JP5449458B2 - Polycarbonate resin composition - Google Patents

Description

  The present invention relates to a polycarbonate resin composition, and in particular, is a polycarbonate resin composition for molding a polycarbonate resin molded body having a thin-walled portion, which has high flame retardancy and impact resistance and excellent surface appearance (matte). Property).

  Polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical characteristics, and is widely used as, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. Yes. 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 a means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-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 method, many polycarbonate resin compositions containing a phosphorus-based flame retardant have been adopted (see, for example, Patent Documents 1 and 2).
Such a method of incorporating a phosphorus-based flame retardant into the polycarbonate resin can effectively shorten the combustion time by forming a film on the surface of the resin with a phosphorus compound or diluting the combustion gas in the gas phase.

  However, the polycarbonate resin blended with the phosphorus-based flame retardant significantly reduces the impact resistance inherent in the polycarbonate resin, so that the prescription blended with the elastomer is performed. The present applicant has made various proposals as disclosed in Patent Documents 3 to 7 for a polycarbonate resin composition containing such a phosphorus-based flame retardant and an elastomer.

  That is, in Patent Document 3, a polycarbonate resin that suppresses the generation of white spot foreign matter on the molding surface by blending a special flame retardant called a phosphorus flame retardant and an organic polymer-coated polyfluoroethylene with an aromatic polycarbonate resin. In Patent Document 4, a polyorganosiloxane-containing graft copolymer obtained by copolymerizing an aromatic polycarbonate resin with a phosphorus flame retardant, polyfluoroethylene, and first and second vinyl monomers at a specific ratio is disclosed in Patent Document 4. A polycarbonate resin composition containing a polymer was proposed. Patent Document 5 proposes a polycarbonate resin composition in which a phosphorus-based flame retardant, a silicone / acrylic composite rubber grafted with a vinyl monomer and an anti-dripping agent are blended in a specific ratio to an aromatic polycarbonate resin.

  In Patent Document 6, talc is essential, and the first, second, and polyfunctional vinyl-based monomers are used in the presence of a specific amount of a phosphorus-based flame retardant, polyfluoroethylene, and polyorganosiloxane particles in an aromatic polycarbonate resin. A polycarbonate resin composition was proposed in which a polyorganosiloxane-containing graft copolymer obtained by copolymerizing a monomer at a specific ratio was blended at a specific ratio. Furthermore, in Patent Document 7, a phosphorous flame retardant, a fluoropolymer, a multilayered polymer having a cross-linked polyalkylacrylate core and an alkyl (meth) acrylate polymer shell, titanium oxide, carbon black, and dye / pigment are added to a polycarbonate resin. A polycarbonate resin composition blended at a specific ratio was proposed.

JP 59-202240 A JP-A-62-2746 JP 2007-154173 A JP 2008-280491 A JP 2009-7487 A JP 2008-285507 A JP 2011-57888 A

However, in recent years, electrical and electronic equipment components have been extremely thin and miniaturized due to the trend toward miniaturization of the equipment itself. For example, battery packs used for portable terminal equipment such as tablet terminals or touch panel terminals In the case of a frame or a casing, a molded product having a thickness of 0.6 mm or less, particularly 0.3 to 0.4 mm is required. V-O to V-1 level flame retardancy is strongly required, and high fluidity and impact resistance, as well as excellent surface appearance, that is, low gloss and high-quality appearance performance are more severe. Product specifications are required.
However, the resin compositions of the above-mentioned patent documents do not always satisfy all of these requirements.
The present invention was devised in view of such problems, and is a polycarbonate resin composition for molding into a molded body having a thin-walled portion, and has high flame retardancy and impact resistance and excellent surface appearance (glossy). It is an object of the present invention to provide a polycarbonate resin composition having erasability.

In order to solve the above-mentioned problems, the present inventors have made extensive studies on a polycarbonate resin composition for molding a polycarbonate resin molded body having a thin portion with a thickness of 0.6 mm or less. It has been found that it exhibits an effect as a flame retardant, and is combined with a siloxane-based core / shell type elastomer having a specific Si content and an average particle size, and as a flame retardant, a condensed phosphate ester flame retardant and a phosphazene system High flame resistance and impact resistance and excellent surface appearance for thin-wall molding by using flame retardant in a specific ratio, and by making the outflow amount (Q value) per unit time of the resin composition into a specific range The present inventors have found that a polycarbonate resin composition having (matte properties) can be obtained and completed the present invention.
The present invention provides the following polycarbonate resin composition.

