JP5540758B2 - Polycarbonate resin composition and molded body - Google Patents

Description

  The present invention relates to a polycarbonate resin composition and a molded body comprising the same. More specifically, the present invention relates to a polycarbonate resin composition having an excellent balance of flame retardancy, impact resistance, brightness, and weather resistance, and an electronic housing for outdoor use comprising the same.

  Polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, as automotive materials, electrical and electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. In particular, since it has excellent impact resistance, it has been widely used for members used in outdoor environments.

  However, the polycarbonate resin is difficult to say in weather resistance (light resistance), and has a drawback that the continuous use in an outdoor environment easily causes discoloration mainly due to yellowing and deteriorates the design of the product. .

On the other hand, the technique of mix | blending an ultraviolet absorber with polycarbonate resin conventionally is known (refer patent document 1). By blending such an ultraviolet absorber, discoloration during outdoor exposure can be suppressed or delayed. Among these, a benzotriazole-based ultraviolet absorber is selected as the ultraviolet absorber to be blended with the polycarbonate from the balance between the initial hue and the weather resistance.

  However, a polycarbonate resin composition containing a benzotriazole-based ultraviolet absorber has an excellent initial hue, but has insufficient weather resistance. In products used in an outdoor environment, it often becomes a problem that the color is changed from the initial hue by exposure to outdoor light. The degree of discoloration varies depending on the color, but light colors such as light gray and beige that are widely used in industrial products are remarkably discolored, and the product appearance is remarkably deteriorated.

  On the other hand, a polycarbonate resin composition in which a triazine ultraviolet absorber is blended with a polycarbonate resin has also been proposed (see Patent Document 2). However, even with such a polycarbonate resin composition, the weather resistance is still inadequate, and the flame retardancy required for electrical / electronic component casings and the like that are expected to be used outdoors is also insufficient. It was.

JP-A-7-216206 JP 2002-114902 A

  The present invention has been made in view of the above problems, and an object thereof is to provide a polycarbonate resin composition excellent in the balance of flame retardancy, impact resistance, lightness, and weather resistance, and a molded body thereof.

  The inventors of the present invention have intensively studied to solve the above problems, and as a result, the polycarbonate resin contains a predetermined amount of an organic sulfonic acid metal salt, a butadiene-based graft copolymer, and a specific triazine-based ultraviolet absorber. The present inventors have found that a polycarbonate resin composition having extremely high flame retardancy and also excellent in impact resistance and weather resistance can be obtained.

That is, the polycarbonate resin composition of the present invention comprises 0.001 to 2 parts by mass of an organic sulfonic acid alkali metal salt (B) and 0.01 to 1 fluoropolymer (C) with respect to 100 parts by mass of the polycarbonate resin (A). Parts by mass, 0.5 to 10 parts by mass of the butadiene-based graft copolymer (D), and the following formulas (1) , (2), (7), (8), (9), (10), ( 11), (12), and a hydroxyphenyl triazine type ultraviolet absorber (E) 0.001 to 1 part by mass selected from at least one selected from the group of (13) .

［式（１）中、Ｒ^１は、炭素数１〜３０の炭化水素基を示し、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、
Ｒ^６、Ｒ^７及びＲ^８は、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１〜３０の炭化
水素基からなる群より選ばれる少なくとも１種を示す。］

[In the formula (1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ represent at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, and a hydrocarbon group having 1 to 30 carbon atoms. ]

In this case, it is also preferable to contain 0.0001 to 1 part by mass of a phosphorus stabilizer and / or a phenolic stabilizer with respect to 100 parts by mass of the polycarbonate resin, and 0.0001 to 0.01 parts by mass of the dye / pigment. It is also preferable to contain -5 mass parts.

The hydroxyphenyltriazine-based ultraviolet absorber is preferably an ultraviolet absorber represented by the following general formula (2).

Furthermore, the butadiene-based graft copolymer is a core / shell composed of a core composed of a butadiene-based rubber and a shell composed of at least one selected from an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic ester compound. It is also preferable that it is a type | mold graft copolymer, and it is also preferable that a dyeing pigment is a titanium oxide.

