example, disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly (2,6-dimethylphenylene oxide) polysulfonate polysodium Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid polycarbonate Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonic acid lithium, potassium benzenesulfonate sulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonate, potassium biphenyl-3,3'-disulfonate, sodium diphenyl sulfone-3-sulfonate, potassium diphenyl sulfone-3-sulfonate, diphenyl sulfone-3,3'-disulfonate dipotassium, diphenyl sulfone -3,4'-disulfonic acid dipotassium, α, α, α-trifluoroacetophenone 4-sodium sulfonate, benzophenone-3,3'-disulfonic acid dipotassium, thiophene-2 Formalin of disodium 5-disulfonate, thiophene-2,5-disulfonate dipotassium, thiophene-2,5-disulfonate calcium, sodium benzothiophene sulfonate, potassium diphenylsulfonate-4-sulfonate, sodium naphthalenesulfonate Examples thereof include condensates and formalin condensates of sodium anthracenesulfonate. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium salts are particularly preferred. Among these aromatic sulfonic acid alkali (earth) metal salts, potassium diphenyl sulfone-3-sulfonate and dipotassium diphenyl sulfone-3,3′-disulfonate are preferable, and particularly, mixtures thereof (the former and the latter) The weight ratio of 15/85 to 30/70) is preferred.

  As an organic metal salt other than a sulfonic acid alkali (earth) metal salt, an alkali (earth) metal salt of a sulfuric ester and an alkali (earth) metal salt of an aromatic sulfonamide are preferably exemplified. As alkali (earth) metal salts of sulfuric acid esters, mention may be made in particular of alkali (earth) metal salts of sulfuric acid esters of monohydric and / or polyhydric alcohols, such monohydric and / or polyhydric alcohols Examples of sulfuric acid esters include methyl sulfuric acid ester, ethyl sulfuric acid ester, lauryl sulfuric acid ester, hexadecyl sulfuric acid ester, sulfuric acid ester of polyoxyethylene alkylphenyl ether, mono-, di-, tri-, tetra-sulfuric acid ester of pentaerythritol, sulfuric acid of monoglyceride laurate And esters of sulfuric acid ester of palmitic acid monoglyceride and sulfuric acid ester of stearic acid monoglyceride. Preferred alkali (earth) metal salts of these sulfates include alkali (earth) metal salts of lauryl sulfate. Examples of alkali (earth) metal salts of aromatic sulfonamides include saccharin, N- (p-tolylsulfonyl) -p-toluenesulfoimide, N- (N'-benzylaminocarbonyl) sulfanylimide, and N- ( And alkali (earth) metal salts of (phenylcarboxyl) sulfanylimide and the like. The content of the organic metal salt-based flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, and still more preferably 0.01 to 0 based on 100 parts by weight of the resin component. 0.3 parts by weight, particularly preferably 0.03 to 0.15 parts by weight.

(Ii) Organophosphorus Flame Retardant As the organophosphorus flame retardant, an aryl phosphate compound is suitable. Such phosphate compounds are generally excellent in hue. In addition, since the phosphate compound has a plasticizing effect, it is advantageous in that molding processability can be enhanced. As such phosphate compounds, various phosphate compounds conventionally known as flame retardants can be used. The compounding amount of the organophosphorus flame retardant is preferably 0.01 to 20 parts by weight, more preferably 2 to 10 parts by weight, and still more preferably 2 to 7 parts by weight with respect to 100 parts by weight of the resin component.

(Iii) Silicone Flame Retardant The silicone compound used as a silicone flame retardant improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants of aromatic polycarbonate resin can be used. A silicone compound which imparts a flame retardant effect to a polycarbonate resin by forming a structure by bonding itself or at the time of combustion with a component derived from the resin, or by a reduction reaction at the time of forming the structure. It is considered. Therefore, it is preferable to contain a group having high activity in such reaction, and more specifically, to contain a predetermined amount of at least one group selected from an alkoxy group and hydrogen (that is, Si-H group). preferable. The content ratio of such groups (alkoxy group, Si-H group) is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and still more preferably 0.15 to 0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by the alkali decomposition method by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group. Generally, the structure of the silicone compound is constituted by arbitrarily combining the four types of siloxane units shown below. That is, M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ CHCH) SiO _{1 /} , Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ CHCH) SiO _1/2 , D units: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ CHCH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. 2 Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ CHCH) SiO _3/2 , (C ₆ H ₅ ) trifunctional siloxane units SiO _3/2, etc., Q unit: 4 represented by SiO ₂ It is a functional siloxane units. Specific examples of the structure of the silicone compound used for the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq as the explicit formulas. Among these, the preferred structures of the silicone compounds are MmDn, MmTp, MmDnTp and MmDnQq, and more preferred structures are MmDn or MmDnTp.

  Here, the coefficients m, n, p and q in the above-mentioned property formula are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each property formula is the average degree of polymerization of the silicone compound. . The average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The more preferable range is, the more excellent in the flame retardancy. Further, as described later, in the case of a silicone compound containing a predetermined amount of an aromatic group, it is also excellent in transparency and hue. As a result, good reflected light is obtained. When one of m, n, p and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms to be bonded or organic residues. .