[1] A polycarbonate resin composition for molding a polycarbonate resin molded body having a thin portion having a wall thickness of 0.6 mm or less,
The total amount of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is 5 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and the siloxane core / shell type elastomer (C) 3 9.7 parts by mass, carbon black (D) 0.8 to 5 parts by mass,
The ratio of the content of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is (B1) 1 to 49% by mass: (B2) 99 to 51% by mass,
In the siloxane-based core / shell type elastomer (C), the siloxane-based core / shell type elastomer (C) has a siloxane-based rubber component as a core layer, and an acrylic or acrylonitrile-styrene (co) polymer component as a shell layer. An elastomer that has a Si content of 9.1 to 30% by mass and a number average particle size of 50 to 1000 nm,
The flow rate per unit time of the resin composition (measured under the conditions of 280 ° C. and load of 160 kgf / cm ² using an elevated flow tester according to the method described in JIS K7210 Annex C) A polycarbonate resin composition, which is 50 × 10 ⁻² cm ³ / sec.
[2] The polycarbonate resin composition according to [1], wherein the polycarbonate resin molded body is a frame or a casing of a battery pack.

（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。）
［４］さらに、含フッ素樹脂（Ｅ）を、ポリカーボネート樹脂（Ａ）１００質量部に対し、０．００１〜１質量部含有する上記［１］〜［３］のいずれかに記載のポリカーボネート樹脂組成物。 [3] The polycarbonate resin composition according to the above [1] or [2], wherein the condensed phosphate ester flame retardant (B1) is a phosphate ester represented by the following general 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.)
[4] The polycarbonate resin composition according to any one of [1] to [ 3 ], further containing 0.001 to 1 part by mass of the fluororesin (E) with respect to 100 parts by mass of the polycarbonate resin (A). object.

According to the polycarbonate resin composition of the present invention, it is a polycarbonate resin composition for a polycarbonate resin molded article having a thin wall portion, and has a high flame retardancy, impact resistance, and excellent surface appearance (matte properties). It is possible to provide a resin composition material.
Conventionally, an example of blending carbon black into a polycarbonate resin composition containing a phosphorus-based flame retardant can be seen in the above-mentioned Patent Document 7 and the like, but is blended for preventing see-through and improving appearance. As described in [0100] column of Document 7, it has been considered undesirable to increase the content. From such conventional knowledge, it is epoch-making that the flame retardancy is improved by adding carbon black in the above-mentioned amount, and has a specific Si content and particle size. By blending with siloxane-based core / shell type elastomers in specific amounts, and using combined phosphate ester flame retardants and phosphazene flame retardants in specific ratios as flame retardants, high flame resistance and resistance It is surprising that the polycarbonate resin material can have all impact properties and surface appearance.

  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.

[Overview]
The polycarbonate resin composition of the present invention is a polycarbonate resin composition for molding a polycarbonate resin molded body having a thin portion having a thickness of 0.6 mm or less,
The total amount of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is 5 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and the siloxane core / shell type elastomer (C) 3 9.7 parts by mass, carbon black (D) 0.8 to 5 parts by mass,
The proportion of the content of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is 1 to 49 mass% for (B1) and 99 to 51 mass% for (B2),
In the siloxane-based core / shell type elastomer (C), the siloxane-based core / shell type elastomer (C) has a siloxane-based rubber component as a core layer, and an acrylic or acrylonitrile-styrene (co) polymer component as a shell layer. An elastomer that has a Si content of 9.1 to 30% by mass and a number average particle size of 50 to 1000 nm,
The amount of outflow per unit time of the resin composition is 15 to 50 × 10 ⁻² cm ³ / sec.

[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.

Polycarbonate resins have the general ^{formula: - (- O-X 2} -O-C (= O) -) - represented by a polymer of a basic structure having a carbonate bond. In the formula, X ² is generally a hydrocarbon group, but for imparting various properties, X ² into which a hetero atom or a hetero bond is introduced may be used.

  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. Further, 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, 1 type may be used for an alkali compound and it 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 o-oxinebenzoic 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, carbonic acid diester may use 1 type and 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, 1 type may be used for a catalyst deactivator and it 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 making the viscosity average molecular weight not more 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 moldability can be improved and the thin-wall molding 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.

[Flame Retardant (B)]
The polycarbonate resin composition of the present invention contains, as a flame retardant, 5 to 30 parts by mass of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) with respect to 100 parts by mass of the polycarbonate resin (A). In that case, the content ratio of both is (B1) 1 to 49% by mass: (B2) 99 to 51% by mass (however, the total of both is 100% by mass). .

（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。） [Condensed phosphate ester flame retardant (B1)]
As the condensed phosphate ester flame retardant (B1), a phosphate ester compound represented by the following general formula (1) is particularly preferable.

(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 phosphate ester compound represented by the above general formula (1) may be a mixture of compounds having different numbers of k, and in the case of a mixture of phosphate esters having different k, k is a mixture of those compounds. Average value. In the case of a mixture of compounds having different k numbers, the average k number is preferably 1 to 2, more preferably 1 to 1.5, still more preferably 1 to 1.2, particularly preferably 1 to 1.15. It is a range.

