JP2012172058A - Polycarbonate resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in flame retardancy and impact resistance, moreover having high impact resistance also in molding at high temperature, and having high impact resistance even under low-temperature environment.SOLUTION: The polycarbonate resin composition contains: 3-30 pts.mass of a phosphorus-based flame retardant (B); 0.001-1 pts.mass of a fluoropolymer (C); and further 0.5-10 pts.mass of a total sum of a graft copolymer (D) formed by graft-copolymerization of a rubbery polymer and a monomer component copolymerizable therewith and having an average particle size of 70 to 180 nm and a graft copolymer (E) having an average particle size of >180 nm and ≤300 nm, based on 100 pts.mass of a polycarbonate resin (A), wherein 10-90 mass% of (D) and 90-10 mass% of (E) are contained on the basis of the total sum of (D) and (E).

Description

  The present invention relates to a polycarbonate resin composition and a molded body. More specifically, a polycarbonate resin composition excellent in flame retardancy and impact resistance, having high impact resistance even at high temperature molding, and having high impact resistance even in a low temperature environment, and molding the polycarbonate resin composition It relates to a molded body.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

  As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were. As an alternative technique, many polycarbonate resin compositions containing a phosphorus-based flame retardant have been employed (see, for example, Patent Document 1).

As described above, the method of incorporating a phosphorus-based flame retardant into the polycarbonate resin can obtain a polycarbonate resin material having high flame retardancy and excellent fluidity, but on the other hand, the impact resistance inherent in the polycarbonate resin is low. It had the disadvantage of being significantly reduced.
For this reason, attempts have been actively made to improve the impact resistance by further blending an elastomer. Among these, a graft copolymer comprising a rubbery polymer and a polymerizable monomer, and more preferably a core comprising a rubbery polymer core and a shell comprising a polymerizable monomer. -Impact resistance can be effectively improved by using a shell type graft copolymer (for example, refer patent document 2).

In addition, a graft copolymer having an average particle size of 0.1 to 0.2 μm using a polyorganosiloxane-butyl acrylate rubber as a core, acrylonitrile and styrene as a shell, and a butadiene-unsaturated carboxylic acid alkyl ester-aromatic vinyl system A resin composition containing a graft copolymer having an average particle diameter of 100 to 180 nm with rubber as a core and styrene and methyl acrylate as a shell has also been proposed (see Patent Documents 3 to 5).
However, since such a graft copolymer is easily combusted, if the graft copolymer is further blended with the polycarbonate resin blended with the phosphorus flame retardant as described above, the flame retardancy is remarkably deteriorated. It was.

In general, the casing of an electronic / electrical device requires a level of V-1 or higher in a flame retardancy test based on UL94. Therefore, in the field of electronic and electrical equipment, a material having a balance between flame retardancy of not less than V-1 and impact resistance is strongly desired. In recent years, along with the downsizing and thinning of notebook computers and various portable devices, their casings and battery pack parts tend to be thin, and the molding process temperature tends to be set higher.
However, the conventionally used polycarbonate resin composition containing a graft copolymer has a drawback in that impact resistance is lowered when the molding temperature is increased.

  Furthermore, due to the recent increase in safety concerns, various materials for portable equipment casings that may be used even in extremely cold regions of several tens of degrees are under extremely low temperatures of minus 30 ° C. However, the conventionally used polycarbonate resin composition containing a graft copolymer has a problem that the impact resistance is remarkably lowered and it is easily broken when dropped.

JP-A-62-2746 Japanese Patent Laid-Open No. 11-21441 JP-A-10-120893 JP-A-11-140295 JP 2009-203269 A

  The present invention was devised in view of the above-mentioned problems of the prior art, and is excellent in flame retardancy and impact resistance while maintaining the excellent fluidity of a polycarbonate resin flame-retardant with a phosphorus-based flame retardant. It is another object of the present invention to provide a polycarbonate resin composition having high impact resistance even during high temperature molding and having high impact resistance even in a low temperature environment, and a molded body formed by molding the polycarbonate resin composition.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have determined that two or more different average particle diameters in a resin composition comprising a polycarbonate resin, a phosphorus-based flame retardant, a fluoropolymer, and a graft copolymer are obtained. By containing a specific amount of a graft copolymer having a high impact resistance, the impact resistance, particularly the impact resistance during high temperature molding and impact resistance in a low temperature environment, is not surprisingly brought about without reducing the flame retardancy. As a result, the present invention has been completed.

