JP2015221850A - Polycarbonate resin composition and molded article containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having good low temperature shock resistance, chemical resistance and further flowability capable of sufficiently responding to thin wall molding.SOLUTION: There is provided a polycarbonate resin composition containing 100 pts.mass of a resin component consisting of (A) a polycarbonate resin (A Component) and (B) a polycarbonate-polydiorganosiloxane copolymer resin (B Component), 0.1 to 5 pts.wt. of (C) a polyolefin resin and 1 to 15 pts.wt. of (D) an acrylic elastic polymer that is a core-shell type and contains no styrene component (D Component).

Description

  The present invention relates to a polycarbonate resin composition having improved chemical resistance. More specifically, the present invention is excellent in fluidity and chemical resistance, comprising a polycarbonate resin, a polycarbonate-polydiorganosiloxane copolymer resin, a polyolefin resin, and a core-shell type acrylic elastic polymer containing no styrene component. In addition, the present invention relates to a polycarbonate resin composition with little decrease in mechanical strength before and after coating, and an injection-molded product 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 mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts 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 under various environments, particularly impact resistance, is required as compared with conventional stationary information terminals. In the case of an exterior material, it is almost always applied from the viewpoint of high designability and high appearance. Accordingly, as a resin for a portable information terminal casing, impact resistance in a painted state has been demanded, and further improvement in mechanical strength is demanded as compared with a conventional polycarbonate resin.

  Patent Document 1 reports an aromatic polycarbonate resin composition having improved low-temperature impact resistance properties comprising an aromatic polycarbonate resin, a polyolefin resin, and an acrylic elastic polymer. However, in such a polycarbonate resin composition, although mechanical strength is satisfactory, a great problem arises in chemical resistance. Patent Documents 2 and 3 report a polycarbonate resin composition specifying an acrylic elastic polymer among the above compositions. However, such a polycarbonate resin composition is insufficient for fluidity and chemical resistance.

  On the other hand, a polycarbonate-polydiorganosiloxane copolymer resin is known as a polycarbonate exhibiting good low-temperature impact resistance (for example, Patent Document 4). Further, Patent Document 5 reports a thermoplastic resin composition in which a polysiloxane domain having an average domain size of 20 to 45 nm or 20 to 40 nm is embedded in a polycarbonate polymer matrix. This report states that the low temperature impact resistance is good when the polysiloxane domain has a specific size. However, these polycarbonate-polydiorganosiloxane copolymer resins may cause poor coating, and the impact resistance after coating is not sufficient. In Patent Document 6, a polycarbonate resin composition in which a rubber-like elastic material is blended with a polycarbonate-polydiorganosiloxane copolymer resin is reported as a polycarbonate resin composition having further excellent impact resistance. Is not mentioned.

  As a polycarbonate composition having both impact resistance and organic solvent resistance, in Patent Document 7, it was graft-modified with an aromatic polycarbonate, a polycarbonate-polydiorganosiloxane copolymer resin, and an unsaturated dicarboxylic acid or an unsaturated dicarboxylic acid anhydride. A polycarbonate resin composition comprising a hydrogenated aliphatic diene-vinyl aromatic block copolymer has been reported. In this report, the impact resistance measured according to ASTM method D256 is evaluated for test pieces having a thickness of 1/4 inch and 1/8 inch. However, not only portable information terminals but also thin cases of electrical and electronic equipment casings have progressed, and there is no correlation between the strength of actual molded products and the impact resistance characteristics according to the standards, and further improvements are required. Patent Document 8 reports a polycarbonate resin composition comprising an aromatic polycarbonate resin, a polyolefin resin, and an acrylic elastic polymer. This report describes improvements in 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 casing made of a polycarbonate-polydiorganosiloxane copolymer resin having a specific siloxane chain length and other aromatic polycarbonates. However, further improvements in chemical resistance are necessary.

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

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

  As a result of intensive research aimed at achieving 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. In addition, the inventors have found that a polycarbonate resin composition having both low temperature impact resistance and chemical resistance sufficient for a portable electronic device casing can be obtained, and the present invention has been achieved. That is, according to the present invention, (1) (A) a polycarbonate resin (component A) and (B) 100 parts by weight of a resin component comprising a polycarbonate-polydiorganosiloxane copolymer resin (component B), Polycarbonate resin composition containing 0.1 to 5 parts by weight of resin (C component) and 1 to 15 parts by weight of (D) core-shell type acrylic elastic polymer (D component) not containing styrene component Is provided.

  One of the more preferred embodiments of the present invention is (2) a polycarbonate-polydisiloxane having a B component comprising a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]. The polycarbonate resin composition according to the above configuration (1), which is an organosiloxane copolymer resin.

[In General Formula [1], R ¹ and R ² are each independently 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. A and b are each 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 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, and 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 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, and R ⁹ and R ¹⁰ are each independently 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, and e and f Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms. .)

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

(In the general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, 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 (4) a polycarbonate-polydiorganosiloxane copolymer resin in which component B is a polydiorganosiloxane domain having an average size of 0.5 to 18 nm in a polycarbonate polymer matrix. It is a polycarbonate resin composition in any one of the said structure (1)-(3) characterized by these.
One of the more preferable embodiments of the present invention is the polycarbonate resin composition according to any one of the above constitutions (1) to (4), wherein (5) component C is polyethylene.
One of the more preferred embodiments of the present invention is (6) an acrylic elastic polymer in which component D 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 said structure (1)-(5) characterized by being.
One of the more preferable embodiments of the present invention is that (7) the component D is an acrylic elastic polymer characterized in that the rubber content is 60% by weight or more. The polycarbonate resin composition according to any one of the above.
One of the more preferable embodiments of the present invention is that (8) a dihydric phenol in which the component A contains (A-1) 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and a carbonate precursor. The above-mentioned constitution characterized by being a polycarbonate resin comprising an aromatic polycarbonate resin (A-2 component) other than the aromatic polycarbonate resin (A-1 component) obtained by reacting and (A-2) A-1 component (1) It is a polycarbonate resin composition in any one of (7).
One of the more preferable embodiments of the present invention is (9) any one of the above constitutions (1) to (8), wherein the viscosity average molecular weight of the component A is in the range of 13,000 to 25,000. It is a polycarbonate resin composition of description.
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 configurations (1) to (9).
One of the more preferable embodiments of the present invention is the injection molded product according to the above configuration (10), wherein the (11) injection molded product is a portable information terminal exterior member.
One of the more preferable embodiments of the present invention is the injection molded product according to the above configuration (10), which is a portable information terminal exterior member obtained by coating (12) an injection molded product.