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 condensed phosphate ester flame retardant represented by the general formula (1) include phenyl resorcin / polyphosphate, cresyl / resorcin / polyphosphate, phenyl / cresyl / resorcin / polyphosphate, xylyl / resorcin / polyphosphate. Phenyl-pt-butylphenyl / resorcin / polyphosphate, phenyl / isopropylphenyl / resorcin / polyphosphate, cresyl / xylyl / resorcin / polyphosphate, phenyl / isopropylphenyl / diisopropylphenyl / resorcin / polyphosphate, etc. .

  The acid value of the condensed phosphate 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. Preferably it 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 polycarbonate resin composition of the present invention tends to be deteriorated in thermal stability and hydrolysis resistance.

[Phosphazene flame retardant (B2)]
Another flame retardant contained in the polycarbonate resin composition of the present invention is a phosphazene flame retardant (B2). The phosphazene flame retardant is an organic compound having a —P═N— bond in the molecule, and preferably a cyclic phosphazene compound represented by the following general formula (2) and a chain represented by the following general formula (3). And at least one selected from the group consisting of a crosslinked phosphazene compound in which at least one phosphazene compound selected from the group consisting of the following general formula (2) and the following general formula (3) is crosslinked by a crosslinking group: One kind of compound. As the crosslinked phosphazene compound, those crosslinked by a crosslinking group represented by the following general formula (4) are preferable from the viewpoint of flame retardancy.
The phosphazene-based flame retardant (B2) has a high flame-retardant effect, and particularly when used in combination with carbon black (D), which will be described later, can exhibit excellent flame retardancy. The reduction in mechanical strength and the generation of gas can be suppressed.

（式（２）中、ｍは３〜２５の整数であり、Ｒ^１は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (2), m is an integer of 3 to 25, and R ¹ may be the same or different and represents an aryl group or an alkylaryl group.)

（式（３）中、ｎは３〜１０，０００の整数であり、Ｘは、−Ｎ＝Ｐ（ＯＲ^１）_３基又は−Ｎ＝Ｐ（Ｏ）ＯＲ^１基を示し、Ｙは、−Ｐ（ＯＲ^１）_４基又は−Ｐ（Ｏ）（ＯＲ^１）_２基を示す。Ｒ^１は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (3), n is an integer of 3 to 10,000, X represents —N═P (OR ¹ ) ₃ group or —N═P (O) OR ¹ group, Y represents — P (OR ¹ ) ₄ group or -P (O) (OR ¹ ) ₂ group is shown, R ¹ may be the same or different and represents an aryl group or an alkylaryl group.

（式（４）中、Ａは−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｌは０又は１である。）

(In the formula (4), A is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, l is 0 or 1.)

Examples of the cyclic and / or chain phosphazene compounds represented by the general formulas (2) and (3) include, for example, phenoxyphosphazene and (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, etc. Cyclic and / or chain C _1-6 alkyl C _6-20 aryloxyphosphazenes and (poly) phenoxytolyloxyphosphazenes (eg, phenoxy o-tolyloxyphosphazenes, phenoxy m-tolyloxyphosphazenes, phenoxy p-tolyloxy) Hospha Phenoxy o, m-tolyloxyphosphazene, phenoxy o, p-tolyloxyphosphazene, phenoxy m, p-tolyloxyphosphazene, phenoxy o, m, p-tolyloxyphosphazene, etc.), (poly) phenoxyxyloxyphosphazene And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene, preferably cyclic and / or chain phenoxy Phosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or chain tolyloxy) Phosphazene, cyclic and Is a or linear phenoxy tolyl phenoxyphosphazene etc.).

As the cyclic phosphazene compound represented by the general formula (2), cyclic phenoxyphosphazene in which R ¹ is a phenyl group 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. . The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (2) is 3 to 5, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less is preferable.

As the chain phosphazene compound represented by the general formula (3), chain phenoxyphosphazene in which R ¹ is a phenyl group 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. N in the general formula (3) of the linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

Examples of the crosslinked phenoxyphosphazene 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. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned.
Moreover, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (2) with a crosslinking group represented by the general formula (4), or the above A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ¹ is a phenyl group in the general formula (3) with a crosslinking group represented by the general formula (4) is preferable from the viewpoint of flame retardancy, and cyclic A crosslinked phenoxyphosphazene compound obtained by crosslinking a phenoxyphosphazene compound with a crosslinking group represented by the general formula (4) 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 (2) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (3) 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 flame retardant (B2) is preferably a cyclic phenoxyphosphazene compound represented by the above general formula (2) from the viewpoint of flame retardancy and mechanical properties.