The silicone compound may be linear or branched. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. As such organic residue, specifically, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, a cycloalkyl group such as cyclohexyl group, an aryl group such as phenyl group, And aralkyl groups such as tolyl group. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl and propyl is particularly preferable. Furthermore, it is preferable that the silicone compound used as a silicone type flame retardant contains an aryl group. On the other hand, silane compounds and siloxane compounds as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone flame retardants in their preferred embodiments in that the preferred effect is obtained if they do not contain an aryl group. . The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group, and examples of such a reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl. Groups, mercapto groups, and methacryloxy groups are exemplified.
The compounding amount of the silicone-based flame retardant is preferably 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and still more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

(Iv) A fibril-forming polytetrafluoroethylene (fibrillated PTFE)
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, ie, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. The fibrillated PTFE has an extremely high molecular weight, and exhibits a tendency to bond the PTFEs to become fibrous by an external action such as shear force. The number average molecular weight is in the range of 1.5 million to several tens of millions. The lower limit is more preferably 3,000,000. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE of component B has a melt viscosity at 380 ° C. in the range of 10 ⁷ to 10 ¹³ poise, preferably 10 ⁸ to 10 ¹² poise, as measured by the method described in the publication. . Such PTFE may be used in the form of an aqueous dispersion in addition to the solid form. Such fibrillated PTFE can also be used in the form of a mixture of PTFE with other resins in order to improve the dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in JP-A-6-145520, one having a structure in which such fibrillated PTFE is used as a core and a low molecular weight polytetrafluoroethylene is used as a shell is also preferably used. As commercially available products of such fibrillated PTFE, for example, Teflon (registered trademark) 6J of Mitsui-Dupont Fluorochemicals Co., Ltd., Polyflon MPA FA 500 of Daikin Chemical Industry Co., Ltd., F-201L and the like can be mentioned. As fibrillated PTFE in a mixed form, (1) a method of mixing an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer and coprecipitating to obtain a co-agglomerated mixture (JP-A-60-258263) (2) Method of mixing an aqueous dispersion of fibrillated PTFE with dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957) (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (Japanese Patent Application Laid-Open No. 06-220210, Japanese Patent Application Laid-open No. Methods described in, for example, JP-B 08-188653), (4) A method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of fibrillated PTFE JP-A-9-95583) and (5) after uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing a vinyl monomer in the mixed dispersion. Then, those obtained by a method of obtaining a mixture (a method described in JP-A-11-29679 or the like) can be used. As commercial products of fibrillated PTFE of these mixed forms, metabrene represented by “Metabrene A3000” (trade name) “Metabrene A3700” (trade name) of Mitsubishi Rayon Co., Ltd. and “Metabrene A3800” (trade name) Examples include A series, SN3300B7 (trade name) of Shine Polymer, and "BLENDEX B 449" (trade name) manufactured by GE Specialty Chemicals.

The proportion of fibrillated PTFE in the mixed form is preferably 1% by weight to 95% by weight, more preferably 10% by weight to 90% by weight, in 100% by weight of the mixture. % By weight to 80% by weight is most preferred.
If the proportion of fibrillated PTFE in the mixed form is in such a range, good dispersibility of the fibrillated PTFE can be achieved. The compounding amount of fibrillated PTFE is preferably 0.001 to 0.2 parts by weight, more preferably 0.01 to 0.2 parts by weight, and 0.01 to 0. 100 parts by weight of the resin component. 18 parts by weight is more preferred. In addition, the weight part shown here shows the weight of the whole mixture, when polytetrafluoroethylene is a mixing form (mixture).

(II) Thermal Stabilizer Various known stabilizers can be blended into the polycarbonate resin composition of the present invention.
As the stabilizer, phosphorus stabilizers, hindered phenol antioxidants, ultraviolet light absorbers, light stabilizers and the like can be mentioned.

(I) Phosphorus-Based Stabilizer In the resin composition of the present invention, it is preferable that a phosphorus-based stabilizer be blended to the extent that the hydrolyzability is not promoted. Such phosphorus stabilizers improve the thermal stability at the time of production or molding, and improve the mechanical properties, the color and the molding stability. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphines. Specifically, as phosphite compounds, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, Tris (2,6-di-tert-butylphenyl) phosphite, Distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphos Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like can be mentioned. Furthermore, as another phosphite compound, one having a cyclic structure by reacting with a dihydric phenol can be used. For example, 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2'-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2'-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite And 2,2'-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and the like. As a phosphate compound, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monooroxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Diisopropyl phosphate and the like can be mentioned, preferably triphenyl phosphate and trimethyl phosphate.

  As a phosphonite compound, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylene di- Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylene diphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-diphenyl) tert-Butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, etc., tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, and tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenyl phosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more of the above-mentioned alkyl groups are substituted, which is preferable. As the phosphonate compound, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. Examples of tertiary phosphines include triethyl phosphine, tripropyl phosphine, tributyl phosphine, trioctyl phosphine, triamyl phosphine, dimethylphenyl phosphine, dibutylphenyl phosphine, diphenylmethyl phosphine, diphenyl octyl phosphine, triphenyl phosphine, tri-p-tolyl. Phosphine, trinaphthyl phosphine, diphenylbenzyl phosphine and the like are exemplified. Particularly preferred tertiary phosphines are triphenyl phosphines. The above-mentioned phosphorus stabilizers can be used alone or in combination of two or more. It is preferable that the alkyl phosphate compound represented by the trimethyl phosphate is mix | blended among the said phosphorus stabilizers. In addition, the combined use of such an alkyl phosphate compound and a phosphite compound and / or a phosphonite compound is also a preferred embodiment.