Hereinafter, the present invention will be specifically described.
(A component: polycarbonate resin)
The polycarbonate resin used as the component A of the present invention is usually obtained by reacting a dihydroxy compound and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate prepolymer by a solid phase transesterification method. Or obtained by polymerizing by a ring-opening polymerization method of a cyclic carbonate compound. The dihydroxy component used here may be any one that is usually used as a dihydroxy component of an aromatic polycarbonate, and may be a bisphenol or an aliphatic diol. Examples of bisphenols include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 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) -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-hydroxypheny) ) 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′-dimethyldiphenyl ether, 4,4′-sulfoni 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 Xylphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane and the like.

  Examples of the 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-tert-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-hydroxyethyl) Xyl) phenyl} propane, 1,1-bis {3-cyclohexyl-4- (2-hydroxyethoxy) phenyl} cyclohexane, bis {(2-hydroxyethoxy) phenyl} diphenylmethane, 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 preferable, and 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'-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, particularly 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 dihydroxy compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  These polycarbonate resins are produced by a reaction means known per se for producing 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 a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed 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. In order to accelerate the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. In that case, reaction temperature is 0-40 degreeC normally, and reaction time is several minutes-5 hours. The transesterification reaction using a carbonic acid diester as a carbonate precursor is performed by a method in which an aromatic dihydroxy component in a predetermined ratio is stirred with a carbonic acid diester while heating with an inert gas atmosphere to distill the generated alcohol or phenols. . The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off the alcohol or phenol produced under reduced pressure from the beginning. Moreover, in order to accelerate | stimulate reaction, the catalyst normally used for transesterification can also be used. Examples of the carbonic acid diester used in the transesterification include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

  In the present invention, a terminal terminator is used in the polymerization reaction. The end terminator is used for molecular weight control, and the obtained polycarbonate resin is excellent in thermal stability as compared with the other one because the end is blocked. Examples of the terminal terminator include monofunctional phenols represented by the following general formulas [5] to [7].

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

[Wherein, X is —R—O—, —R—CO—O— or —R—O—CO—, wherein R is a single bond or a carbon number of 1 to 10, preferably 1 to 5; A valent aliphatic hydrocarbon group, and n represents an integer of 10 to 50. ]

  Specific examples of the monofunctional phenols represented by the general formula [5] include, for example, phenol, isopropylphenol, p-tert-butylphenol, p-cresol, p-cumylphenol, 2-phenylphenol, 4-phenyl. Phenol, isooctylphenol, etc. are mentioned. The monofunctional phenols represented by the general formulas [6] to [7] are phenols having a long-chain alkyl group or an aliphatic ester group as a substituent, and using these, the terminal of the polycarbonate resin is used. These not only function as a terminal terminator or molecular weight regulator, but also improve the melt fluidity of the resin and facilitate molding, as well as reducing the water absorption rate of the resin. used. The substituted phenols represented by the general formula [7] preferably have n of 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, Examples include eicosylphenol, docosylphenol, and triacontylphenol. Further, as the substituted phenols represented by the general formula [7], compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26. 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 preferably alkyl-substituted or phenylalkyl-substituted phenols, and particularly preferably p-tert-butylphenol, p -Cumylphenol or 2-phenylphenol. It is desirable that these monofunctional phenolic terminal terminators be introduced at least 5 mol%, preferably at least 10 mol%, based on the total terminals of the obtained polycarbonate resin. Or a mixture of two or more thereof.

  The polycarbonate resin used as the component A of the present invention may be a polyester carbonate copolymerized with an aromatic dicarboxylic acid, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid or a derivative thereof, as long as the gist of the present invention is not impaired. Good.

The viscosity average molecular weight of the polycarbonate resin used as the component A of the present invention is preferably in the range of 13,000 to 25,000, more preferably 13,000 to 21,000, and in the range of 16,000 to 21,000. Even more preferred is the range of 16,000 to 20,000, most preferred. If the molecular weight exceeds 25,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 13,000, there may be a problem in mechanical strength. In addition, the viscosity average molecular weight as used in the field of this invention was calculated | required and calculated | required first using the Ostwald viscometer from the solution which melt | dissolved the polycarbonate resin 0.7g in 20 ml of methylene chloride in the specific viscosity computed by following Formula. The viscosity average molecular weight M is determined by inserting the specific viscosity by the following formula.
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

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

  The polycarbonate resin used as the component A of the present invention can be used singly or in combination of two or more. As an example of combining two or more kinds of 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. The A-1 component alone is less effective for low temperature impact resistance, but is preferable because the low temperature impact resistance is further improved as compared with the case where the A-1 component is not added when the polycarbonate resin composition of the present invention is used. Although there is no restriction | limiting in particular about the ratio (A-1 / A-2) of A-1 component and A-2 component, Preferably it is 0.1 / 99.9-50 / 50, More preferably, it is 0.1 /99.9 to 20/80, even more preferably 0.1 / 99.9 to 10/90, and most preferably 0.1 / 99.9 to 5/95. The 9,9-bis (4-hydroxy-3-methylphenyl) fluorene constituting the A-1 component is preferably 10 to 70% by weight, more preferably 100% by weight of the total dihydroxy compound constituting the A-1 component. 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>
The polycarbonate-polydiorganosiloxane copolymer resin used as component B of the present invention is a polycarbonate-polydiorganosiloxane copolymer in which a polydiorganosiloxane domain having an average size of 0.5 to 18 nm is present in the matrix of the polycarbonate polymer. A resin is preferred. 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 this 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 product and paintability. In addition, the average size of this polydiorganosiloxane domain was measured by the small angle X-ray scattering method (Small Angel X-ray Scattering: SAXS). The small-angle X-ray scattering method is a method for measuring diffuse scattering diffraction that occurs in a small-angle region where 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 which the electron density is different in a substance, the X-ray diffuse scattering is measured by the difference in electron density. Based on the scattering angle and the scattering intensity, the particle diameter of the measurement object is obtained. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domain. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10 ° is measured, the small-angle X-ray scattering profile is measured, the polydiorganosiloxane domain is a spherical domain, and the particle size distribution varies. Assuming the presence of, the simulation is performed using a commercially available analysis software from the temporary particle size and the temporary particle size distribution model to obtain the average size of the polydiorganosiloxane domain. According to the small-angle X-ray scattering method, the average size of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy, can be measured accurately, simply, and with good reproducibility. Can do.