[Contents of condensed phosphate ester flame retardant (B1) and phosphazene flame retardant (B2)]
As described above, the content of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is 5 to 30 parts by mass in total with respect to 100 parts by mass of the polycarbonate resin (A). . When the content is less than 5 parts by mass, the flame retardancy is insufficient, and when it exceeds 30 parts by mass, a significant decrease in heat resistance and a decrease in mechanical properties are caused.
Moreover, the content ratio of (B1) and (B2) is (B1) 1-49 mass% and (B2) 99-51 mass% on the basis of the total of 100 mass% of (B1) and (B2). . When the content ratio of (B2) is less than 51% by mass, a decrease in heat resistance and a significant decrease in mechanical properties are caused. A preferable content rate is (B1) 5-45 mass%: (B2) 95-55 mass%.

The content of the condensed phosphate ester flame retardant (B1) is preferably 1 part by mass or more and preferably 20 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).
The content of the phosphazene flame retardant (B2) is preferably 9 parts by mass or more and preferably 25 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (A).

[Siloxane-based core / shell type elastomer (C)]
The polycarbonate resin composition of the present invention contains a siloxane-based core / shell type elastomer (C) as an elastomer, but the Si content is 9.1 to 30% by mass, and the number average particle diameter is 50 to 1000 nm. Some siloxane based core / shell elastomers are used.
In the present invention, such a siloxane-based core / shell type elastomer (C) is used in combination with a condensed phosphate ester-based flame retardant (B1), a phosphazene-based flame retardant (B2), and carbon black (D). In addition, by properly balancing the Si content and the carbon black content at this time, it is possible to obtain a polycarbonate resin composition having excellent impact resistance while having high flame retardancy and excellent surface appearance. It becomes possible.

  As the siloxane-based core / shell type elastomer (C), a silicone rubber polymer is used as a core layer, and an acrylic polymer or copolymer component such as an acrylic ester or a methacrylic ester is formed around the core layer. Alternatively, a core / shell type elastomer having an acrylonitrile-styrene copolymer component as a shell layer is particularly preferable.

The silicone rubber constituting the core layer is preferably a polyorganosiloxane, for example, a polymer containing a dimethylsiloxane unit as a constituent unit or a siloxane containing a vinyl polymerizable functional group as a constituent component.
A siloxane containing a vinyl polymerizable functional group is one that contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. Among the siloxanes containing vinyl polymerizable functional groups, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferable in consideration of reactivity with dimethylsiloxane. These siloxanes containing vinyl polymerizable functional groups can be used alone or as a mixture of two or more.
The polyorganosiloxane may be crosslinked with a siloxane-based crosslinking agent. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

The component constituting the shell of the siloxane-based core / shell type elastomer (C) includes acrylic, preferably polyalkyl (meth) acrylate, and includes an alkyl (meth) acrylate unit and a polyfunctional alkyl (meta) ) A polymer containing an acrylate unit as a constituent component is preferred.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and alkyl methacrylates such as 2-ethylhexyl methacrylate and n-lauryl methacrylate. Or two or more can be used together.

Examples of the polyfunctional alkyl (meth) acrylate include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and the like. These can be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in content of a polyfunctional alkyl (meth) acrylate unit, It is preferable that it is 0.1-2.0 mass% in 100 mass% of polyalkyl (meth) acrylate, 0.3- More preferably, it is 1.0 mass%.

  Moreover, as a component which comprises the shell of a siloxane type core / shell type elastomer (C), an acrylonitrile styrene type copolymer is also mentioned as a preferable component.

  There are no particular limitations on the production of the siloxane-based core / shell type elastomer (C). Usually, the alkyl (meth) acrylate component and the polyfunctional alkyl (meth) acrylate component are contained in the latex of the polyorganosiloxane component. Or a radical polymerization initiator such as a redox polymerization initiator in which an acrylonitrile component and a styrene component are added and a peroxide, an azo initiator, or an oxidizing agent / reducing agent is combined, preferably a redox polymerization initiator. A method of producing by emulsion graft polymerization or the like is preferred.

  The number average particle diameter of the siloxane-based core / shell type elastomer (C) used in the present invention is 1000 nm or less, preferably 800 nm or less, more preferably 650 nm or less. The lower limit is 50 nm or more, preferably 80 nm or more, and more preferably 100 nm or more. By making the number average particle diameter of the siloxane-based core / shell type elastomer (C) in such a range, the impact resistance, heat resistance and appearance of the molded product can be improved.