That is, according to the first aspect of the present invention, 3 to 30 parts by mass of the phosphorus-based flame retardant (B) and 0.001 to 1 of the fluoropolymer (C) with respect to 100 parts by mass of the polycarbonate resin (A). Part by mass,
A graft copolymer (D) having an average particle size of 70 to 180 nm obtained by graft copolymerization of a monomer component copolymerizable with the rubber polymer;
0.5 to 10 parts by mass in total of the graft copolymer (E) having an average particle size of more than 180 to 300 nm or less obtained by graft copolymerization of a monomer component copolymerizable with the rubber polymer. And the polycarbonate resin composition characterized by containing (D) 10-90 mass% and (E) 90-10 mass% on the basis of the total amount of (D) and (E). .

  According to a second aspect of the present invention, there is provided a polycarbonate resin composition according to the first aspect, wherein the rubbery polymer is a butadiene rubber.

  According to a third aspect of the present invention, in the first or second aspect, the monomer component copolymerizable with the rubber polymer is a (meth) acrylic ester compound. A polycarbonate resin composition is provided.

（式中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｐ、ｑ、ｒおよびｓは、それぞれ０または１であり、ｋは１から５の整数であり、Ｘ^１はアリーレン基を示す。） According to the fourth invention of the present invention, in any one of the first to third inventions, the phosphorus-based flame retardant (B) is a phosphate ester represented by the following formula (1). A polycarbonate resin composition is provided.

(Wherein R ¹ , R ² , R ³ and R ⁴ each represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q , R and s are each 0 or 1, k is an integer of 1 to 5, and X ¹ represents an arylene group.)

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, the flame retardancy in a UL94 vertical combustion test at a thickness of 0.8 mm is V-1 or more. A polycarbonate resin composition is provided.

  Moreover, according to the 6th invention of this invention, the molded object formed by shape | molding the polycarbonate resin composition of the invention in any one of the 1st-5th is provided.

  Furthermore, according to the seventh aspect of the present invention, there is provided the molded body according to the sixth aspect, wherein the molded body is a battery pack housing.

  According to the polycarbonate resin composition of the present invention, a polycarbonate resin material having excellent flame resistance and impact resistance, high impact resistance even at high temperature molding, and high impact resistance even in a low temperature environment. It is possible to provide.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, unless otherwise specified, “to” is used in a sense that includes numerical values described before and after it as a lower limit value and an upper limit value. Further, “part” means a part by mass based on the mass standard unless otherwise specified.

[1. Overview]
The polycarbonate resin composition of the present invention comprises a phosphorus-based flame retardant (B) and a fluoropolymer (C), a graft copolymer (D) having an average particle size of 70 to 180 nm and an average particle size of more than 180 A specific amount of each of the graft copolymers (E) of 300 nm or less is contained.

[2. Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin used for the polycarbonate resin composition of this invention. In addition, one type of polycarbonate resin may be used, or two or more types may be used in any combination and in any ratio.

In addition, the polycarbonate resin in this invention is a polymer of the basic structure which has a carbonic acid bond represented by following General formula (2). In formula (2), X ² is generally a hydrocarbon group, but X ² into which a hetero atom or a hetero bond is introduced may be used for imparting various properties.

  The polycarbonate resin can be classified into an aromatic polycarbonate resin in which carbon directly bonded to a carbonic acid bond is aromatic carbon and an aliphatic polycarbonate resin in which aliphatic carbon is aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

  Although there is no restriction | limiting in the specific kind of polycarbonate resin, For example, the polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1-bis (4-hydroxyphenyl) ethane,
2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1-bis (4-hydroxyphenyl) butane,
2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1-bis (4-hydroxyphenyl) octane,
2-bis (4-hydroxyphenyl) octane,
1-bis (4-hydroxyphenyl) hexane,
2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
10-bis (4-hydroxyphenyl) decane,
1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1-bis (4-hydroxyphenyl) cyclopentane,
1-bis (4-hydroxyphenyl) cyclohexane,
4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

Among these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (ie, from the viewpoint of impact resistance and heat resistance). Bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the monomer that is a raw material for the aliphatic polycarbonate resin include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as

  Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

Glycols such as 2,2'-oxydiethanol (ie, ethylene glycol), diethylene glycol, triethylene glycol, propylene glycol, spiroglycol, etc .;

  1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyl diols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

  1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl And cyclic ethers such as -1,2-epoxycyclohexane, 2,3-epoxynorbornane, and 1,3-epoxypropane;

  Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin The manufacturing method of polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case where a polycarbonate resin is produced by the interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

  The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like. Of these, aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where a polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. Is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In the polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing a polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the polycarbonate resin and the polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters regarding polycarbonate resin The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16,000. Above, more preferably 17,000 or more, and usually 40,000 or less, preferably 30,000 or less, more preferably 24,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the polycarbonate resin composition of the present invention can be further improved. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the polycarbonate resin composition of this invention can be improved more.

  In addition, the unit of a terminal hydroxyl group density | concentration represents the mass of the terminal hydroxyl group with respect to the mass of polycarbonate resin in ppm. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The polycarbonate resin is a polycarbonate resin alone (the polycarbonate resin alone is not limited to an embodiment containing only one type of polycarbonate resin, and is used in a sense including an embodiment containing a plurality of types of polycarbonate resins having different monomer compositions and molecular weights, for example. .), Or an alloy (mixture) of a polycarbonate resin and another thermoplastic resin may be used in combination. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the polycarbonate resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[3. Phosphorus flame retardant (B)]
The polycarbonate resin composition of the present invention contains 3 to 30 parts by mass of the phosphorus-based flame retardant (B) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing a phosphorus flame retardant.

  The phosphorus flame retardant in the present invention is a compound containing phosphorus in the molecule and may be a low molecule, an oligomer, or a polymer. From the viewpoint of thermal stability, for example, the following The phosphate compound represented by the general formula (1) and the phosphazene compounds represented by the following general formulas (3) and (4) are particularly preferable.

[3-1. Phosphate ester compound]
The phosphate ester compound represented by the general formula (1) may be a mixture of compounds having different numbers of k. In the case of a mixture of condensed phosphate esters having different k, k is a mixture thereof. The average value of k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably. Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

  Further, p, q, r and s in the general formula (1) each represent 0 or 1, and 1 is particularly preferable.

R ¹ , R ² , R ³ and R ⁴ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, and p-cumylphenyl group. Group, cresyl group and xylyl group are more preferred.

Specific examples of the phosphate ester compound represented by the general formula (1) include
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

  The acid value of the phosphoric acid ester compound represented by the general formula (1) is preferably 0.2 mgKOH / g, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH or less, particularly preferably Is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and still more preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermal stability and hydrolysis resistance of the polycarbonate resin composition of the present invention are reduced.

  As the phosphate ester compound used in the present invention, in addition to the above-mentioned compounds, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,3 -Dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,4-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phosphoric acid Naturally, polyester resins, polycarbonate resins or epoxy resins containing an ester moiety are also included.

[3-2. Phosphazene compound]
Examples of the phosphazene compounds represented by the general formulas (3) and (4) include phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene). O, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene and / or cyclic and chain C _1-6 alkyl C _6-20 aryloxy phosphazene, (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- tolyloxy phosphazene, phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxysilyloxyphosphazene, (poly ) Cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as _{phenoxytolyloxyxyloxyphosphazene} .
Of these, cyclic and / or chain phenoxyphosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 Aryloxyphosphazenes (eg, cyclic and / or chain tolyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.).

In the cyclic phosphazene compound represented by the general formula (3), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in formula (3), t represents an integer of 3 to 25. Among them, a compound in which t is an integer of 3 to 8 is preferable, and a mixture of compounds having different t may be used. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

In formula (4), R ⁷ and R ⁸ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, a benzyl group, and the like, and a chain phenoxyphosphazene in which R ⁷ and R ⁸ are phenyl groups is particularly preferable.
Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group.

Also, R ⁹ is represented by -N = P (OR ⁷ ) ₃ groups, -N = P (OR ⁸ ) ₃ groups, -N = P (O) OR ⁷ groups, and -N = P (O) OR ⁸ groups. At least one selected is shown, and R ¹⁰ is -P (OR ⁷ ) ₄ group, -P (OR ⁸ ) ₄ group, -P (O) (OR ⁷ ) ₂ group, -P (O) (OR ⁸ ) At least one selected from _two groups.