  The 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 General Formula [1], R ¹ and R ² are each independently 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. A and b are each 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 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, and 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 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, and R ⁹ and R ¹⁰ are each independently 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, and e and f Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms. .)

  Examples of the dihydric phenol (I) for deriving the carbonate structural unit represented by the general formula [1] include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis ( 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-tert-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'- 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-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6 Decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  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, especially 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 general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently 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, carbon An alkyl group of 1 to 6 or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently 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. An alkyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the above formula [3], for example, a compound represented by the following general formula (I) is preferably used.

  P and q representing the degree of diorganosiloxane polymerization are natural numbers, 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, 30 ~ 60 is most preferred.

The polydiorganosiloxane component content 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, even more preferably 3.0 to 10.0% by weight, 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 product and paintability. In addition, this diorganosiloxane polymerization degree and polydiorganosiloxane component content can be calculated by ¹ H-NMR measurement.

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

  In producing the chloroformate compound from the dihydric phenol (I), all the dihydric phenol (I) derived from the carbonate structural unit represented by the general formula [1] can be converted to the chloroformate compound at once. Alternatively, a part thereof may be added as a reaction raw material to a subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.
The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.

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, organic bases such as pyridine, and mixtures thereof. Is used.
The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, 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, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the production of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention, the dihydric phenol (I) having the chloroformate and terminal chloroformate groups of the dihydric phenol (I) is thus obtained. The dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [3] while preparing the mixed solution of the chloroformate compound containing the carbonate oligomer of 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 dihydric phenol (I) charged in preparing the mixed solution. Polycarbonate by interfacial polycondensation Obtaining a lysine organosiloxane copolymer resin.

  The polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention can be made into a branched polycarbonate-polydiorganosiloxane copolymer resin by using a branching agent in combination with a dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, 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- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

Even when the branched polycarbonate-polydiorganosiloxane copolymer resin is produced by a method in which the branching agent is contained in the mixed solution during the production reaction of the chloroformate compound, the interfacial polycondensation after the completion of the production reaction is performed. It may be a method in which a branching agent is added during the reaction. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol%, in the total amount of carbonate constituent units constituting the copolymer resin. Especially preferably, it is 0.05-1.0 mol%. Such a 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 can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours. In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduction. It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin having a viscosity [η _SP / c]. The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin having a desired purity (purity) after various post-treatments such as a known separation and purification method.

  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, with a range of 16,000-20,000 being most preferred. If the molecular weight exceeds 25,000, the melt viscosity becomes too high and the moldability may be inferior, and if the molecular weight is less than 13,000, there may be a problem in mechanical strength.

The viscosity average molecular weight of the polycarbonate-polydiorganosiloxane copolymer resin used as the component B of the present invention is calculated as follows. First, the specific viscosity (η _SP ) calculated by the following formula is obtained from an solution obtained by dissolving 0.7 g of a polycarbonate-polydiorganosiloxane copolymer resin in 100 ml of methylene chloride at 20 ° C. using an Ostwald viscometer,
Specific viscosity (η _SP ) = (t−t ⁰ ) / t ⁰
[T ⁰ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ^{2 c} (where [η] is the intrinsic 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 general formula [3] contained in the B component is 1.0 based on the total weight of the polycarbonate resin composition of the present invention. It is preferably ˜10.0% by weight, more preferably 1.0 to 8.0% by weight, further preferably 1.0 to 5.0% by weight, and most preferably 1.0 to 3.0% by weight. . If this ratio is less than 1.0% by weight, the low-temperature impact resistance after coating the molded product becomes insufficient, and if it exceeds 10.0% by weight, problems may occur in heat resistance and surface appearance, which is not preferable.

(In the general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, 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 B component is adjusted so that the content of the polydiorganosiloxane component contained in the B component is within the above-mentioned preferable range, but is preferably 1 to 90 parts by weight in 100 parts by weight of the resin component. -80 parts by weight is more preferable, 5-50 parts by weight is further preferable, 5-30 parts by weight is particularly preferable, and 10-30 parts by weight is most preferable. If the B component is less than 1 part by weight, the low-temperature impact resistance after coating the molded product is not sufficient, and if it exceeds 90 parts by weight, problems may occur in the heat resistance and the surface appearance.

(C component: polyolefin resin)
The component C polyolefin resin in the present invention is known per se, such as 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, ethylene and / or olefin copolymer of unsaturated carboxylic acid ester with α-olefin having 3 or more carbon atoms, ethylene-propylene copolymer Examples thereof include a copolymer, an ethylene-glycidyl (meth) acrylate copolymer, a propylene-vinyl acetate copolymer, and a 1-alkene polymer.

  The olefin polymer of component C includes, among others, polyethylene, polypropylene, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer. An olefin-based copolymer of ethylene, ethylene and / or an α-olefin having 3 or more carbon atoms and an unsaturated carboxylic acid ester, or a 1-alkene polymer can be preferably used. These polyolefins and their copolymers are available through 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 the C component, it is particularly preferable to use polyethylene. Examples of the polyethylene used 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, a Ziegler-based catalyst in linear low-density polyethylene, Various currently known catalysts such as metallocene catalysts can be used. Further, it is not subject to limitations such as the catalyst amount of the residue contained in polyethylene and the amount of unreacted unsaturated bonds. Furthermore, the polyethylene once prepared 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, particularly preferably 3,000 to 300,000. Examples of such polyethylene include commercially available products such as Hi-Zex 2100JP and 3300F [all are trade names of Mitsui Chemicals, Inc.], GML2420 [trade names of Nippon Unica Co., Ltd.], and the like.