The number average particle diameter of the siloxane-based core / shell type elastomer (C) in the present invention is a siloxane-based core / shell type dispersed in the matrix polycarbonate resin (A) by observation with a transmission electron microscope (TEM). This is a value obtained by measuring the primary particle size of the elastomer (C).
Specifically, for example, it can be obtained in the following manner.
An ultra-thin section having a thickness of 100 nm cut out from the resin composition pellet of the present invention was further stained with osmium tetroxide vapor for 60 minutes and further with ruthenium tetroxide vapor for 60 minutes, and then observed with TEM and obtained by TEM observation. Using the obtained image, the primary particle diameter (average diameter) of 50 siloxane-based core / shell type elastomers (C) dispersed in the matrix is measured, and the number average is defined as the number average particle diameter in the present invention.

Further, the Si content of the siloxane-based core / shell type elastomer (C) needs to be 9.1 to 30% by mass, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass. Or less, more preferably 15% by mass or less, and particularly preferably 12% by mass or less. By making Si content into such a range, impact resistance, heat resistance, and a molded article external appearance can be made favorable. Adjustment of Si content can be easily performed by adjusting the quantity of the silicone type rubber | gum at the time of manufacturing a siloxane type core / shell type elastomer (C).
The Si content of the siloxane-based core / shell elastomer (C) is measured as a value detected by inductively coupled plasma emission analysis (ICP / AES method).

  Content of a core / shell type elastomer (C) is 3-9.7 mass parts with respect to 100 mass parts of polycarbonate resin (A). When the content of the core / shell type elastomer (C) is smaller than 3 parts by mass, the impact resistance improving effect is insufficient, and when the content exceeds 9.7 parts by mass, the flame retardancy is deteriorated. To do.

[Carbon black (D)]
The polycarbonate resin composition of the present invention contains 0.8 to 5 parts by mass of carbon black (D) with respect to 100 parts by mass of the polycarbonate resin (A). As described above, conventionally, carbon black is usually blended for coloring purposes, but in the present invention, carbon black is blended as a component for improving the flame-retardant effect. Therefore, the amount of carbon black (D) in the present invention expresses more performance when blended in a larger amount than the conventional blending amount, and 0.8 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Add more amount. Conventionally, it has been considered undesirable to increase the amount of carbon black, but the use of such a high amount is specific in the resin composition of the present invention.

  Carbon black (D) used in the present invention is not limited in its kind, raw material type, and production method, and any of furnace black, channel black, acetylene black, ketjen black, and the like can be used. The number average particle diameter is not particularly limited, but is preferably about 5 to 60 nm. By using carbon black having a number average particle diameter in such a range, it becomes easy to obtain a composition in which blisters hardly occur at high temperatures.

Nitrogen adsorption specific surface area of the carbon black (D) ^{(unit: m} 2 / g) is preferably usually less than 1000 m ² / g, is preferably Among them 50 to 400 m ² / g. By making the nitrogen adsorption specific surface area less than 1000 m ² / g, the flowability of the polycarbonate resin composition of the present invention and the appearance of the molded product tend to be improved, which is preferable. The nitrogen adsorption specific surface area is JIS
It can be measured according to K6217.

The DBP (dibutyl phthalate) absorption amount of carbon black (D) ^is preferably less than 300 cm 3/100 g, is preferably Among them 30~200cm ³ / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, preferably tends to increase the appearance of fluidity and a molded article of the polycarbonate resin composition of the present invention.
Incidentally, DBP absorption ^(unit: cm 3 / 100g) can be measured according to JIS K6217. The carbon black used in the present invention is not particularly limited with respect to its pH, but it is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

  Carbon black (D) can be used alone or in combination of two or more. Furthermore, carbon black can be granulated using a binder, and can also be used in a masterbatch that is melt-kneaded at a high concentration in another resin. By using the melt-kneaded master batch, the handling property during extrusion and the dispersibility improvement in the resin composition can be achieved. Examples of the resin include polystyrene resin, polycarbonate resin, acrylic resin, and the like.

  As described above, the content of carbon black (D) is 0.8 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), preferably 0.9 parts by mass or more, more preferably It is 1 part by mass or more, preferably 4 parts by mass or less, more preferably 3 parts by mass or less.

[Fluorine-containing resin (E)]
It is preferable that the polycarbonate resin composition of this invention contains a fluorine-containing resin (E), and it is preferable that the quantity is 0.001-1 mass part with respect to 100 mass parts of polycarbonate resin (A). One type of fluorine-containing resin (E) may be used, or two or more types may be used in any combination and in any ratio. By containing the fluorine-containing resin in this way, the melting characteristics of the resin composition can be improved, and the dripping prevention property during combustion can be improved.

  If the content of the fluorine-containing resin (E) is less than 0.001 part by mass, the effect of improving flame retardancy tends to be insufficient, and if it exceeds 1 part by mass, the molded product obtained by molding a thermoplastic resin composition Appearance defects and mechanical strength are likely to decrease. The lower limit of the content is more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, particularly preferably 0.1 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). The upper limit of the content is more preferably 0.9 parts by mass or less, further preferably 0.8 parts by mass or less, and particularly preferably 0.6 parts by mass or less.