  Moreover, the electronic device casing for outdoor use in the present invention is formed by molding the polycarbonate resin composition described above.

  According to the polycarbonate resin composition and the molded body of the present invention, flame retardancy, impact resistance, lightness, and weather resistance can be enhanced at the same time, and even when exposed to outdoor light, discoloration from the initial hue is sufficient. Can be suppressed.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

[1. Overview]
The polycarbonate resin composition of the present invention comprises at least a polycarbonate resin (A), an alkali metal sulfonic acid alkali metal salt (B), a fluoropolymer (C), a butadiene-based graft copolymer (D), and a hydroxyphenyltriazine. System ultraviolet absorber (E). Moreover, the polycarbonate resin composition of this invention may contain the other component as needed.

[2. Polycarbonate resin]
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.
Among them, it is preferable to use a polycarbonate resin having a structural viscosity index N in a predetermined range at a certain ratio or more.

  The polycarbonate resin in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the following general formula (3).

In formula (3), X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or 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. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. The polycarbonate polymer may be linear or branched. Further, the polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

  Among monomers used as raw materials for aromatic polycarbonate resins, examples of aromatic dihydroxy compounds include:

Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;

Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

-Other matters regarding the polycarbonate resin The molecular weight of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably Is 17000 or more, and is usually 40000 or less, preferably 30000 or less, more preferably 24000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

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

  The terminal hydroxyl group concentration of the polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1000 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.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the polycarbonate resin. 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 1500 or more, preferably 2000 or more, and is usually 9500 or less, preferably 9000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

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

[3. Organic sulfonic acid metal salt]
The polycarbonate resin composition of the present invention contains an organic sulfonic acid metal salt. By containing the organic sulfonic acid metal salt as described above, the flame retardancy of the polycarbonate resin composition of the present invention can be improved, and surprisingly, the weather resistance of the polycarbonate resin composition of the present invention is effectively improved. Can be increased.

  The types of metals possessed by organic sulfonic acid metal salts include alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); magnesium (Mg), calcium (Ca ), Alkaline earth metals such as strontium (Sr), barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Zinc (Zn), zirconium (Zr), molybdenum (Mo) and the like can be mentioned, among which alkali metals or alkaline earth metals are preferable. The polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further increase the flame retardancy, and the mechanical properties such as impact resistance of the polycarbonate resin, heat resistance, electrical characteristics, etc. This is because the properties can be maintained well. Therefore, the organic sulfonic acid metal salt is preferably at least one metal salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, more preferably alkali metal salts, sodium, potassium, cesium. Is particularly preferred.

  Examples of such organic sulfonic acid metal salts include organic sulfonic acid lithium (Li) salt, organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, organic sulfonic acid rubidium (Rb) salt, Examples thereof include cesium (Cs) organic sulfonate, magnesium (Mg) organic sulfonate, calcium (Ca) organic sulfonate, strontium (Sr) organic sulfonate, and barium (Ba) organic sulfonate. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt compound, and organic sulfonic acid cesium (Cs) salt compound are particularly preferable.

  Preferred examples of organic sulfonic acid metal salts include fluorine-containing aliphatic sulfonic acid metal salts, fluorine-containing aliphatic sulfonic acid imide metal salts, aromatic sulfonic acid metal salts, and aromatic sulfonamide metal salts. Is mentioned. Among them, specific examples of preferable ones include potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, Alkali metal salts of fluorine-containing aliphatic sulfonic acids having at least one C—F bond in the molecule, such as potassium trifluoromethanesulfonate, potassium perfluoroethanesulfonate, potassium perfluoropropanesulfonate;

At least one CF in the molecule, such as magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, magnesium trifluoromethane sulfonate, calcium trifluoromethane sulfonate, barium trifluoromethane sulfonate, etc. An alkaline earth metal salt of a fluorine-containing aliphatic sulfonic acid having a bond;