(Ii) Hindered phenolic stabilizer The resin composition of the present invention may further contain a hindered phenolic stabilizer. Such a combination exerts, for example, an effect of suppressing hue deterioration at the time of molding processing and deterioration of the hue in long-term use. Examples of hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4'-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene bis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert) -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-Methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl) -6-tert-Butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-Butylanilino) -1,3,5-triazine, N, N′-hexamethylene bis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, and tetrakis [methylene-3- (3 ′, 5′-di-tert) -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The above hindered phenolic stabilizers can be used alone or in combination of two or more. The compounding amount of the phosphorus stabilizer and the hindered phenol stabilizer is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, further preferably 100 parts by weight of the resin component. Is 0.005 to 0.3 parts by weight.

(Iii) Heat Stabilizers Other Than the Above Heat stabilizers other than the above-mentioned phosphorus stabilizers and hindered phenol stabilizers can be blended into the resin composition of the present invention. As such other heat stabilizers, for example, lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene are suitably exemplified. Be done. The details of such stabilizers are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Furthermore, stabilizers obtained by mixing the compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the company is preferably exemplified. The amount of the lactone stabilizer blended is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the resin component. Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. The compounding amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the resin component. An epoxy compound can be blended with the resin composition of the present invention as required. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically, all epoxy functional groups can be applied. Specific examples of preferred epoxy compounds are 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-2, 4-bis (hydroxymethyl) -1-butanol. Examples thereof include (2-oxiranyl) cyclotexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The addition amount of such an epoxy compound is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and still more preferably 0.005 to 100 parts by weight of the resin component. It is 0.1 parts by weight.

(III) Releasing Agent The polycarbonate resin composition of the present invention further comprises a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound It is also possible to blend known release agents such as fluorine oil represented by fluoroalkyl ether, paraffin wax and beeswax. The polycarbonate resin composition of the present invention has good flowability, so that pressure propagation is good, and a molded article with uniform strain is obtained. On the other hand, in the case of a molded article having a complicated shape in which the mold release resistance is increased, there is a possibility that the molded article may be deformed at the time of mold release. The blending of the above specific components solves this problem without impairing the properties of the polycarbonate resin composition. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having two or more valences. The carbon number of the alcohol is preferably 3 to 32, more preferably 5 to 30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferred in that all the esters (full esters) are excellent in thermal stability at high temperatures. The acid value of the fatty acid ester of the present invention is preferably 20 or less (can be substantially 0). Moreover, as for the hydroxyl value of fatty acid ester, the range of 0.1-30 is more preferable. Furthermore, the iodine value of the fatty acid ester is preferably 10 or less (can be substantially 0). These properties can be determined by the method defined in JIS K 0070. As polyolefin-based waxes, ethylene homopolymers, homopolymers or copolymers of α-olefins of 3 to 60 carbon atoms, or ethylene and 3 to 3 carbon atoms, having a molecular weight of 1,000 to 10,000 Examples are copolymers of 60 with an alpha-olefin. The molecular weight is a number average molecular weight measured in terms of standard polystyrene by GPC (gel permeation chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, still more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferable specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Preferred polyolefin-based waxes are ethylene homopolymers or copolymers of ethylene and α-olefins of 3 to 60 carbon atoms. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably at most 20 mol%, more preferably at most 10 mol%. What is marketed as what is called polyethylene wax is utilized suitably.
The content of the above releasing agent is 0.005 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 3 parts by weight, still more preferably 100 parts by weight of the resin component. 0
. It is 01 to 1 part by weight.

(IV) Ultraviolet Absorber In the resin composition of the present invention, an ultraviolet absorber may be blended for the purpose of imparting light resistance. Specific examples of UV absorbers include benzophenone series compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4 4,4'-Dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy- 4-n-dodecyloxy bensophenone, and 2- Hydroxy-4-methoxy-2'-carboxybenzophenone and the like are exemplified. Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole as benzotriazole-based compounds. , 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'- Methylene bis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole , 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-) tert-Butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and Copolymerizable with 2- (2'-hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and the monomer 2-hydroxy such as a copolymer with a vinyl monomer or a copolymer of 2- (2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer Examples thereof include polymers having a phenyl-2H-benzotriazole skeleton. The UV absorber is specifically a hydroxyphenyl triazine type, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,4, 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol , 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) And 5-butyloxyphenol etc. are illustrated. Furthermore, the phenyl group of the above exemplified compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl The compound which became a phenyl group is illustrated. The UV absorber is specifically a cyclic imino ester type, for example, 2,2'-p-phenylenebis (3,1-benzoxazin-4-one), 2,2'-m-phenylenebis (3,1) -Benzoxazin-4-one), and 2,2'-p, p'-diphenylene bis (3,1-benzoxazin-4-one) and the like. Further, as the ultraviolet absorber, specifically, in the case of cyanoacrylate type, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane, and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene. Furthermore, the above-mentioned ultraviolet absorber takes such a structure as a monomer compound capable of radical polymerization, and thus the amount of such an ultraviolet-absorbing monomer and / or a light-stable monomer and a single amount of alkyl (meth) acrylate etc. It may be a polymer type UV absorber copolymerized with the body. As the UV absorbing monomer, compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in an ester substituent of (meth) acrylic acid ester are suitably exemplified. Ru. Among the above, benzotriazole-based and hydroxyphenyltriazine-based ones are preferable in view of ultraviolet light absorbing ability, and cyclic imino ester-based ones and cyanoacrylate-based ones are preferable in view of heat resistance and hue. Specifically, for example, Chemi-Pur Chemical Co., Ltd. “Chemisorb 79” and the like can be mentioned. The UV absorbers may be used alone or in combination of two or more. The compounding amount of the ultraviolet light absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 parts by weight, particularly preferably 100 parts by weight of the resin component. Is 0.05 to 0.5 parts by weight.