As the fluorine-containing resin (E), a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as this fluorine-containing resin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Moreover, an organic polymer covering fluoroolefin resin can also be used suitably as a fluorine-containing resin (E). By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

  From the viewpoint of dispersibility when blended with a polycarbonate resin, a monomer having a high affinity with the polycarbonate resin is preferable as the monomer for producing the organic polymer that coats the fluoroolefin resin. Monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers are more preferred.

[Phosphorus stabilizer]
The polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, 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.

[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 “Irganox 1010” and “Irganox 1076” manufactured by Ciba Specialty Chemicals, “Adekastab AO-50” and “Adekastab AO” manufactured by Adeka. -60 "and the like.
In addition, 1 type may be contained for the phenol type stabilizer, and 2 or more types may be contained by arbitrary combinations and ratios.

  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.

[Lubricant]
Further, the polycarbonate resin composition of the present invention preferably contains a lubricant (release agent). 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 and comprise one ester may each be used 1 type, and may use 2 or more types together by arbitrary combinations and a 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.

[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;
Styrenic resin such as polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin); polyolefin resin such as polyethylene resin and polypropylene resin; polyamide resin; polyimide resin; polyetherimide resin; Polyphenylene ether resin; polyphenylene sulfide resin; polysulfone resin; polymethacrylate resin and the like.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and a ratio.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. 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, Examples include 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”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinubin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals , “Tinuvin 327”, “tinuvin 328”, etc.

  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 ”,“ Chemsorb 21 ”,“ Chemsorb 22 ”manufactured by Chemipro Kasei Co., Ltd.

  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”, “Ubinur N-N-” 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. “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 acid 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.

[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), condensed phosphate ester flame retardant (B1), phosphazene flame retardant (B2), siloxane core / shell elastomer (C) and carbon black (D), and Other ingredients to be blended as necessary are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader Examples of the method include melt kneading with a mixer such as the above.

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.

[Outflow (Q value) per unit time of resin composition]
The polycarbonate resin composition of the present invention conforms to the method described in JIS K7210 Appendix C, and uses an elevated flow tester to measure the amount of effluent per unit time measured under the conditions of 280 ° C. and a load of 160 kgf / cm ² ( Q value) is 15 × 10 ⁻² to 50 × 10 ⁻² cm ³ / sec. The Q value is preferably 18 × 10 ⁻² to 40 × 10 ⁻² cm ³ / sec, and more preferably 20 × 10 ⁻² to 30 × 10 ⁻² cm ³ / sec. By making Q value into such a range, the polycarbonate resin molding which has a thin part can be shape | molded in the state provided with the high flame retardance and impact resistance, and the outstanding surface appearance.
The Q value can be adjusted by adjusting the type and molecular weight of the polycarbonate resin (A) and the siloxane-based core / shell elastomer (C), the conditions for melt-kneading, and the like according to a known method. is there.

[Molded body]
The obtained polycarbonate resin composition is used as a molded body having a thin part with a thickness of 0.6 mm or less. Since the polycarbonate resin composition of the present invention is excellent in fluidity, particularly thin wall fluidity, it is possible to reduce the thickness to a level of 0.6 mm or less. The thickness of the thin portion is preferably 0.5 mm or less, more preferably 0.4 mm or less, and the upper limit is usually 0.2 mm or more.
The molded body having a thin portion may have a thin portion having a thickness of 0.6 mm or less at least partially, and there is no limitation on the shape, size, and the like.

  Examples of the molded body include parts such as electric / 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, and particularly suitable for use in parts such as electrical and electronic equipment.

  Examples of the electric / electronic devices include display devices such as personal computers, 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 tablet terminal, a touch panel terminal, a battery pack for these, a drive and reading device for a recording medium, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player. Especially, it can use suitably for the frame or housing | casing of the battery pack of the portable device represented by the tablet-type terminal or the touch panel type terminal.

  The manufacturing method of a molded object can employ | adopt arbitrarily the shaping | molding method generally employ | adopted about the polycarbonate resin composition. 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, and a molding method using a hot runner method can also be used. Of these, injection molding methods such as injection molding, ultra-high speed injection molding, and injection compression molding are preferred.

  In particular, in order to mold a molded product having a thin portion using the polycarbonate resin composition of the present invention, the molding surface in the cavity is made of a material having a thermal conductivity of 0.3 to 6.3 W / m · K. It is preferable to mold using a mold (hereinafter, this mold may be referred to as “heat-insulating mold”). By using such a heat-insulating mold, the composition component is prevented from floating on the surface of the molded product due to the rapid cooling of the resin composition in the mold cavity during thin-wall molding, and a transparent resin layer is formed on the surface of the molded product. By improving the transferability of the mold surface, it is possible to enhance the transparency and further improve the appearance of the molded product.