Disodium perfluoromethane disulfonate, dipotassium perfluoromethane disulfonate, sodium perfluoroethane disulfonate, dipotassium perfluoroethane disulfonate, dipotassium perfluoropropane disulfonate, dipotassium perfluoroisopropane disulfonate, dipotassium perfluorobutane disulfonate Fluorine-containing aliphatic sulfonic acid such as sodium, alkali metal salt of fluorine-containing aliphatic disulfonic acid having at least one C—F bond in the molecule, such as dipotassium perfluorobutane disulfonate and dipotassium perfluorooctane disulfonate; Metal salts,

Bis (perfluoropropanesulfonyl) imide lithium, bis (perfluoropropanesulfonyl) imide sodium, bis (perfluoropropanesulfonyl) imide potassium, bis (perfluorobutanesulfonyl) imide lithium, bis (perfluorobutanesulfonyl) imide sodium, In the molecule, such as potassium bis (perfluorobutanesulfonyl) imide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane, etc. An alkali metal salt of a fluorine-containing aliphatic disulfonic imide having at least one C—F bond;

Cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide lithium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide sodium, cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide potassium An alkali metal salt of a cyclic fluorinated aliphatic sulfonimide having at least one C—F bond in the molecule; a metal salt of a fluorinated aliphatic sulfonic imide, such as

Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule An alkaline earth metal salt of an aromatic sulfonic acid having an aromatic group of: an aromatic sulfonic acid metal salt, etc.

Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonamides such as alkali metal salts of aromatic sulfonamides having at least one aromatic group in the molecule, such as salts.

Among the examples described above, fluorine-containing aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts are more preferable, and fluorine-containing aliphatic sulfonic acid metal salts are particularly preferable.
The fluorine-containing aliphatic sulfonic acid metal salt is more preferably an alkali metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, and particularly preferably an alkali metal salt of perfluoroalkanesulfonic acid. Specifically, potassium perfluorobutane sulfonate is preferred. As the aromatic sulfonic acid metal salt, an alkali metal salt of an aromatic sulfonic acid is more preferable, and diphenylsulfone-sulfonic acid alkali metal such as diphenylsulfone-3,3′-disulfonic acid dipotassium, diphenylsulfone-3-sulfonic acid potassium, etc. Particularly preferred are salts; sodium paratoluenesulfonate, and alkali metal salts of paratoluenesulfonic acid such as potassium paratoluenesulfonate and cesium paratoluenesulfonate, and more preferably alkali metal salts of paratoluenesulfonic acid.
In addition, 1 type may be used for organic sulfonic acid metal salt, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the organic sulfonic acid metal salt in the polycarbonate resin composition of the present invention is 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.03 part by mass with respect to 100 parts by mass of the polycarbonate resin. Part or more, particularly preferably 0.05 part by weight or more, 2 parts by weight or less, preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, particularly preferably 0.3 parts by weight or less. If the content of the organic sulfonic acid metal salt is too small, the flame retardancy and weather resistance of the obtained polycarbonate resin composition may be insufficient. Conversely, if the content is too large, the thermal stability of the polycarbonate resin is reduced. In addition, the appearance of the molded product may be poor and the mechanical strength may be reduced.

[4. Fluoropolymer]
The polycarbonate resin composition of the present invention contains a fluoropolymer. Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing a fluoropolymer.

  There is no restriction | limiting in the kind of fluoropolymer used for the polycarbonate resin composition of this invention. Moreover, 1 type may be used for a fluoropolymer and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

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

  Examples of the fluoroethylene resin having fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemicals, “Polyflon F201L”, “Polyflon F103”, “Polyflon FA500B” manufactured by Daikin Chemical Industries, Ltd. Can be mentioned. Further, as commercially available products of aqueous dispersions of fluoroethylene resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Teflon (registered trademark) 31-JR” manufactured by Daikin Chemical Industries, Ltd. 1 "etc. are mentioned. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the fluoropolymer is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight or more, and usually 1 part by weight with respect to 100 parts by weight of the polycarbonate resin. Part or less, preferably 0.75 part by weight or less, more preferably 0.5 part by weight or less. When the fluoropolymer content is less than or equal to the lower limit of the above range, the flame retardant improvement effect by the anti-drip agent may be insufficient, and the anti-drip agent content exceeds the upper limit of the above range. May cause a poor appearance or a decrease in mechanical strength of a molded product obtained by molding the polycarbonate resin composition.