(V) Dyeing and Pigmenting The polycarbonate resin composition of the present invention can further provide a molded article which contains various dyes and pigments and expresses various design properties. Dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Dioxazine dyes, isoindolinone dyes, phthalocyanine dyes and the like can be mentioned. Furthermore, the polycarbonate resin composition of the present invention can also be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is preferred as the metallic pigment. Further, by blending a fluorescent whitening agent and a fluorescent dye that emits light other than that, it is possible to impart a better design effect utilizing the luminescent color.

(VI) Fluorescent Brightening Agent In the resin composition of the present invention, the fluorescent brightening agent is not particularly limited as long as it is used to improve the color tone of a resin or the like to white or bluish white. An imidazole type, a benzoxazole type, a naphthalimide type, a rhodamine type, a coumarin type, an oxazine type compound etc. are mentioned. Specific examples thereof include CI Fluorescent Brightener 219: 1, EASTOBRITE OB-1 manufactured by Eastman Chemical Co., and “Hakkol PSR” manufactured by HAKKOR CHEMICAL CO., LTD. Here, the fluorescent whitening agent has the function of absorbing the energy of the ultraviolet portion of light and emitting the energy to the visible portion. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, and more preferably 0.001 to 0.05 parts by weight with respect to 100 parts by weight of the resin component. Even if it exceeds 0.1 parts by weight, the effect of improving the color tone of the composition is small.

(VII) Compound having heat ray absorbing ability The polycarbonate resin composition of the present invention can contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, ATO, ITO, iridium oxide and ruthenium oxide, metal oxide-based near-infrared absorbers such as immonium oxide, metal borides such as lanthanum boride, cerium boride and tungsten boride Preferred examples thereof include various metal compounds excellent in near-infrared absorptivity, such as tungsten oxide-based near-infrared absorbers, and carbon fillers. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene and the like, with preference given to carbon black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and more preferably 0.001 to 0. 100 parts by weight of the resin component. 07 parts by weight is more preferred. The content of the metal oxide near infrared absorber, the metal boride near infrared absorber and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the polycarbonate resin composition of the present invention. The range of 5 to 100 ppm is more preferable.

(VIII) Light Diffusing Agent A light diffusing agent can be blended into the polycarbonate resin composition of the present invention to impart a light diffusing effect. Examples of such light diffusing agents include polymer particles, inorganic particles having a low refractive index such as calcium carbonate, and composites of these. Such polymer particles are particles already known as a light diffusing agent for polycarbonate resin. More preferably, acrylic crosslinked particles having a particle diameter of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane are exemplified. Examples of the shape of the light diffusing agent include a sphere, a disc, a pillar, and an amorphous. Such spheres need not be perfect spheres, but include those that are deformed, and such pillars include cubes. The preferred light diffusing agent is spherical, and its particle size is preferably as uniform as possible. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight based on 100 parts by weight of the resin component. In addition, 2 or more types of light diffusing agents can be used together.

(IX) White pigment for high light reflection The polycarbonate resin composition of the present invention can be blended with a white pigment for high light reflection to give a light reflection effect. As such a white pigment, titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferable. The content of the white light reflecting pigment is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight, based on 100 parts by weight of the resin component. Incidentally, two or more kinds of white pigments for high light reflection can be used in combination.

(X) Antistatic Agent The polycarbonate resin composition of the present invention may be required to have antistatic properties, and in such a case, it is preferable to include an antistatic agent. Such antistatic agents include, for example, (1) arylsulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkylsulfonic acid phosphonium salts, and phosphonium tetrafluoroborate salts And boric acid phosphonium salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3 based on a total of 100 parts by weight of the components A, B and C. The amount is 5 parts by weight, more preferably 1.5 to 3 parts by weight. Examples of the antistatic agent include (2) lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonic acid alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the organic sulfonic acid alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably 0 based on 100 parts by weight of the resin component. .005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium and rubidium are preferred.

  Examples of the antistatic agent include (3) ammonium ammonium sulfonates and organic sulfonic acid ammonium salts such as ammonium arylsulfonic acid salts. The appropriate amount of the ammonium salt is 0.05 parts by weight or less based on 100 parts by weight of the components A, B and C in total. Examples of the antistatic agent include polymers containing a poly (oxyalkylene) glycol component such as (4) polyether ester amide as its component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of the resin component.