Such a heat insulating mold is preferably a molding surface in the cavity, and a molding surface corresponding to at least the largest of the contour constituent surfaces of the outer surface of the resin molded product has a thermal conductivity of 0.3 to 6. A mold composed of a material of 3 W / m · K, for example, various materials having the above-described thermal conductivity on the inner surface of the cavity, for example, zirconia-based material, alumina-based material, K ₂ O—TiO ₂ Those coated with a coating material such as various types of glass selected from the group of ceramics, soda glass, quartz glass, heat-resistant glass, and crystallized glass selected from the group can be used. Specific examples of the ceramics include ZrO ₂ , ZrO ₂ —CaO, ZrO ₂ —Y ₂ O ₃ , ZrO ₂ —MgO, ZrO ₂ —SiO ₂ , K ₂ O—TiO ₂ , Al ₂ O ₃ , Al _2. Examples include O ₃ —TiC, Ti ₃ N ₂ , 3Al ₂ O ₃ -2SiO ₂ , MgO—SiO ₂ , 2MgO—SiO ₂ , MgO—Al ₂ O ₃ —SiO ₂ , and the coating materials include ZrO ₂ and ZrO. Any material selected from the group of _2- Y ₂ O ₃ , quartz glass, and crystallized glass is preferable.

  The structure of the covering material may be, for example, any of a coating structure, a thermal spray structure, and a sticking structure (ie, a nesting type) depending on the type of material. Moreover, although the thickness of a coating | covering material also depends on heat conductivity and said structure, it is 0.1-10 mm normally, Preferably it is 0.5-5 mm. Moreover, the surface roughness of a coating | covering material is 0.01-15 micrometers normally as Rz.

  Furthermore, a metal layer can be provided in order to improve the scratch resistance of the mold surface layer and increase the surface hardness. In this case, the metal layer is made of at least one material selected from the group consisting of Cr materials such as Cr and Cr alloys, Cu materials such as Cu and Cu alloys, Ni materials such as Ni and Ni alloys, The metal layer may be composed of one layer or a plurality of layers. Specific examples of the Cr alloy include a nickel-chromium alloy. Specific examples of the Cu alloy include a copper-zinc alloy, a copper-cadmium alloy, and a copper-tin alloy. Further, as the Ni alloy, specifically, nickel-phosphorus alloy (Ni-P alloy), nickel-iron alloy, nickel-cobalt alloy, nickel-tin alloy, nickel-iron-phosphorus alloy (Ni-Fe- P-based alloy) and nickel-cobalt-phosphorous alloy (Ni-Co-P-based alloy). When high scratch resistance is required for the metal layer, for example, the metal layer is preferably composed of a chromium (Cr) material. On the other hand, the metal layer is not required to have much scratch resistance, but when the thickness is required, for example, the metal layer is preferably made of a copper (Cu) material. Furthermore, when the metal layer is required to have a certain degree of scratch resistance and also needs a thickness, for example, the metal layer is preferably made of a nickel (Ni) material. Further, when the metal layer is required to have a thickness and surface hardness is required, the metal layer has a two-layer structure, for example, the lower layer is formed of a copper (Cu) material or a nickel (Ni) material. It is preferable to adjust the thickness to a desired thickness, while the upper layer is preferably made of a thin chromium (Cr) material.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

[Production of resin pellets]
Each component described in Table 1 was blended in the ratio (mass ratio) described in Table 3 below, mixed for 20 minutes with a tumbler, and then a twin screw extruder (TEX30HSST) manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. , Kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 280 ° C., the molten resin extruded into a strand is quenched in a water tank, pelletized using a pelletizer, and polycarbonate resin composition A product pellet was obtained.

[Flame retardancy evaluation UL94 test]
After drying the pellets obtained by the above-mentioned manufacturing method at 80 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Machine Co., Ltd., a cylinder temperature of 290 ° C., and a heat insulating mold in which the molding surface is coated with zirconia ceramics Was used for injection molding under the conditions of a mold temperature of 90 ° C., and a test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 0.5 mm was formed.
The flame resistance of each polycarbonate resin composition was evaluated by conditioning the test specimen for UL test obtained by the above method for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic materials for equipment parts) defined by 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 2 below.