[5. Butadiene-based graft copolymer]
The polycarbonate resin composition of the present invention contains a butadiene-based graft copolymer. By containing a butadiene-based graft copolymer, the impact resistance of the polycarbonate resin composition can be improved. Conventionally, it has been considered that when a butadiene-based graft copolymer is blended with a polycarbonate resin, flame retardancy and weather resistance are lowered. However, in the polycarbonate resin composition of the present invention, the butadiene-based graft copolymer is organic. When blended with the sulfonic acid metal salt and the triazine-based UV absorber, the flame retardancy and weather resistance are surprisingly improved.

  The butadiene-based graft copolymer of the present invention is obtained by graft copolymerization of a rubber component (butadiene-based rubber) containing at least a butadiene component and a monomer component copolymerizable therewith. As the rubber component, the butadiene rubber may be used alone or in combination with two or more other rubbers.

The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Ethylene-α olefins such as silicone rubber, butadiene-acrylic composite rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber System rubber, ethylene-acrylic rubber, fluorine rubber and the like.
These may be used alone or in admixture of two or more, but it is necessary to contain at least butadiene.
Among these, polybutadiene rubber and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance.

Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more.
Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

Preferable specific examples of these graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and acrylonitrile-butadiene-styrene copolymer (ABS). ), Methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acryl-butadiene rubber copolymer, methyl methacrylate-acryl-butadiene rubber-styrene copolymer, and the like. Such rubbery polymers may be used alone or in combination of two or more.

The graft copolymer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among these, a core / shell type graft copolymer comprising a shell layer formed by using polybutadiene-containing rubber as a core layer and copolymerizing (meth) acrylic acid ester around it is particularly preferable.

The method for producing the graft copolymer may be any method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft. Good.

The butadiene content of the graft copolymer of the present invention is preferably 50% by mass or more, more preferably 55% by mass or more, further preferably 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass. Hereinafter, it is more preferably 85% by mass or less. By setting the butadiene content within the above range, flame retardancy and impact resistance can be dramatically improved.
If the butadiene content is below the lower limit, the flame retardancy and impact resistance improvement effects may be insufficient, and if the butadiene content exceeds the upper limit of the above range, the graft copolymer polycarbonate The dispersibility in the resin is extremely lowered, and there is a possibility that the impact resistance of the polycarbonate resin composition of the present invention is lowered and the appearance is poor.

Examples of such graft copolymers include ABS resins such as “CHT” manufactured by Chail Industries, “B602” manufactured by UMGABS, “Paraloid EXL2602”, “Paraloid EXL2603” manufactured by Rohm and Haas Japan. , "Paraloid EXL2655", manufactured by Mitsubishi Rayon Co., Ltd., "Metablene C-223A", "Metablene E-901", Gantz Kasei Co., Ltd. "Staffyroid IM-601", Kaneka Corporation "Kaneace M-511", "Kaneace M" Core / shell type graft copolymers such as “−600”.

The content of the graft copolymer is usually 0.5 parts by mass or more, preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, and usually 10 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Part or less, preferably 7.5 parts by weight or less, more preferably 6 parts by weight or less, and particularly preferably 3 parts by weight or less. If the content of the graft copolymer is less than or equal to the lower limit of the above range, the effect of improving the flame retardancy and impact resistance of the graft copolymer may be insufficient, and the content of the graft copolymer may be insufficient. When exceeding the upper limit of the said range, a flame retardance, heat resistance, a fall of impact resistance, and the external appearance defect of the molded article which shape | molded the polycarbonate resin composition may arise.