  Content of C component is 0.1-5 weight part with respect to 100 weight part of resin components, Preferably it is 0.3-5 weight part, More preferably, it is 0.3-3.5 weight part. If the amount is less than 0.1 parts by weight, the chemical resistance and low temperature impact resistance are not improved, and if it exceeds 5 parts by weight, the appearance is deteriorated.

(D component: acrylic elastic polymer)
The acrylic elastic polymer of component D in the present invention is a rubbery polymer having a glass transition temperature of preferably 0 ° C. or lower, more preferably −20 ° C. or lower, and a monomer component copolymerizable therewith. A copolymerized polymer containing an acrylic component in either a rubber elastic body or a monomer. The acrylic elastic polymer used in the present invention is an acrylic elastic polymer that is a core-shell type and does not substantially contain a styrene component. As a result of intensive studies, the polycarbonate resin composition using an acrylic elastic polymer containing a styrene component is affected by the low temperature impact properties and chemical resistance of the styrene component itself, and the desired low temperature impact properties and It has been found that chemical resistance cannot be achieved. Therefore, 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) cannot be used in 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: In addition to silicone rubber such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, ethylene-α olefin rubber (ethylene-propylene rubber, ethylene -Butene rubber, ethylene-octene rubber, etc.), ethylene-acrylic rubber, fluororubber and the like. Two or more of these may be used in combination. Among these, in terms of chemical resistance in addition to impact resistance, any one selected from the group of polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber One is preferred.

  Specific examples of monomer components copolymerizable with the rubber 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-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their An anhydride (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, it is preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Yes, and more preferably a (meth) acrylic acid ester compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. It is done.

  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 of IPN (interpolating polymer network) type composite rubbers comprising polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber and polyalkyl acrylate rubber. Preferably, the shell layer is formed of (meth) acrylic acid ester.

Preferred examples of the core-shell type graft copolymer include methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), and methyl methacrylate- (acrylic silicone IPN rubber). A copolymer etc. are mentioned. Two or more of these may be used in combination.
Examples of the core-shell type graft copolymer include EXL series such as “Paraloid EXL2315”, “EXL2602”, and “EXL2603” manufactured by Rohm and Haas Japan.

Content of D component is 1-15 weight part with respect to 100 weight part of resin components, Preferably it is 1-10 weight part, More preferably, it is 2-9 weight part, Most preferably, it is 2-6 weight part. If the amount is less than 1 part by weight, the low temperature impact characteristics are not improved. If the amount exceeds 15 parts by weight, in addition to the decrease in mechanical strength such as heat resistance and low temperature impact characteristics, the chemical resistance is remarkably deteriorated and the appearance is reduced. This 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, the low temperature impact characteristics may not be improved, which is not preferable.

(Other additives)
In order to improve the flame retardancy, light diffusibility, antioxidant property, light stability (ultraviolet light stability), stabilizer, fluorescent whitening property, releasability and mold corrosion of the resin composition of the present invention. Additives used to improve 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 for polycarbonate resins. The compounding of such a compound brings about an improvement in flame retardancy, but besides that, based on the properties of each compound, for example, an improvement in antistatic property, fluidity, rigidity and thermal stability is brought about. Examples of such flame retardants include (i) organic metal salt flame retardants (for example, organic sulfonate alkali (earth) metal salts, organic borate metal salt flame retardants, organic stannate metal salt flame retardants, etc.), ii) organophosphorous flame retardants (for example, organic group-containing monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, etc.), (iii) silicone flame retardants comprising silicone compounds (Iv) fibrillated PTFE, among which organometallic salt flame retardants and organic phosphorus flame retardants are preferred.

(I) Organometallic salt flame retardant The organometallic salt compound is an alkali (earth) metal salt of an organic acid having 1 to 50 carbon atoms, preferably 1 to 40, preferably an alkali (earth) metal salt of an organic sulfonate. It is preferable that The alkali (earth) metal salt of the organic sulfonate 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 an alkaline earth metal. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and alkali metals or alkaline earth metals are included. Examples of the alkali metal constituting the metal salt include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, rubidium and cesium having larger ionic radii are suitable when the requirement for transparency is higher, but these are not general-purpose and difficult to purify, resulting in cost. It may be disadvantageous. On the other hand, metals with smaller ionic radii such as lithium and sodium may be disadvantageous in terms of flame retardancy. Considering these, the alkali metal in the sulfonic acid alkali metal salt can be properly used. In any respect, the sulfonic acid potassium salt having an excellent balance of properties is most preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.

Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, 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 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8. Of these, potassium perfluorobutanesulfonate is particularly preferred. The alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal is usually mixed with not less than fluoride ions (F ⁻ ). The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency. Such alkali (earth) metal salt of perfluoroalkylsulfonic acid having a reduced amount of fluoride ion is contained in a raw material when producing a fluorine-containing organometallic salt using a known production method. A method for reducing the amount of fluoride ions, a method for removing hydrogen fluoride and the like obtained by the reaction by a gas generated during the reaction or heating, and a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt Can be produced by a method of reducing the amount of fluoride ions using, for example. In particular, organic metal salt flame retardants are relatively soluble in water, and therefore ion-exchanged water, especially water that has an electric resistance of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less is used. In addition, it is preferable to produce by a process of dissolving at a temperature higher than room temperature and washing, then cooling and recrystallization. Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate 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, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate 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) polysulfonate, potassium sulfonate benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -Potassium 3,4'-disulfonate, sodium α, α, α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiophene-2 Formalin of disodium 5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, sodium naphthalenesulfonate Examples thereof include condensates and formalin condensates of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable. Among these aromatic sulfonate alkali (earth) metal salts, potassium diphenylsulfone-3-sulfonate and dipotassium diphenylsulfone-3,3′-disulfonate are preferable, and particularly a mixture thereof (the former and the latter). Is preferably 15/85 to 30/70).