(XI) Filler In the polycarbonate resin composition of the present invention, various fillers known as reinforcing fillers can be blended. As such a filler, various fibrous fillers, plate fillers and granular fillers can be used. Here, the fibrous filler is in the form of fiber (in the form of a rod, needle, or the axis of which extends in a plurality of directions), and the sheet filler is in the form of a plate (surface And the like, and the plate having a curve). The particulate filler is a filler of other shapes including irregular shapes.
The fibrous or plate-like shape is often apparent from the observation of the shape of the filler, but as a difference from, for example, so-called indeterminate form, those having an aspect ratio of 3 or more can be said to be fibrous or plate-like.

  Examples of the plate-like filler include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and plate-like fillers obtained by surface-coating such fillers with different materials such as metals and metal oxides. Materials are preferably exemplified. The particle size is preferably in the range of 0.1 to 300 μm. This particle size refers to the median diameter (D50) of the particle size distribution measured by X-ray transmission method which is one of the liquid phase sedimentation methods in the region up to about 10 μm, and the laser diffraction in the region of 10 to 50 μm The value according to the median diameter (D50) of the particle size distribution measured by the scattering method, which is a value according to vibration sieving in the region of 50 to 300 μm. The particle size is the particle size in the resin composition. The plate-like filler may be surface-treated with various silane based, titanate based, aluminate based, and zirconate based coupling agents, and also olefin based resins, styrene based resins, acrylic based resins, polyester based resins It may be a granulated material which is subjected to a convergence treatment or compression treatment with various resins such as an epoxy resin and a urethane resin or a higher fatty acid ester.

  The fibrous filler preferably has a fiber diameter in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is preferably 13 μm, more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm. The fiber diameter herein refers to the number average fiber diameter. The number average fiber diameter may be determined by dissolving the molded product in a solvent or scanning the residue collected after the resin is decomposed with the basic compound, and the ashing residue collected after ashing in a crucible. It is a value calculated from an image observed by an electron microscope. As such a fibrous filler, for example, glass fiber, flat cross section glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whisker, boron whisker Fibrous inorganic fillers such as aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, sonotolite, palygorskite (attapulgite), and sepiolite, heat-resistant organic fibers such as aramid fibers, polyimide fibers and polybenzthiazole fibers Fibrous heat-resistant organic fillers represented by the above, and fibrous fillers coated with different fillers such as metals and metal oxides on these fillers It is exemplified. As a filler which carried out the surface coating of the dissimilar material, a metal coating glass fiber, a metal coating glass flake, a titanium oxide coating glass flake, a metal coating carbon fiber etc. are illustrated, for example. There is no particular limitation on the method of surface coating of different materials, and various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum evaporation method, ion plating method, CVD method (for example) For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method etc. can be mentioned. Here, the fibrous filler refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is the value in the resin composition. Further, the flat cross section glass fiber means that the average value of the major axis of the fiber cross section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm and the average value of the major axis / minor axis ratio (major axis / minor axis) is 1 0.5 to 8, preferably 2 to 6, more preferably 2.5 to 5; The fibrous filler may also be surface-treated with various coupling agents in the same manner as the above-mentioned plate-like filler, may be converged with various resins, etc., and may be granulated by compression treatment. The content of the filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, still more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less based on 100 parts by weight of the resin component.

(XII) Other Additives In the polycarbonate resin composition of the present invention, thermoplastic resins other than the components A to D, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents And photochromic agents can be blended.
As thermoplastic resins other than the components A to D, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexane dimethanol copolymerized polyethylene terephthalate resin (so-called PETG resin), polyethylene Naphthalate resin, polybutylene naphthalate resin, and polyethylene terephthalate-adipate copolymer, etc., polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluorine resin (for example, polyfluorinated resin) (Represented by vinylidene resin). The content of the other thermoplastic resin is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on a total of 100 parts by weight of the components A to D.

  The resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. In order to produce such pellets, the various flame retardants, reinforcing fillers and additives described above can also be blended. The resin composition of the present invention can usually be produced by injection molding the pellets produced as described above to produce various products. Furthermore, it is also possible to make the resin melt-kneaded by an extruder directly into a sheet, a film, a profiled extrusion molded article, a direct blow molded article, and an injection molded article without passing through pellets. In such injection molding, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection of a supercritical fluid), insert molding, as well as ordinary molding methods according to the purpose as appropriate. Molded articles can be obtained using injection molding methods such as in-mold coating molding, insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either cold runner method or hot runner method can be selected. The resin composition of the present invention can also be used in the form of various profile extrusions, sheets, films and the like by extrusion molding. Further, an inflation method, a calendar method, a casting method and the like can be used to form a sheet and a film. It is also possible to form a heat-shrinkable tube by subjecting it to a specific drawing operation. Moreover, it is also possible to use the resin composition of the present invention as a molded article by rotational molding, blow molding or the like.

<Production of Resin Composition>
Any method is adopted to produce the resin composition of the present invention. For example, after thoroughly mixing Component A, Component B, Component C, Component D and optionally other components using a V-blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Accordingly, granulation is carried out using an extrusion granulator, a briquetting machine or the like, followed by melt-kneading using a melt kneader represented by a vent type twin-screw router, and pelletization using equipment such as a pelletizer.