ここで残炎時間とは、着火源を遠ざけた後の、試験片の有炎燃焼を続ける時間の長さである。また、ドリップによる綿着火とは、試験片の下端から約３００ｍｍ下にある標識用の綿が、試験片からの滴下（ドリップ）物によって着火されるかどうかによって決定される。さらに、５試料のうち、１つでも上記基準を満たさないものがある場合、Ｖ−２を満足しないとしてＮＲ（Ｎｏｔ Ｒａｔｅｄ）と評価した。
結果を表３に示す。なお、表中、「ＵＬ難燃性」と表記する。

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.
The results are shown in Table 3. In the table, “UL flame retardancy” is indicated.

[Appearance evaluation of molded products]
The UL test specimen (0.5 mm thickness) obtained above was visually observed, and appearance evaluation was determined according to the following criteria.
○: Good matte property.
X: Glossy and defective.
The results are shown in Table 3. In the table, it is expressed as “appearance evaluation”.

[Impact resistance evaluation Charpy impact strength (unit: kJ / m ² )]
Based on ISO179-1 and 179-2, it measured in the following procedures.
The obtained pellet was 3 mm based on ISO 179-1, 2 on an injection molding machine (“SG75MII” manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 45 seconds. Thick notched impact resistance test pieces were prepared, and Charpy impact strength (kJ / m ² ) was measured at a temperature of 23 ° C. The larger the value, the better the impact resistance.
The results are shown in Table 3. In the table, “Charpy” is indicated.

[Heat resistance evaluation DTUL (deflection temperature under load) (unit: ° C)]
After the obtained pellets were dried at 80 ° C. for 5 hours, the cylinder temperature was 280 ° C., the mold temperature was 80 ° C. with an injection molding machine (Sumitomo Heavy Industries, Psycap M-2, clamping force 75T), Injection molding was performed under the condition of a molding cycle of 50 seconds, a 4 mm-thick ISO multipurpose test piece was prepared, and the measurement was performed under the condition (Method A) under a load of 1.80 MPa according to ISO75-1 & 2.
The results are shown in Table 3. In the table, “DTUL” is used.

[Outflow per unit time Q value (unit: × 10 ⁻² cm ³ / sec)]
After drying the pellets obtained by the production method described later at 80 ° C. for 4 hours or more, using an elevated flow tester, the effluent Q value per unit time (unit: 280 ° C., load 160 kgf) : × 10 ⁻² cm ³ / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used.
The results are shown in Table 3. In the table, it is expressed as “Q value”.

From Examples 1 to 5 shown in Table 3, to the polycarbonate resin (A), the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2), the siloxane core / shell type elastomer defined in the present invention ( It can be seen that the polycarbonate resin composition containing a predetermined amount of each of C) and carbon black (D) has high flame retardancy and impact resistance and excellent surface appearance (matte properties).
On the other hand, it can be seen that the polycarbonate resin composition of the comparative example that does not satisfy the requirements defined in the present invention has poor flame retardancy and poor impact resistance and appearance.
Therefore, from the above examples and comparative examples, the effects of having high flame retardancy and impact resistance and excellent surface appearance (matte properties) in thin-wall molding can be obtained for the first time by the configuration of the present invention. Was confirmed.

  The polycarbonate resin composition of the present invention is a polycarbonate resin material for thin wall molding having high flame retardancy and impact resistance and excellent surface appearance (matte property), particularly electric and electronic equipment, OA equipment, information terminal equipment. It can be used widely and suitably for parts such as home appliances, and industrial applicability is particularly high.

Claims (4)

A polycarbonate resin composition for molding a polycarbonate resin molded body having a thin portion with a wall thickness of 0.6 mm or less,
The total amount of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is 5 to 30 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A), and the siloxane core / shell type elastomer (C) 3 9.7 parts by mass, carbon black (D) 0.8 to 5 parts by mass,
The ratio of the content of the condensed phosphate ester flame retardant (B1) and the phosphazene flame retardant (B2) is (B1) 1 to 49% by mass: (B2) 99 to 51% by mass,
In the siloxane-based core / shell type elastomer (C), the siloxane-based core / shell type elastomer (C) has a siloxane-based rubber component as a core layer, and an acrylic or acrylonitrile-styrene (co) polymer component as a shell layer. An elastomer that has a Si content of 9.1 to 30% by mass and a number average particle size of 50 to 1000 nm,
The flow rate per unit time of the resin composition (measured under the conditions of 280 ° C. and load of 160 kgf / cm ² using an elevated flow tester according to the method described in JIS K7210 Annex C) A polycarbonate resin composition, which is 50 × 10 ⁻² cm ³ / sec.   The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin molded body is a frame or a casing of a battery pack. The polycarbonate resin composition according to claim 1 or 2, wherein the condensed phosphate ester flame retardant (B1) is a phosphate ester represented by the following general 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.) Furthermore, the polycarbonate resin composition in any one of Claims 1-3 which contains 0.001-1 mass part of fluororesin (E) with respect to 100 mass parts of polycarbonate resin (A).