  Moreover, in Formula (4), u shows the integer of 3-10,000, Preferably it is 3-1,000, More preferably, it is 3-100, More preferably, it is 3-25.

The phosphazene compound used in the present invention may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
Examples of such a crosslinked phosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Having a crosslinked structure of 4,4′-diphenylene group, such as a compound having a crosslinked structure of 4,4′-oxydiphenylene group, a compound having a crosslinked structure of 4,4′-thiodiphenylene group, etc. Compounds and the like.

［式（５）中、Ｘ^３は−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｖは０又は１である。］

[In Formula (5), X ³ is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

Further, as the crosslinking phosphazene compound of the general formula (3) R ⁵ and R ⁶ are cyclic phenoxyphosphazene compound is cross-linked by a cross-linking group represented by the above general formula (5) the crosslinked phenoxyphosphazene compound is a phenyl group Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (4) with a crosslinking group represented by the general formula (5) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (5) is more preferable.

  The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (3) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (4) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (3) and the cyclic phenoxyphosphazene compound represented by the general formula (4) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  The content of the phosphorus-based flame retardant (B) is 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 30 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin (A). Preferably it is 25 parts by weight or less, more preferably 20 parts by weight or less. When the blending amount of the phosphorus-based flame retardant is less than 3 parts by mass, the flame retardancy is insufficient, and when it exceeds 30 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[4. Fluoropolymer (C)]
The polycarbonate resin composition of the present invention contains 0.001 to 1 part by mass of the fluoropolymer (C) with respect to 100 parts by mass of the polycarbonate resin (A). One type of fluoropolymer (C) may be used, or two or more types may be used in any combination and in any ratio.

  Examples of the fluoropolymer (C) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

  Examples of the fluoroethylene resin having a fibril forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon F201L”, “Polyfluorocarbon” manufactured by Daikin Chemical Industries, Ltd. F103 "," Polyfluorocarbon FA500B "," Polyfluorocarbon FA500H "and the like. Furthermore, as a commercial item of the aqueous dispersion liquid of fluoroethylene resin, "Teflon (registered trademark) 31-JR" by Mitsui DuPont Fluorochemical Co., Ltd., "Fluon D-1" by Daikin Chemical Industries, etc. are mentioned, for example. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The fluoropolymer (C) in the present invention preferably has a standard specific gravity value of 2.15 to 2.22. When the standard specific gravity is less than 2.15, the appearance of the molded product tends to deteriorate, which is not preferable. On the other hand, when the standard specific gravity exceeds 2.22, the drip resistance tends to decrease, such being undesirable. The standard specific gravity value is preferably 2.155 to 2.215, more preferably 2.16 to 2.1, particularly preferably 2.16 to 2.20, 2.165. Most preferred is ˜2.19. The standard specific gravity (also referred to as SSG) is a value measured by a water displacement method using a sample molded according to ASTM D4895.

  The average particle size of the fluoropolymer (C) in the present invention is not particularly limited, but is preferably 300 to 1,000 μm. When the average particle size is less than 300 μm, the drip resistance of the polycarbonate resin composition of the present invention may be reduced. When the average particle size is more than 1,000 μm, the fluoropolymer is likely to aggregate, resulting in a molded product. In such a case, it is not preferable because it may cause appearance defects such as white spot foreign matter. From such a viewpoint, the average particle size of the fluoropolymer is more preferably 350 to 800 μm, further preferably 380 to 750 μm, and particularly preferably 400 to 700 μm.

  The content of the fluoropolymer (C) is 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, relative to 100 parts by mass of the polycarbonate resin (A). Especially preferably, it is 0.1 mass part or more, and is 1 mass part or less, Preferably it is 0.75 mass part or less, More preferably, it is 0.5 mass part or less. When the content of the fluoropolymer (C) is less than or equal to the lower limit of the above range, the flame retardancy effect due to the anti-dripping agent becomes insufficient, and when the content exceeds the upper limit of the above range, the polycarbonate resin composition There is a possibility that the appearance defect or the mechanical strength of the molded product formed from the above will be deteriorated.