  Preferable examples of the organic metal salt other than the alkali (earth) metal sulfonate include an alkali (earth) metal salt of a sulfate ester and an alkali (earth) metal salt of an aromatic sulfonamide. Examples of alkali (earth) metal salts of sulfates include alkali (earth) metal salts of sulfates of monovalent and / or polyhydric alcohols, and such monovalent and / or polyhydric alcohols. Examples of sulfuric acid esters include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono-, di-, tri-, tetra-sulfate, and lauric acid monoglyceride sulfate. Examples include esters, sulfates of palmitic acid monoglyceride, and sulfates of stearic acid monoglyceride. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate. Alkali (earth) metal salts of aromatic sulfonamides include, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfanilimide, and N- ( And an alkali (earth) metal salt of phenylcarboxyl) sulfanilimide. The content of the organometallic salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 0 part per 100 parts by weight of the resin component. .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. This is because such phosphate compounds are generally excellent in hue. Moreover, since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability can be improved. As the phosphate compound, various phosphate compounds known as conventional flame retardants can be used. The compounding amount of the organic phosphorus flame retardant is preferably 0.01 to 20 parts by weight, more preferably 2 to 10 parts by weight, and further preferably 2 to 7 parts by weight with respect to 100 parts by weight of the resin component.

(Iii) Silicone Flame Retardant A 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 a flame retardant for aromatic polycarbonate resin can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group. Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. 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 = CH) SiO _{1 / 2} , monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 , D unit: _{2 such as} (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Functional siloxane unit, T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) 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 in the silicone-based flame retardant include Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq. Among these, preferred structures of the silicone compound are MmDn, MmTp, MmDnTp, and MmDnQq, and a more preferred structure is MmDn or MmDnTp.

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This 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 better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue. As a result, good reflected light can be obtained. When any 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 or organic residues to be bonded. .

The silicone compound may be linear or have a branched structure. 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. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. 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 a methyl group, an ethyl group, and a propyl group is particularly preferable. Further, the silicone compound used as the silicone flame retardant preferably 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-based flame retardants in their preferred embodiments in that it is preferable to contain no 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. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
The 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) Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability
The fibrillated PTFE may be fibrillated PTFE alone or a mixed form of fibrillated PTFE, that is, a polytetrafluoroethylene-based mixture composed of fibrillated PTFE particles and an organic polymer. Fibrilized PTFE has an extremely high molecular weight and tends to be bonded to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. 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 the component B has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. . Such PTFE can be used in solid form or in the form of an aqueous dispersion. Such fibrillated PTFE can also be used in the form of a PTFE mixture with other resins in order to improve dispersibility in the resin and to obtain better flame retardancy and mechanical properties. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used. Examples of such commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A-11-29679, etc.) can be used. Commercially available products of these mixed forms of fibrillated PTFE include methabrene represented by Mitsubishi Rayon Co., Ltd.'s "methabrene A3000" (trade name), "methabrene A3700" (trade name), and "methabrene A3800" (trade name). Examples include A series, SN3300B7 (trade name) manufactured by Shine Polymer, and “BLENDEX B449” (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, and more preferably 20% by weight in 100% by weight of the mixture. Most preferred is from 80% to 80% by weight.
When the ratio of fibrillated PTFE in the mixed form is within such a range, good dispersibility of the fibrillated PTFE can be achieved. The blending amount of fibrillated PTFE is preferably 0.001 to 0.2 parts by weight, more preferably 0.01 to 0.2 parts by weight, with respect to 100 parts by weight of the resin component. More preferred is 18 parts by weight. In addition, the weight part shown here shows the weight of the whole mixture, when polytetrafluoroethylene is a mixed form (mixture).

(II) Thermal stabilizer Various known stabilizers can be blended in the polycarbonate resin composition of the present invention.
Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

(I) Phosphorus stabilizer It is preferable that the resin composition of the present invention contains a phosphorus stabilizer to the extent that it does not promote hydrolyzability. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Specifically, as the phosphite compound, 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, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like. Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure 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 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite 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-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- Examples include 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis. (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted. Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. The tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine. The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, an alkyl phosphate compound typified by trimethyl phosphate is preferably blended. A combination of such an alkyl phosphate compound and a phosphite compound and / or phosphonite compound is also a preferred embodiment.

(Ii) Hindered phenol stabilizer A hindered phenol stabilizer can be further blended in the resin composition of the present invention. Such blending exhibits an effect of suppressing, for example, hue deterioration during molding and hue deterioration during long-term use. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir 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-hydroxybenzylphosphonate 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'-butylidenebis (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 Nbis- [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′-hexamethylenebis- (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-tris 2 [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 said hindered phenol type stabilizer can be used individually or in combination of 2 or more types. The blending 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, and further preferably 100 parts by weight of the resin component. Is 0.005 to 0.3 parts by weight.

(Iii) Heat stabilizer other than the above The resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizer and the hindered phenol stabilizer. Preferable examples of such other heat stabilizers include lactone stabilizers represented by a reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Is done. Details of such a stabilizer are described in JP-A-7-233160. Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 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. Illustrated. The 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 with respect to 100 parts by weight of the resin component. An epoxy compound can be mix | blended with the resin composition of this invention as needed. Such an epoxy compound is blended for the purpose of suppressing mold corrosion, and basically any compound having an epoxy functional group can be applied. Specific examples of preferable epoxy compounds include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate, 1,2-epoxy-4-butane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include (2-oxiranyl) cyclosexane adduct, a copolymer of methyl methacrylate and glycidyl methacrylate, and a copolymer of styrene and glycidyl methacrylate. The amount of the epoxy compound added 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. -0.1 parts by weight.

(III) Mold Release Agent The polycarbonate resin composition of the present invention is further prepared with a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (polyester) for the purpose of improving productivity during molding and improving the dimensional accuracy of the molded product. Known release agents such as fluoro oil represented by fluoroalkyl ether), paraffin wax, beeswax and the like can also be blended. Since the polycarbonate resin composition of the present invention has good fluidity, the pressure propagation is good and a molded article with uniform strain can be obtained. On the other hand, in the case of a molded product having a complicated shape that increases the mold release resistance, the molded product may be deformed at the time of release. The compounding of the specific component solves such a problem without impairing the properties of the polycarbonate resin composition. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 5-30. 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. Of these, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070. As the polyolefin wax, an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or ethylene and a carbon atom having 3 to 3 carbon atoms. A copolymer with 60 α-olefins is exemplified. 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, and 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 preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like. A suitable polyolefin wax is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 60 carbon atoms. The proportion of the α-olefin having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. What is marketed as what is called polyethylene wax is used suitably.
The content of the release 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, and still more preferably 100 parts by weight of the resin component. 0
. 01 to 1 part by weight.