<Manufacturing of molded articles>
The resin composition of the present invention can usually be molded by injection molding such pellets. In such injection molding, it is also possible to manufacture by a hot runner which enables runnerless as well as a usual cold runner type molding method. Also in injection molding, not only ordinary molding methods but also gas assisted injection molding, injection compression molding, super high speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (super It is possible to use molding methods such as rapid heating / cooling mold forming, insulation mold forming and in-mold remelt forming, and combinations thereof, and the like, including those utilizing critical fluid. Furthermore, it is possible to perform various surface treatments on a molded article formed from the resin composition. As surface treatment, decorative coating, hard coat, water repellent / oil repellent coat, hydrophilic coat, ultraviolet ray absorbing coat, infrared ray absorbing coat, electromagnetic wave absorbing coat, heat generation coat, antistatic coat, antistatic coat, conductive coat, and meta Various surface treatments such as rising (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed. In particular, a transparent sheet coated with a transparent conductive layer is preferred.

  Molded articles made of the polycarbonate resin composition of the present invention are various electronic / electrical device parts (particularly, mobile information terminal casings), camera parts, OA equipment parts, precision machine parts, machine parts, vehicle parts, other agricultural materials, transportation It is useful for various uses such as containers, play equipment and sundries, and its industrial effects are outstanding.

  The form of the present invention which the present inventor considers to be the best is an aggregation of the preferred ranges of the above-mentioned respective requirements, and for example, representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

(I) Evaluation of Polycarbonate Resin Composition (i) Charpy Impact Strength, Low-Temperature Impact Properties Measured in accordance with ISO 179 (measurement conditions 23 ° C., -30 ° C.). The test pieces were molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) after drying the obtained various pellets at 120 ° C. for 5 hours .

(Ii) Chemical resistance Sumitomo Heavy Industries, Ltd. SG-150U molding machine, cylinder temperature 300 ° C, mold temperature 90 ° C, 150 mm long × 100 mm wide × 0.8 mm thick mobile information terminal simulated type It molded (with the back surface rib). The resulting molded product was spray-painted (Nippe Home Products Co., Ltd. Mini Hobby Spray), and impact resistance properties before and after painting were evaluated by a Dupont type drop-out impact test according to ISO 6272 (shooting tip : R = 4.5, pedestal: brass cylinder (outside diameter: 60 mm, inside diameter: 45 mm) Dupont impact strength G and impact strength retention ratio R after coating were determined by the following equation. The drop position of the hanging was near the rib on the back side of the molded product, and the maximum value of height without the crack of the surface, the crack of the rib, and the penetration of the hammer core was taken as the impact strength.
G (J) = M × h
(M: Weight of weight (kg), h: Height of dropping weight)
R (%) = [G1 / G2] × 100
(G1: Dupont impact strength after painting, G2: Dupont impact strength before painting)

(Iii) Heat resistance The mobile information terminal simulated molded article was allowed to stand for 120 hours in a dry heat environment at 120 ° C., and the molded article after the dry heat test was evaluated based on the following criteria.
:: no deformation of the molded product :: warped to the molded product ×: warped or deformed to the molded product

(Iv) Appearance of Molded Article The appearance of the mobile information terminal simulated molded article was visually observed and evaluated. The evaluation was conducted according to the following criteria.
○: Abnormality not observed ×: Abnormality such as peeling or gloss reduction

(V) Flowability The flow length was measured with an Archimedean spiral flow mold (flow passage thickness 1 mm, flow passage width 8 mm) using Sumitomo Heavy Industries, Ltd. SG-150U forming machine. The conditions were a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 98 MPa. The evaluation was conducted according to the following criteria.
○: Flow length is 200 mm or more ×: Flow length is less than 200 mm

[Examples 1 to 15 and Comparative Examples 1 to 9]
After mixing the components A to D and the various additives in respective blend amounts shown in Table 1 in a blender, they were melt-kneaded using a vented twin-screw extruder to obtain pellets. The various additives to be used were preliminarily mixed with a polycarbonate resin in advance with a concentration of 10 to 100 times that of the compounding amount as a standard, and then overall mixing was performed by a blender. The vent type twin-screw extruder manufactured by Japan Steel Works, Ltd .: TEX30α (complete meshing, co-rotation, double thread screw) was used. The extrusion conditions are: discharge amount 20 kg / h, screw rotation speed 150 rpm, vent vacuum 3 kPa, and extrusion temperature 270 ° C. from the first supply port to the second supply port and 290 ° C. from the second supply port to the die portion did.

The details of each component used are as follows.
(A component)
PC-1: polycarbonate resin powder having a viscosity average molecular weight of 19,800 obtained by the following production method [production method]
Charge 2340 parts of ion-exchanged water, 947 parts of 25% aqueous sodium hydroxide solution, and 0.7 parts of hydrosulfite into a reactor equipped with a thermometer, a stirrer and a reflux condenser, and stir 2,2-bis (4-hydroxyphenyl) under stirring Dissolve 710 parts of propane (sometimes referred to as "bisphenol A" hereinafter) (bisphenol A solution), add 2299 parts of methylene chloride and 112 parts of 48.5% aqueous sodium hydroxide solution, and then at 15 to 25 ° C. The phosgenation reaction was carried out by bubbling 354 parts of phosgene over about 90 minutes. After completion of phosgenation, 148 parts of a 11% strength p-tert-butylphenol solution in methylene chloride and 88 parts of a 48.5% aqueous solution of sodium hydroxide are added, the stirring is stopped, and the mixture is left to stand for 10 minutes and then stirred. After 5 minutes of emulsification, the mixture was treated with a homomixer (Tokushu Kika Kogyo Co., Ltd.) at a rotational speed of 1200 rpm and a bath number of 35 to obtain a high emulsification dope. The highly emulsified dope was reacted in a polymerization tank (with a stirrer) at a temperature of 35 ° C. for 3 hours under non-stirring conditions to complete the polymerization. After completion of the reaction, the organic phase is separated, diluted with methylene chloride and washed with water, then made acidic with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as ion exchanged water, it is put into a kneader covered with warm water. The methylene chloride was evaporated with stirring to give a polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulating dryer to obtain polycarbonate resin powder.