[5. Graft copolymers (D) and (E)]
The polycarbonate resin composition of the present invention is a graft copolymer (D) having an average particle diameter of 70 to 180 nm obtained by graft copolymerization of a monomer component copolymerizable with a rubber polymer. It contains a graft copolymer (E) having an average particle size of more than 180 to 300 nm obtained by graft copolymerizing a rubbery polymer with a monomer component copolymerizable therewith.
As a method for producing a graft copolymer obtained by graft copolymerizing a monomer component copolymerizable with a rubber polymer, any method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization may be used. In particular, emulsion polymerization is preferred.
The copolymerization method may be single-stage or multistage grafting, but multistage graft copolymerization is preferred.

The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower.
Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate-2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, composite rubber made of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-α-olefin system such as ethylene-octene rubber Examples thereof include rubber, ethylene-acrylic rubber, and fluorine rubber. These may be used alone or in combination of two or more.
Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. More preferred are butadiene rubbers such as rubber and styrene-butadiene rubber.

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. 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 anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more.
Of these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and more preferably aromatic vinyl compounds, A vinyl cyanide compound and a (meth) acrylic acid ester compound are preferred, and a (meth) acrylic acid ester compound is more preferred. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meta ) Phenyl acrylate and the like.

The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among these, at least one rubber component selected from a polybutadiene-containing rubber, a polybutyl acrylate-containing rubber, a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl acrylate rubber (Interpenetrating Polymer Network (IPN) type) composite rubber is used. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester around the core layer is particularly preferred.
The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

The average particle diameter of the graft copolymer (D) in the present invention is 70 nm to 180 nm, preferably 90 nm to 170 nm, and more preferably 100 nm to 160 nm.
On the other hand, the average particle size of the graft copolymer (E) is larger than 180 nm to 300 nm, preferably from 185 nm to 250 nm, and more preferably from 190 nm to 230 nm.

  In addition, an average particle diameter is calculated | required by the volume average particle diameter D50 when the graft copolymer solution after superposition | polymerization is measured with a dynamic light scattering method. For example, “Microtrac particle size analyzer 9230UPA” manufactured by Nikkiso Co., Ltd. can be used.

In a system comprising a polycarbonate resin, a phosphorus-based flame retardant, a fluoropolymer, and a graft copolymer, it is surprising that the graft copolymers (D) and (E) having different average particle diameters are mixed and contained. It should be possible to improve impact resistance, particularly impact resistance during high temperature molding and impact resistance in a low temperature environment without causing a decrease in flame retardancy.
The mixing ratio of the graft copolymer (D) and the graft copolymer (E) is 10 to 90% by mass of (D) and 90 to 90% of (E), based on the total amount of (D) and (E). 10% by mass, preferably 15 to 85% by mass of (D), 85 to 15% by mass of (E), more preferably 20 to 60% by mass of (D) and 80 to 40% by mass of (E). Particularly preferably, (D) is 25 to 40% by mass and (E) is 75 to 60% by mass.
When the amount of the graft copolymer (D) is less than 10% by mass and the amount of the graft copolymer (E) is more than 90% by mass, the UL flame retardancy deteriorates, as will be apparent from the comparative examples described later. Therefore, it is not preferable. On the other hand, if the amount of the graft copolymer (D) exceeds 90% by mass and the amount of the graft copolymer (E) is less than 10% by mass, the impact resistance is remarkably lowered, which is not preferable.

  Moreover, a graft copolymer (D) and a graft copolymer (E) are 0.5-10 mass parts in total with respect to 100 mass parts of polycarbonate resin (A). If the total content of both is less than 0.5 parts by mass, the impact resistance improvement effect is insufficient, and if it exceeds 10 parts by mass, the appearance defect or heat resistance of the molded product molded from the polycarbonate resin composition, Reduced flame retardancy. The content is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, further preferably 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 7.5 parts by mass. Hereinafter, it is more preferably 6 parts by mass or less.

[6. Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer as necessary. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10” manufactured by Adeka Corporation, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 "," JP-3CP "," Irgaphos 168 "manufactured by Ciba Specialty Chemicals, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phosphorus stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Moreover, it is 1 mass part or less normally, Preferably it is 0.7 mass part or less, More preferably, it is 0.5 mass part or less. If the content of the phosphorus stabilizer is less than or equal to the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

[7. Phenolic stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phenol-based stabilizer. As a phenol type stabilizer, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-te t- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include, for example, “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab” manufactured by Adeka. AO-60 "etc. are mentioned.
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the phenol-based stabilizer is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 1 part by mass or less, preferably 100 parts by mass of the polycarbonate resin (A). 0.5 parts by mass or less. When the content of the phenolic stabilizer is not more than the lower limit of the above range, the effect as the phenolic stabilizer may be insufficient, and the content of the phenolic stabilizer exceeds the upper limit of the above range. If this is the case, the effect may reach its peak and not economical.