(IV) Ultraviolet Absorber In the resin composition of the present invention, an ultraviolet absorber can be blended for the purpose of imparting light resistance. Specific examples of the ultraviolet absorber include benzophenone-based 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′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy- 4-n-dodecyloxybenzophenone, and 2- Examples thereof include hydroxy-4-methoxy-2′-carboxybenzophenone. Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [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 copolymers with vinyl monomers and copolymers of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and vinyl monomers copolymerizable with the monomers Examples thereof include a polymer having a phenyl-2H-benzotriazole skeleton. Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 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) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups. Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like. Further, as the ultraviolet absorber, specifically, for cyanoacrylate, 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 ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The Among them, benzotriazole and hydroxyphenyltriazine are preferable in terms of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable in terms of heat resistance and hue. Specifically, Chemipro Kasei Co., Ltd. “Chemisorb 79” and the like can be mentioned. You may use the said ultraviolet absorber individually or in mixture of 2 or more types. The compounding amount of the ultraviolet 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 part by weight, particularly preferably 100 parts by weight of the resin component. Is 0.05 to 0.5 parts by weight.

(V) Dye / pigment The polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. Examples of dyes 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, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

(VI) Fluorescent whitening agent In the resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used for improving the color tone of the resin or the like to white or bluish white. Examples include imidazole, benzoxazole, naphthalimide, rhodamine, coumarin, and oxazine compounds. Specific examples include CI Fluorescent Brightener 219: 1, Eastman Chemical OB-1 manufactured by Eastman Chemical Co., and “Hackol PSR” manufactured by Hakkor Chemical Co., Ltd. Here, the fluorescent whitening agent has an action of absorbing energy in the ultraviolet part of the light and radiating this energy to the visible part. The content of the fluorescent brightening agent is preferably 0.001 to 0.1 parts by weight, 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 may contain a compound having heat ray absorbing ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide and imonium oxide, and metal borides such as lanthanum boride, cerium boride and tungsten boride. Preferable examples include various metal compounds having excellent near-infrared absorptivity such as a system and tungsten oxide near-infrared absorber, and carbon filler. 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 carbon black and graphite are preferable. 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, based on 100 parts by weight of the resin component, and 0.001 to 0.00. More preferred is 07 parts by weight. The content of the metal oxide near-infrared absorber, the metal boride-based 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. A range of 5 to 100 ppm is more preferable.

(VIII) Light Diffusing Agent The polycarbonate resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. 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, still more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the resin component. Two or more light diffusing agents can be used in combination.

(IX) White pigment for high light reflection The polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on 100 parts by weight of the resin component. 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 require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate 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 parts based on the total of 100 parts by weight of the A component, B component and C component. 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, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate 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. 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

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

(XI) Filler The polycarbonate resin composition of the present invention can be blended with various known fillers as reinforcing fillers. As such a filler, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, the fibrous filler has a fibrous shape (including a rod shape, a needle shape, or a shape whose axis extends in a plurality of directions), and the plate-like filler has a plate shape (surface) (Including those having irregularities and those having a curved plate). The granular filler is a filler having a shape other than these including an indefinite shape.
The fiber-like and plate-like shapes are often clear from the observation of the shape of the filler. For example, a difference from a so-called indeterminate shape can be said to be a fiber-like or plate-like one having an aspect ratio of 3 or more.

  As plate-like fillers, glass-flake, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, and these fillers are coated with different materials such as metals and metal oxides. A material etc. are illustrated preferably. The particle size is preferably in the range of 0.1 to 300 μm. The particle size is about 10 μm in terms of the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods. In the region of 10-50 μm, laser diffraction is performed. -The value by the median diameter (D50) of the particle size distribution measured by the scattering method is referred to, and in the region of 50 to 300 μm, the value is by the vibration sieving method. Such a particle size is a particle size in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane, titanate, aluminate, and zirconate, and olefin resin, styrene resin, acrylic resin, polyester resin. It may be a granulated product that has been subjected to a bundling treatment or compression treatment with various resins such as epoxy resins and urethane resins, higher fatty acid esters, and the like.

  The fiber diameter of the fibrous filler is preferably 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 here refers to the number average fiber diameter. The number average fiber diameter is obtained by scanning the residue collected after dissolving the molded product in a solvent, or decomposing the resin with a basic compound, and the ash residue collected after ashing with a crucible. It is a value calculated from an image observed with an electron microscope. Examples of the fibrous filler include 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, and boron whisker. , Aluminum inorganic whisker, calcium carbonate whisker, titanium oxide whisker, wollastonite, zonotolite, palygorskite (attapulgite), and fibrous inorganic fillers such as sepiolite, heat-resistant organic fibers such as aramid fiber, polyimide fiber and polybenzthiazole fiber And heat-resistant organic fillers represented by the above, as well as fibrous fillers whose surfaces are coated with different materials such as metals and metal oxides. It is exemplified. Examples of the filler whose surface is coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The surface coating method of different materials is not particularly limited. For example, various known plating methods (for example, electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition methods, ion plating methods, CVD methods ( For example, thermal CVD, MOCVD, plasma CVD, etc.), PVD method, sputtering method, etc. can be mentioned. Here, the fibrous filler means a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, 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 a value in the resin composition. The flat cross-section glass fiber has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average value of the ratio of major axis to minor axis (major axis / minor axis) of 1. .5-8, preferably 2-6, more preferably 2.5-5 glass fiber. The fibrous filler may be surface-treated with various coupling agents in the same manner as the plate-like filler, may be converged with various resins, and may be granulated by compression. The content of the filler is preferably 200 parts by weight or less based on 100 parts by weight of the resin component, 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.