[6. Hydroxyphenyltriazine UV absorber]
The polycarbonate resin composition of the present invention contains a hydroxyphenyltriazine-based ultraviolet absorber. By including hydroxyphenyltriazine-based ultraviolet absorption, the weather resistance, impact resistance, and brightness of the polycarbonate resin composition can be effectively improved.

Examples of the hydroxyphenyltriazine-based ultraviolet absorber used in the present invention include the general formulas (1), (2), (7), (8), (9), (10), (11), (12), ( A triazine-based ultraviolet absorber represented by at least one selected from the group of 13) .

In the general formula (1) , R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms, an aryl group, an arylalkyl group, and the like, and these are linear chains, branched chains, and cyclic chains. May be. In the skeleton, an ether residue (—O—), an ester residue (—COO—), a carbonyl residue (—CO—), an amide residue (—CONH—), an imide residue (—CONCCO—) May have a residue such as a thiosulfide residue (—S—), a hydroxy group (—OH), a cyano group (—CN), a nitro group (—NO ₂ ), a carboxy group (—COOH). ) And the like.

  Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclohexyl, octyl, and octyldodecyl. It is done. At this time, it preferably has an ether residue (—O—) or an ester residue (—COO—), and is preferably substituted with a hydroxy group (—OH). Thus, by having an ether residue, an ester residue, and a hydroxy group, the heat resistance of the hydroxyphenyltriazine-based ultraviolet absorber of the present invention tends to be improved, and the compatibility with the polycarbonate resin is improved. There is a tendency for the thermal stability of the polycarbonate resin to improve.

  Examples of the aryl group having 1 to 30 carbon atoms include a phenyl group, a naphthyl group, a biphenyl group, and a terphenyl group. Moreover, a benzyl group etc. are mentioned as a C1-C30 arylalkyl group. In addition, a part of the aromatic ring such as phenyl group, naphthyl group, biphenyl group, terphenyl group, benzyl group, alkyl group such as methyl group, ethyl group, propyl group, butyl group, methoxy group, ethoxy group, It may be substituted with an alkoxy group such as a propoxy group or a butoxy group.

In the general formula ^{(1), R 2, R} 3, R 4, R 5, R 6, R 7 and ^{R 8} are hydrogen atom, halogen atom, hydroxy group, consisting of hydrocarbon groups having 1 to 30 carbon atoms At least one selected from the group

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. By containing a halogen atom in this way, the heat resistance of the hydroxyphenyltriazine-based ultraviolet absorber of the present invention tends to be improved, and the ultraviolet absorption characteristics are mainly shifted to the longer wavelength side, and the polycarbonate of the present invention There exists a tendency for the weather resistance of a resin composition to improve more.

The hydrocarbon group of the 1 to 30 carbon atoms, is similar to the description of the hydrocarbon group having 1 to 30 carbon atoms in R ^1.

Examples of such hydroxyphenyltriazine-based ultraviolet absorbers include those having the following structure. However, the hydroxyphenyltriazine-based ultraviolet absorber is not limited to the following examples. Moreover, the polycarbonate resin composition of this invention may contain only 1 type of hydroxyphenyl triazine type ultraviolet absorbers, and may contain 2 or more types by arbitrary combinations and arbitrary ratios.

Hydroxyphenyl such as formula (3) contained in formula (1) and formulas (2), (7), (8), (9), (10), (11), (12), and (13) As triazine-based ultraviolet absorbers, “LA-46” manufactured by ADEKA, “Tinuvin 1577ED”, “Tinubin 400”, “Tinubin 405”, “Tinubin 460”, “Tinubin 477-DW”, “Tinubin 479” manufactured by Ciba And the like.

Of the hydroxyphenyl triazine-based ultraviolet absorbers used in the present invention, the hydroxyphenyl triazine-based ultraviolet absorbers represented by the above formulas (2) and (3) are preferable, and the hydroxyphenyl triazine-based ultraviolet absorber represented by the above formula (2) is preferred. An ultraviolet absorber is more preferable.