[8. Lubricant]
Moreover, it is also preferable to contain a lubricant if necessary. Examples of the lubricant include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including alicyclic compounds.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the lubricant mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the lubricant is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the polycarbonate resin (A). It is as follows. When the content of the lubricant is less than or equal to the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the lubricant exceeds the upper limit of the above range, the hydrolysis resistance is reduced, injection There is a possibility of mold contamination during molding.

[9. Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of the other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) And the like; polyolefin resins such as polyethylene resins and polypropylene resins; polyamide resins; polyimide resins; polyetherimide resins; polyurethane resins; polyphenylene ether resins; polyphenylene sulfide resins;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additive Examples of the resin additive include ultraviolet absorbers, dyes and pigments, antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition of this invention is demonstrated concretely.

... Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds And organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the polycarbonate resin composition of the present invention has good transparency and mechanical properties.

Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4 (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], particularly 2- (2 ′ -Hydroxy-5'-tert-octylphenyl) benzotriazole is preferred.
Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Kemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals, “Tinuvin 327”, “Tinuvin 328” and the like can be mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by Adeka Corporation and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35” manufactured by BASF, 539 "and the like.

  Examples of the triazine compound include a compound having a 1,3,5-triazine skeleton. Specific examples of such a triazine compound include, for example, “LA-46” manufactured by ADEKA Corporation, Ciba Specialty Chemicals Co., Ltd. “Tinuvin 1577ED”, “tinuvin 400”, “tinuvin 405”, “tinuvin 460”, “tinuvin 477-DW”, “tinuvin 479”, and the like are available.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such an oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

... Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead and Molybdate Orange; Ferrocyan Pigment such as Bitumen Etc.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the dye / pigment is usually 5 parts by mass or less, preferably 3 parts by mass or less, more preferably 2 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A). If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[10. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), phosphorus flame retardant (B), fluoropolymer (C), graft copolymers (D) and (E), and other components blended as necessary. Are mixed in advance using various mixers such as tumblers and Henschel mixers, and then melt kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. Can be mentioned.

In addition, for example, without mixing each component in advance, or only a part of the components is mixed in advance, and fed to an extruder using a feeder and melt-kneaded to produce the polycarbonate resin composition of the present invention. You can also
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The polycarbonate resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

  The polycarbonate resin composition of the present invention is flame retardant by a UL94 vertical combustion test at a thickness of 0.8 mm in the UL94 test (combustion test of plastic materials for equipment parts) defined by US Underwriters Laboratories (UL). It has a high flame retardancy of V-1 or higher, that is, V-1 or V-0, preferably V-0.

[11. Molded body]
The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment.

Examples of the electric and electronic devices include display devices such as personal computers, video game machines, televisions, and electronic paper, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, and videos. Examples include a camera, a mobile phone, a battery pack, a recording medium drive and reading device, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player.
Especially, it can use suitably for the battery pack (battery case) of the portable apparatus used also in a cold region represented by a notebook personal computer, a mobile telephone, a camera, and a video camera.

The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. A molding method using a hot runner method can also be used.
As described above, the obtained molded article of the present invention has flame retardancy and impact resistance (high impact resistance even during high temperature molding and high resistance under low temperature environment without impairing the excellent properties of the polycarbonate resin as described above. It can be used as a practical molded body having impact properties.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is limited to a following example and is not interpreted.

[Production of resin pellets]
Each component described in Tables 2 and 3 to be described later is blended in proportions (mass ratios) described in Tables 4 to 5, mixed for 20 minutes with a tumbler, and manufactured by Nippon Steel Works Co., Ltd. equipped with 1 vent. Supplied to a twin screw extruder (TEX30HSST), kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 280 ° C. To obtain pellets of a polycarbonate resin composition.