(XII) Other Additives The polycarbonate resin composition of the present invention includes thermoplastic resins other than components A to D, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, and photocatalytic antifouling agents. And a photochromic agent etc. can be mix | blended.
As thermoplastic resins other than A component to D component, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PETG resin), polyethylene Naphthalate resin, polybutylene naphthalate resin, polyethylene terephthalate-adipate copolymer, etc.), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, and thermoplastic fluororesin (for example, polyfluoride resin). Exemplarily represented by vinylidene chloride 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 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 producing such pellets, the above-mentioned various flame retardants, reinforcing fillers and additives can be blended. The resin composition of the present invention can be usually produced by injection-molding pellets produced as described above to produce various products. Furthermore, the resin melt-kneaded by an extruder can be directly made into a sheet, a film, a profile extrusion molded product, a direct blow molded product, and an injection molded product without going through pellets. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding. Moreover, the resin composition of this invention can also be utilized in the form of various profile extrusion-molded articles, a sheet | seat, a film, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

<About production of resin composition>
Arbitrary methods are employ | adopted in order to manufacture the resin composition of this invention. For example, after thoroughly mixing A component, B component, C component, D component and optionally other components using pre-mixing means such as V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Accordingly, there is a method in which granulation is performed by an extrusion granulator or a briquetting machine, followed by melt kneading with a melt kneader represented by a vent type biaxial ruder, and pelletization with an apparatus such as a pelletizer.

<Manufacture of molded products>
The resin composition of the present invention can usually be obtained by injection molding such pellets. In such injection molding, not only a normal cold runner type molding method but also a hot runner that enables runnerlessness can be used. Also in injection molding, not only ordinary molding methods, but also gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (ultra-molding) Including those using critical fluids), rapid heating / cooling mold forming, heat insulating mold forming and in-mold remelt molding, and combinations of these, etc. can be used. Furthermore, various surface treatments can be performed on the molded product formed from the resin composition. Surface treatment includes decorative coating, hard coat, water / oil repellent coat, hydrophilic coat, UV absorbing coat, infrared absorbing coat, electromagnetic wave absorbing coat, heat generating coat, antistatic coat, antistatic coating, conductive coating, and meta coating. 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 include various electronic / electric equipment parts (particularly portable information terminal housings), 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, playground equipment, and miscellaneous goods, and the industrial effects that it plays are exceptional.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are 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 according to ISO 179 (measurement conditions 23 ° C, -30 ° C). The test pieces were formed by drying the various pellets obtained at 120 ° C. for 5 hours, and then using an injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. .

(Ii) Chemical resistance Using a SG-150U molding machine, Sumitomo Heavy Industries, Ltd., a portable information terminal simulation type of length 150 mm × width 100 mm × thickness 0.8 mmt at a cylinder temperature of 300 ° C. and a mold temperature of 90 ° C. (With back rib) was molded. The resulting molded product was spray-coated (spray for mini hobby manufactured by Nippe Home Products Co., Ltd.), and the impact resistance before and after coating was evaluated by a DuPont drop impact test in accordance with ISO6272. : R = 4.5, cradle: brass cylinder (outer diameter: 60 mm, inner diameter: 45 mm) DuPont impact strength G and impact strength retention ratio R after coating were determined by the following formulas. The dropping position of the droop was set near the rib on the back side of the molded product, and the value of the maximum height at which there was no crack on the surface, no crack on the rib, and no penetration of the strike core was taken as the impact strength.
G (J) = M × h
(M: Weight of the weight (kg), h: Height to drop the weight)
R (%) = [G1 / G2] × 100
(G1: DuPont impact strength after painting, G2: DuPont impact strength before painting)

(Iii) Heat resistance The portable information terminal simulated mold was allowed to stand in a 120 ° C dry heat environment for 120 hours, and the molded product after the dry heat test was evaluated according to the following criteria.
○: No deformation of the molded product △: Warping in the molded product ×: Warping and deformation in the molded product

(Iv) Appearance of molded product The appearance of the portable information terminal simulated mold product was visually observed and evaluated. The evaluation was performed according to the following criteria.
○: No abnormality is observed ×: Abnormality such as peeling or gloss reduction is observed

(V) Fluidity Using a Sumitomo Heavy Industries, Ltd. SG-150U molding machine, the flow length was measured with an Archimedes spiral flow mold (channel thickness 1 mm, channel width 8 mm). The conditions were a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and an injection pressure of 98 MPa. Evaluation was performed 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]
The components A to D and various additives were mixed in the blending amounts shown in Table 1 with a blender, and then melt-kneaded using a vent type twin screw extruder to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin screw extruder used was TEX30α (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. did.

In addition, the detail of each used component is as follows.
(Component A)
PC-1: Polycarbonate resin powder having a viscosity average molecular weight of 19,800 obtained by the following production method [Production method]
A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 2340 parts of ion-exchanged water, 947 parts of a 25% aqueous sodium hydroxide solution and 0.7 parts of hydrosulfite, and 2,2-bis (4-hydroxyphenyl) under stirring. ) After dissolving 710 parts of propane (hereinafter sometimes referred to as “bisphenol A”) (bisphenol A solution), 2299 parts of methylene chloride and 112 parts of 48.5% aqueous sodium hydroxide solution were added, and the temperature was 15-25 ° C. The phosgenation reaction was performed by blowing 354 parts of phosgene over about 90 minutes. After the completion of phosgenation, 148 parts of 11% strength p-tert-butylphenol in methylene chloride and 88 parts of 48.5% aqueous sodium hydroxide solution were added, stirring was stopped, and the mixture was allowed to stand for 10 minutes, followed by stirring. After 5 minutes of emulsification, the mixture was processed with a homomixer (Special Machine Industries Co., Ltd.) at a rotation speed of 1200 rpm and a bath frequency of 35 times to obtain a highly emulsified 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, washed with water, acidified with hydrochloric acid and washed with water. Then, methylene chloride was evaporated with stirring to obtain polycarbonate powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate resin powder.

PC-2: Polycarbonate resin powder having a viscosity average molecular weight of 16,500 obtained by the following production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the production method of PC-1, except that it 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 production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the production method of PC-1, except that it was changed to 294 parts of a methylene chloride solution of 11% concentration of p-tert-butylphenol.