The content of the hydroxyphenyltriazine-based ultraviolet absorber is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin. Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part or less, More preferably, it is 0.4 mass part or less. When the content of the hydroxyphenyl triazine UV absorber is not more than the lower limit of the above range, the effect of improving the weather resistance by the hydroxyphenyl triazine UV absorber may be insufficient, and the hydroxyphenyl triazine UV absorber When the content of C exceeds the upper limit of the above range, there is a possibility that mold contamination or poor appearance of a molded product obtained by molding the polycarbonate resin composition may occur.

[7. Phosphorus stabilizer]
The polycarbonate resin composition of the present invention may contain a phosphorus stabilizer. By containing a phosphorus stabilizer, the hue of the polycarbonate resin composition of the present invention is improved, and the thermal stability can be improved.

Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 10 metal phosphates such as potassium, sodium phosphate, cesium phosphate, 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 0.0001 parts by mass or more, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, based on 100 parts by mass of the polycarbonate resin. 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass 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.

[8. Phenolic stabilizer]
The polycarbonate resin composition of the present invention may contain a phenol-based stabilizer. By containing a phosphorus stabilizer, the hue of the polycarbonate resin composition of the present invention is improved, and the thermal stability can be improved.

Specific examples of the phenol-based stabilizer 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 Ru-a, a ′, a ″-(mesitylene-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 and the like.

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

The content of the phenol-based stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.5 parts, relative to 100 parts by mass of the polycarbonate resin. It is below mass parts. When the content of the phenol-based stabilizer is not more than the lower limit of the above range, the effect as an antioxidant may be insufficient, and when the content of the phenol-based stabilizer exceeds the upper limit of the above range May end in effect and become less economical.

[9. Dyeing pigment]
The polycarbonate resin composition of the present invention may contain a dye / pigment. By containing the dye / pigment, the design of the molded article made of the polycarbonate resin composition of the present invention can be improved, and the concealability can be improved.

Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.

  Examples of the inorganic pigment include carbon black; 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 Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  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, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability, and titanium oxide and carbon black are more preferable from the viewpoint of concealment. Titanium is more preferred.

Titanium oxide used in the present invention is not particularly limited in terms of production method, crystal form, average particle size, etc., and production methods of titanium oxide include sulfuric acid method and chlorine method, but were produced by sulfuric acid method. Titanium oxide is preferably produced by a chlorine method in order to effectively achieve the object of the present invention because the whiteness of the composition to which titanium oxide is added tends to be poor and the colorability tends to be low.

The crystal form of titanium oxide includes a rutile type and an anatase type, but a rutile type crystal form is preferred from the viewpoint of light resistance. It is preferable that the average particle diameter of a titanium oxide type additive is 0.1-0.7 micrometer, More preferably, it is 0.1-0.4 micrometer. When the average particle diameter is less than 0.1 μm, the light shielding property of the molded product is inferior, and when it exceeds 0.7 μm, the surface of the molded product is roughened or the mechanical strength of the molded product is lowered. In the present invention, two or more types of titanium oxide having different average particle diameters may be mixed and used.

  Titanium oxide is preferably pretreated with an alumina surface treatment agent before being surface treated with an organosiloxane surface treatment agent described later. Alumina hydrate is preferably used as the alumina-based surface treatment agent. Furthermore, it may be pretreated with silicic acid hydrate together with alumina hydrate. The pretreatment method is not particularly limited, and any method can be used. The pretreatment with alumina hydrate and, if necessary, silicic acid hydrate is preferably carried out in the range of 1 to 15% by weight with respect to titanium oxide.

Titanium oxide pretreated with alumina hydrate and, if necessary, silicic acid hydrate can be further improved in thermal stability by surface treatment with an organosiloxane surface treatment agent. In addition, the uniform dispersibility in the polycarbonate resin composition and the stability of the dispersion state are improved.

As the organosiloxane surface treating agent, a reactive functional group-containing organosilicon compound having a reactive functional group that reacts with the surface of the inorganic compound particles is particularly preferable. Examples of reactive functional groups include Si—H groups, Si—OH groups, Si—NH groups, and Si—OR groups.
Those having H group, Si-OH group, Si-OR group are more preferred, and Si-- having Si-H group is preferred.
H group-containing organosilicon compounds are particularly preferred.