[Preparation of test piece]
After drying the pellets obtained by the above production method at 80 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was injection molded under the following conditions.
Moreover, after drying the pellet obtained by said manufacturing method at 80 degreeC for 5 hours, using a Sumitomo Heavy Industries, Ltd. injection molding machine (Cycap M-2, clamping force 75T), cylinder temperature 280 ISO multipurpose test pieces (thickness 3 mm) were injection-molded under the conditions of ℃ and 330 ℃ and mold temperature of 80 ℃.

[Flame retardance evaluation]
The flame retardant evaluation of each polycarbonate resin composition was performed by conditioning the test piece for UL test (0.8 mm thickness) obtained by the above method for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%. The test was conducted in accordance with the UL94 test (combustion test of plastic materials for equipment parts) established by the US Underwriters Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.
As materials for electronic and electrical equipment casings including battery packs, it is required to have flame retardancy of V-1 or higher. Therefore, in this example and comparative example, V-0 or V-1 is acceptable. To do.

[Impact resistance evaluation]
Using the ISO multi-purpose test piece (3 mm thickness) molded at 280 ° C. obtained by the above method, in accordance with ISO 179, R = 0.25 V notch, at 23 ° C. and −30 ° C., The Charpy impact strength (unit: kJ / m ² ) with each notch was measured. Similarly, an ISO multipurpose test piece (3 mm thick) molded at 330 ° C. was measured for notched Charpy impact strength by the same method as described above under the condition of 23 ° C.

From Examples 1 to 5 shown in Table 4, polycarbonate flame retardant (B1 or B2), fluoropolymer (C), and graft copolymer (D1 or D2) and (E1 or E2) are added to the polycarbonate resin (A). The polycarbonate resin composition containing a predetermined amount of UL flame retardant exhibits excellent flame retardancy at V-0 or V-1, and has good impact resistance at -30 ° C, and at 330 ° C. It can be seen that even when high temperature molding is performed, the impact resistance is excellent.
On the other hand, the polycarbonate resin composition of the comparative example of Table 5 that does not satisfy the requirements specified in the present invention has poor flame retardancy such as NR or V-2, and in the case of V-0, impact resistance at -30 ° C. I understand that is bad.
Therefore, from the above examples and comparative examples, the effects of excellent flame resistance, impact resistance, high impact resistance even during high temperature molding, and high impact resistance even in a low temperature environment, It was confirmed that it was obtained for the first time by the configuration of the present invention.

  According to the polycarbonate resin composition of the present invention, a polycarbonate resin molding material having excellent flame retardancy, high impact resistance even at high temperature molding, and high impact resistance even in a low temperature environment can be obtained. In particular, it can be suitably used for parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and the industrial applicability is very high.

Claims (7)

3 to 30 parts by mass of the phosphorus-based flame retardant (B), 0.001 to 1 part by mass of the fluoropolymer (C), and 100 parts by mass of the polycarbonate resin (A),
A graft copolymer (D) having an average particle size of 70 to 180 nm obtained by graft copolymerization of a monomer component copolymerizable with the rubber polymer;
0.5 to 10 parts by mass in total of the graft copolymer (E) having an average particle size of more than 180 to 300 nm or less obtained by graft copolymerization of a monomer component copolymerizable with the rubber polymer. And the polycarbonate resin composition characterized by containing 10-90 mass% of (D) and 90-10 mass% of (E) on the basis of the total amount of (D) and (E).   2. The polycarbonate resin composition according to claim 1, wherein the rubber polymer is a butadiene rubber.   The polycarbonate resin composition according to claim 1 or 2, wherein the monomer component copolymerizable with the rubber polymer is a (meth) acrylic ester compound. The polycarbonate resin composition according to any one of claims 1 to 3, wherein the phosphorus-based flame retardant (B) is a phosphate ester represented by the following formula (1).

(Wherein R ¹ , R ² , R ³ and R ⁴ each represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and p, q , R and s are each 0 or 1, k is an integer of 1 to 5, and X ¹ represents an arylene group.)   The polycarbonate resin composition according to any one of claims 1 to 4, wherein flame retardancy in a UL94 vertical combustion test at a thickness of 0.8 mm is V-1 or more.   The molded object formed by shape | molding the polycarbonate resin composition in any one of Claims 1 thru | or 5.   The molded body according to claim 6, wherein the molded body is a battery pack casing.