PC-2: Polycarbonate resin powder having a viscosity average molecular weight of 16,500 obtained by the following method [Manufacturing method]
A polycarbonate resin powder was obtained in the same manner as in the method for producing PC-1, except that the solution was changed to 193 parts of a methylene chloride solution of 11% concentration of p-tert-butylphenol.

PC-3: Polycarbonate resin powder having a viscosity average molecular weight of 12,300 obtained by the following method [Manufacturing method]
A polycarbonate resin powder was obtained in the same manner as in the method for producing PC-1, except that the solution was changed to 294 parts of a methylene chloride solution of 11% concentration p-tert-butylphenol.

PC-4: Polycarbonate resin powder having a viscosity average molecular weight of 23,200 obtained by the following method [Manufacturing method]
A polycarbonate resin powder was obtained in the same manner as in the method for producing PC-1, except that the solution was changed to 118 parts of a methylene chloride solution of 11% concentration p-tert-butylphenol.

PC-5: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as "biscresol fluorene") having a viscosity average molecular weight of 16,500 obtained by the following production method and bisphenol A Copolycarbonate resin powder having a molar ratio of 50:50.
[Production method]
23030 parts of ion-exchanged water and 3957 parts of 48.5% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer and a reflux condenser, and 3026 parts of biscresol fluorene were dissolved in 1826 parts of bisphenol A and 10 parts of hydrosulfite Thereafter, 17183 parts of methylene chloride were added, and 1900 parts of phosgene was blown for 60 minutes at 15 to 25 ° C. with stirring. After phosgene blowing, add a solution of 96 parts of p-tert-butylphenol in 1300 parts of methylene chloride and 660 parts of 48.5% aqueous sodium hydroxide solution to emulsify, then add 5.6 parts of triethylamine and add 28 to 28 The reaction was terminated by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride and washed with water, then made acidic with hydrochloric acid and washed with water. When the conductivity of the aqueous phase becomes almost the same as that of ion exchanged water, the methylene chloride phase is concentrated and dehydrated for polycarbonate A solution with a concentration of 20% was obtained. The polycarbonate obtained by removing the solvent from this solution had a molar ratio of biscresol fluorene to bisphenol A of 50:50.

(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin powder of viscosity average molecular weight 19,400 obtained by the following production method [Production method]
In a reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, 21591 parts of ion-exchanged water, 3674 parts of 48.5% aqueous sodium hydroxide solution, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) And after dissolving 7.6 parts of hydrosulfite, add 14565 parts of methylene chloride (14 moles per 1 mole of dihydroxy compound (I)) and take 60 minutes of 1900 parts of phosgene under stirring at 22 to 30 ° C. Blew in. Next, a solution of 1131 parts of a 48.5% aqueous sodium hydroxide solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride is added, and a polydiorganosiloxane compound represented by the following formula [8] with stirring A solution of 430 parts of an average repeating number p = about 37) in 1600 parts of methylene chloride is prepared, and the dihydroxyaryl-terminated polydiorganosiloxane (II) is 0.0008 mol per mol of dihydric phenol (I) The mixture was emulsified at a rate of / min and stirred vigorously again. While the reaction solution was at 26 ° C., 4.3 parts of triethylamine was added to the reaction solution and stirring was continued for 45 minutes at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride and washed with water, then made acidic with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase becomes almost the same as ion exchanged water, it is put into a kneader covered with warm water. The methylene chloride was evaporated while stirring to obtain a powder of polycarbonate-polydiorganosiloxane copolymer resin. After dehydration, drying was carried out at 120 ° C. for 12 hours using a hot air circulating dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content: 8.2%, average size of polydiorganosiloxane domain: 9 nm, viscosity average molecular weight: 19,400)

B-2: Polycarbonate-polydiorganosiloxane copolymer resin powder of viscosity average molecular weight 15,000 obtained by the following production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the method for producing B-1, except that p-tert-butylphenol was changed to 132 parts. (Polydiorganosiloxane component content: 8.2%, average size of polydiorganosiloxane domain: 9 nm, viscosity average molecular weight: 15,000)

B-3: Polycarbonate-polydiorganosiloxane copolymer resin powder of viscosity average molecular weight 19,300 obtained by the following production method [Production method]
A polycarbonate-polydiorganosiloxane copolymer resin powder is obtained in the same manner as in the method for producing B-1, except that 204 parts of the polydiorganosiloxane compound represented by the above formula [5] is used and the stirring time is 60 minutes. The (Polydiorganosiloxane component content: 4.1%, average size of polydiorganosiloxane domain: 8 nm, viscosity average molecular weight: 19,300)