The Si—H group-containing organosilicon compound is not particularly limited as long as it is a compound having a Si—H group in the molecule, and may be appropriately selected and used. Among them, poly (methyl hydrogensiloxane), polycyclo (Methylhydrogensiloxane), poly (ethylhydrogensiloxane), poly (phenylhydrogensiloxane), poly [(methylhydrogensiloxane) (dimethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (ethylmethylsiloxane) )] Copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (hexylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (octylmethy) Siloxane)] copolymer, poly [(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethoxysiloxane)] copolymer, poly [(methylhydrogensiloxane) (dimethoxysiloxane)] Copolymer, poly [(methylhydrogensiloxane) (3,3,3-trifluoropropylmethylsiloxane)] copolymer,
Poly [(dihydrogensiloxane) ((2-methoxyethoxy) methylsiloxane)
] Copolymer, Poly [(Dihydrogensiloxane) (Phenoxymethylsiloxane)
Polyorganohydrogensiloxanes such as copolymers are preferred.

There are (1) a wet method and (2) a dry method as a surface treatment method using an organosiloxane-based surface treatment agent of titanium oxide. In the wet method, a mixture of an organosiloxane-based surface treatment agent and a solvent is added with alumina hydrate, and if necessary, titanium oxide pretreated with silicic acid hydrate. Furthermore, it is a method of heat-processing at 100-300 degreeC after that. In the dry method, pretreated titanium oxide and polyorganohydrogensiloxane are mixed with a Henschel mixer in the same manner as described above, and an organic solution of polyorganohydrogensiloxane is sprayed on the pretreated titanium oxide. And a method of heat-treating at 100 to 300 ° C.

  In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

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

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

-Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, light-proofing agents (HALS), flame retardants, antistatic agents, antifogging agents, lubricants, antiblocking agents, and fluidity improvements. Agents, plasticizers, dispersants, antibacterial agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the polycarbonate resin composition of this invention is demonstrated concretely.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oil, and the like. .

  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. In addition, an aliphatic includes an alicyclic compound here.

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

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

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

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 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 5000 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 mold release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent 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 or less with respect to 100 parts by mass of the polycarbonate resin. It is. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

[11. 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 the polycarbonate resin and organic sulfonic acid metal salt, butadiene-containing graft copolymer, triazine-based ultraviolet absorber, and other components blended as necessary, such as a tumbler or Henschel mixer. Examples of the method include premixing using various mixers such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, and the like.

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.

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

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

  Examples of the electric and electronic devices include display devices such as personal computers, game machines, and televisions, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, recording medium drives, Examples include readers, mice, numeric keys, CD players, MD players, portable radio / audio players, outdoor lighting equipment, various meters such as wattmeters and gas meters, and electric transport equipment members such as electric bicycles, electric motorcycles, and electric cars. .

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

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.

[Production of resin pellets]
Each component described in Table 2 to be described later is blended in the ratio (mass ratio) described in Tables 3 to 4, and mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works (TEX30HSST) equipped with 1 vent. Supplied, 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 in a strand form is quenched in a water tank, pelletized using a pelletizer, and a polycarbonate resin composition Pellets were obtained.

[Preparation of test piece]
After drying the pellets obtained by the above-mentioned production method at 120 ° C. for 5 hours, injection was performed under the conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using a J50-EP type injection molding machine manufactured by Nippon Steel. A UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.2 mm was molded.
Similarly, after the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature was 280 ° C. and the mold temperature was 80 ° C. Then, injection molding was carried out under the condition of a molding cycle of 55 seconds, and flat plate test pieces (90 mm × 50 mm × 2 mm thickness) and ASTM test pieces (3.2 mm thick notched test pieces) were formed.

[Flame retardance evaluation]
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 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied. In addition, in Tables 3-4, it describes with "flame retardance."