PC-4: Polycarbonate resin powder having a viscosity average molecular weight of 23,200 obtained by the following production method [Production method]
A polycarbonate resin powder was obtained in the same manner as in the production method of PC-1, except that it was changed to 118 parts of a methylene chloride solution of 11% 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 in molar ratio.
[Production method]
A reactor equipped with a thermometer, a stirrer and a reflux condenser was charged with 23030 parts of ion exchange water and 3957 parts of 48.5% aqueous sodium hydroxide solution, and 3026 parts of biscresol fluorene, 1826 parts of bisphenol A and 10 parts of hydrosulfite were dissolved. Thereafter, 17183 parts of methylene chloride was added, and 1900 parts of phosgene was blown in for 60 minutes at 15 to 25 ° C. with stirring. After completion of the phosgene blowing, a solution obtained by dissolving 96 parts of p-tert-butylphenol in 1300 parts of methylene chloride and 660 parts of a 48.5% aqueous sodium hydroxide solution were added and emulsified. The reaction was terminated by stirring at 33 ° C. for 1 hour. After completion of the reaction, the product is diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water, the methylene chloride phase is concentrated and dehydrated to remove 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 biscresolfluorene to bisphenol A in the molar ratio of 50:50.

(B component)
B-1: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 19,400 obtained by the following production method [Production method]
Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21591 parts of ion-exchanged water and 3673 parts of 48.5% aqueous sodium hydroxide solution were placed, and 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). , And 7.6 parts of hydrosulfite were dissolved, 14565 parts of methylene chloride (14 moles relative to 1 mole of dihydroxy compound (I)) was added, and 1900 parts of phosgene was required for 60 minutes at 22-30 ° C. with stirring. Blew in. Next, a solution obtained by dissolving 1131 parts of 48.5% sodium hydroxide aqueous solution and 105 parts of p-tert-butylphenol in 800 parts of methylene chloride was added, and the polydiorganosiloxane compound represented by the following formula [8] ( In the formula, an average number of repetitions p = about 37) of 430 parts of methylene chloride dissolved in 1600 parts of methylene chloride was dissolved in 0.008 mol of dihydroxyaryl-terminated polydiorganosiloxane (II) per mol of dihydric phenol (I). The mixture was added at a rate of / min to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., 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, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. After dehydration, it was dried at 120 ° C. for 12 hours with a hot air circulation dryer to obtain a polycarbonate-polydiorganosiloxane copolymer resin powder. (Polydiorganosiloxane component content 8.2%, polydiorganosiloxane domain average size 9 nm, viscosity average molecular weight 19,400)

B-2: Polycarbonate-polydiorganosiloxane copolymer resin powder having a viscosity average molecular weight of 15,000 obtained by the following production method [Production method]
Except having changed p-tert- butylphenol into 132 parts, it carried out similarly to the manufacturing method of B-1, and obtained polycarbonate resin powder. (Polydiorganosiloxane component content 8.2%, polydiorganosiloxane domain average size 9 nm, viscosity average molecular weight 15,000)

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

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

(C component)
PE: Polyethylene resin (Hi-Zex 2100JP manufactured by Mitsui Chemicals)
EA: ethylene-ethyl acrylate copolymer (Rexpearl (trademark) A-4250 manufactured by Nippon Polyethylene Co., Ltd.)
(D component)
MB: Polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (
Core-shell type graft copolymer (“M-711” manufactured by Kaneka Corporation) (butadiene rubber amount 70%)
MBS-1: Butadiene-2-ethylhexyl acrylate copolymer rubber reinforced -styrene-
Methyl methacrylate copolymer (HIA15 manufactured by Kureha Chemical Co., Ltd.) (copolymer rubber amount 6
0%)
MBS-2: Methyl methacrylate / butadiene / styrene (MBS) copolymer (Mittabrene C223A manufactured by Mitsubishi Rayon Co., Ltd.) (80% rubber)
(Other ingredients)
A: Tris (2,4-di-t-butylphenyl) phosphite) (manufactured by Ciba Specialty Chemicals)
CB: 30 parts by weight of carbon black (carbon black MA-10 manufactured by Mitsubishi Chemical Corporation)
0) 3 parts by weight of white mineral oil (Crystol N35 manufactured by ExxonMobil)
2), 0.2 parts by weight of a montanic acid ester wax (Ricorb 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 pellets TiO2: titanium dioxide (manufactured by Resino Color Industry Co., Ltd., White DCF-T) produced by melt-mixing 100 parts by weight of the four components having a viscosity average molecular weight of 16,000) using a twin screw extruder -17007)

Claims (12)

  (C) Polyolefin resin (C component) 0.1-5 weight with respect to 100 weight part of resin component which consists of (A) polycarbonate resin (A component) and (B) polycarbonate polydiorganosiloxane copolymer resin (B component) Part and (D) a core-shell type polycarbonate resin composition containing 1 to 15 parts by weight of an acrylic elastic polymer (D component) that does not contain a styrene component. The component B is 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]. 2. The polycarbonate resin composition according to 1.

[In General Formula [1], R ¹ and R ² are each independently 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. A and b are each 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 are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and Represents a group selected from the group consisting of carboxyl groups, and when there are a plurality of them, they may be the same or different, c is an integer of 1 to 10, and 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 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, and R ⁹ and R ¹⁰ are each independently 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, and e and f Is an integer of 1 to 4, p is a natural number, q is 0 or a natural number, p + q is a natural number of 4 or more and 150 or less, and X is a divalent aliphatic group having 2 to 8 carbon atoms. .) 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 general formula [3] is 1.0 to 10.0% by weight. The polycarbonate resin composition according to claim 1 or 2.

(In the general formula [4], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, 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 component B is a polycarbonate-polydiorganosiloxane copolymer resin in which a polydiorganosiloxane domain having an average size of 0.5 to 18 nm is present in a polycarbonate polymer matrix. Polycarbonate resin composition.   C component is polyethylene, The polycarbonate resin composition in any one of Claims 1-4 characterized by the above-mentioned.   The component 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. The polycarbonate resin composition described in 1.   The polycarbonate resin composition according to claim 1, wherein the component D is an acrylic elastic polymer having a rubber content of 60% by weight or more.   A component is an aromatic polycarbonate resin (A-1 component) obtained by reacting a dihydric phenol containing (A-1) 9,9-bis (4-hydroxy-3-methylphenyl) fluorene with a carbonate precursor. ) And (A-2) A polycarbonate resin composition according to any one of claims 1 to 7, which is an aromatic polycarbonate resin comprising an aromatic polycarbonate resin (component A-2) other than the component A-1. object.   The polycarbonate resin composition according to claim 1, 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 9.   The injection molded product according to claim 10, wherein the injection molded product is a portable information terminal exterior member.   The injection molded product according to claim 10, which is a portable information terminal exterior member coated with the injection molded product.