B-4: Polycarbonate-polydiorganosiloxane copolymer resin powder of viscosity average molecular weight 19,200 obtained by the following production method [Production method]
A polycarbonate-polydiorganosiloxane copolymer resin powder was obtained in the same manner as in the production method of B-1 except that 204 parts of the polydiorganosiloxane compound having an average repeating number p of the above formula [5] of about 100 was used. . (Polydiorganosiloxane component content: 4.2%, average size of polydiorganosiloxane domains: 25 nm, viscosity average molecular weight: 19,200)

(C ingredient)
PE: Polyethylene resin (HIZEX 2100JP manufactured by Mitsui Chemicals, Inc.)
EA: ethylene-ethyl acrylate copolymer (Nippon Polyethylene Co., Ltd. product Rexpearl (trademark) A-4250)
(D component)
MB: polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (
Core-shell type graft copolymer (manufactured by Kaneka Corporation "M-711") (70% of butadiene rubber)
MBS-1: Butadiene-2-ethylhexyl acrylate copolymer reinforced with rubber-styrene-
Methyl methacrylate copolymer (HIBA15 manufactured by Toha Chemical Industry Co., Ltd.) (copolymer rubber amount 6)
0%)
MBS-2: methyl methacrylate butadiene styrene (MBS) copolymer (Mitsubishi Rayon Co., Ltd. Metabrene C 223 A) (80% rubber content)
(Other ingredients)
A: Tris (2,4-di-t-butylphenyl) phosphite) (Ciba Specialty Chemicals Co., Ltd. product)
CB: 30 parts by weight of carbon black (Mitsubishi Chemical Corporation carbon black MA-10
0), 3 parts by weight of white mineral oil (Crystol N35 from Exxon Mobil
2) 0.2 parts by weight of a montanic acid ester wax (Recolub WE-1 powder manufactured by Clariant Japan Co., Ltd.), and 66.8 parts by weight of a bisphenol A-type polycarbonate resin (CM-1000 manufactured by Teijin Chemicals Ltd.) Carbon black master pellet TiO2 manufactured by melt mixing 100 parts by weight of four components having a viscosity average molecular weight of 16,000) using a twin-screw extruder: titanium dioxide (made by Resino Color Industry Co., Ltd. White DCF-T -17007)

Claims (7)

(A) Polycarbonate resin (component A) and (B) Polycarbonate-polydiorganosiloxane copolymer comprising polycarbonate block represented by the following general formula [1] and polydiorganosiloxane block represented by the following general formula [3] (C) 0.1-5 parts by weight of a polyethylene resin (C component) and (D) a core-shell type with 100 parts by weight of a resin component comprising a resin (component B), and the rubber polymer is polybutadiene rubber Acrylic polymer containing no styrene component, which is a rubbery polymer selected from the group consisting of polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate) and butyl acrylate / 2-ethylhexyl acrylate copolymer Polycarbonate tree containing 1 to 15 parts by weight of component (D) A composition, based on the total weight of the polycarbonate resin composition, the content of the polydiorganosiloxane block represented by the following general formula (4) included in the following general formula [3] is 1.0 to 10 The polycarbonate resin composition which is .0 weight% .

[In the above general formula [1], R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group and a carboxyl group, and when there are plural groups, they may be the same or different And a and b each represent an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. .

(In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon number of 1 to 18 selected from the group consisting of an aryl group of 3 to 14 atoms and an aralkyl group of 7 to ²⁰ carbon atoms. Alkyl group, alkoxy group having 1 to 10 carbon atoms, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, alkenyl group having 2 to 10 carbon atoms, and 3 carbon atoms To 14 aryl groups, aryloxy groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, aralkyloxy groups having 7 to 20 carbon atoms, nitro groups, aldehyde groups, cyano groups, Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of groups, they may be the same or different, c is an integer of 1 to 10, d is an integer of 4 to 7)]

(In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms And R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; Is an integer of 1 to 4 respectively, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 to 37. X is a divalent aliphatic group having 2 to 8 carbon atoms. )

(In the above general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution of 6 to 12 carbon atoms Or p is a natural number, q is 0 or a natural number, and p + q is a natural number of 4 to 37 . The polycarbonate resin composition according to claim 1, wherein the component B is a polycarbonate-polydiorganosiloxane copolymer resin in which polydiorganosiloxane domains having an average size of 0.5 to 18 nm are present in a matrix of a polycarbonate polymer. . Aromatic polycarbonate resin (component A-1) obtained by reacting component (A-1) 9, 9-bis (4-hydroxy-3-methylphenyl) fluorene-containing dihydric phenol with carbonate precursor 3) The polycarbonate resin composition according to claim 1 or 2 , which is an aromatic polycarbonate resin comprising an aromatic polycarbonate resin (component A-2) other than the component (A-2) and the component A-1. The polycarbonate resin composition according to any one of claims 1 to 3 , wherein the viscosity average molecular weight of the component A is in the range of 13,000 to 25,000. An injection molded article formed from the polycarbonate resin composition according to any one of claims 1 to 4 . The injection molded article according to claim 5 , wherein the injection molded article is a portable information terminal exterior member. The injection molded article according to claim 5 , which is a portable information terminal exterior member formed by coating the injection molded article.