[Impact resistance evaluation]
In accordance with ASTM D256, using the ASTM test piece (3.2 mm thick notched test piece) prepared above, Izod impact strength (unit: J / m) was measured at 23 ° C.

[Brightness evaluation]
In accordance with JIS K-7105, the above-mentioned flat test piece (2 mm thickness) was used as a test piece, and the L value was measured by a reflection method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. A larger value of L indicates higher brightness. A polycarbonate resin composition having high brightness is preferable because of its high degree of freedom in coloring.

[Weather resistance evaluation]
Plate test piece above the (2mm thick) as a test piece, in Suga Test Instruments Co., Ltd. SX75-AP type Sunshine Super Long Life Weather Meter (SWOM), irradiance 156kW / ^{m 2,} black panel temperature 63 ° C., water spray The treatment was performed for 150 hours and 300 hours under the condition of 12 minutes in 60 minutes of the cycle.
In accordance with JIS K-7105, the above flat plate test piece (2 mm thickness) was used as a test piece, and the L value, a value, and b value were measured by the reflection method with a SE2000 type official color meter manufactured by Nippon Denshoku Industries Co., Ltd. The color difference (ΔE) before and after processing was calculated. A smaller ΔE is preferable because it indicates that the discoloration by the weather resistance test is small.
ΔE (150h) = ((L _150h −L _0h ) ² + (a _150h −a _0h ) ² + (b _150h −b _0h ) ² ) ^0.5
ΔE (300h) = ((L _300h −L _0h ) ² + (a _300h −a _0h ) ² + (b _300h −b _0h ) ² ) ^0.5
[ΔE (150h): ΔE after SWOM 150h treatment,
ΔE (300h): ΔE after SWOM300h treatment
L _150h , a _150h , b _150h : L value, a value, and b value after _SWOM 150h processing. L _300h , a _300h , b _300h : L value, a value, and b value after SWOM 150h processing. L _0h , a _0h , b _0h : L value, SW value, and SW value before SWOM processing. ]

According to Tables 3 to 4, the resin composition of the present invention is excellent in flame retardancy, impact resistance, lightness, and weather resistance, and the molded product made of the resin composition of the present invention is a molded product for outdoor use, particularly Useful for electronic enclosures for outdoor applications.

Claims (7)

For 100 parts by mass of the polycarbonate resin (A),
0.001 to 2 parts by mass of organic sulfonic acid alkali metal salt (B),
0.01-1 part by mass of fluoropolymer (C),
Butadiene-based graft copolymer (D) 0.5 to 10 parts by mass,
And hydroxy represented by at least one selected from the group of the following formulas (1) , (2), (7), (8), (9), (10), (11), (12), and (13) A polycarbonate resin composition comprising 0.001 to 1 part by mass of a phenyltriazine-based ultraviolet absorber (E).

[In the formula (1), R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ⁸ represent at least one selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxy group, and a hydrocarbon group having 1 to 30 carbon atoms. ]

  Furthermore, 0.0001-1 mass part of phosphorous stabilizer (F) and / or a phenolic stabilizer (G) are contained with respect to 100 mass parts of polycarbonate resin (A), It is characterized by the above-mentioned. Polycarbonate resin composition.   Furthermore, 0.0001-5 mass parts of dye / pigments (H) are contained with respect to 100 mass parts of polycarbonate resin (A), The polycarbonate resin composition of Claim 1 or 2 characterized by the above-mentioned. The hydroxyphenyltriazine-based ultraviolet absorber (E) is an ultraviolet absorber represented by at least one selected from the following general formula (2) and the following general formula (3): 4. The polycarbonate resin composition according to any one of 3.

  A butadiene-based graft copolymer (D) includes a core composed of a butadiene-based rubber and a shell composed of at least one selected from an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic ester compound. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polycarbonate resin composition is a shell-type graft copolymer.   The polycarbonate resin composition according to any one of claims 3 to 5, wherein the dye / pigment (H) is titanium oxide. An electronic device casing for outdoor use, which is formed by molding the polycarbonate resin composition according to any one of claims 1 to 6.