JP6147595B2 - Polycarbonate resin composition, molded article comprising the same, and method for producing the same - Google Patents

Description

  The present invention relates to a polycarbonate resin composition, a molded article comprising the same, and a method for producing the same, and more specifically, a polycarbonate resin composition having excellent flame retardancy, rigidity, surface appearance, surface hardness, and texture appearance, and further comprising the same. The present invention relates to a molded body and a manufacturing method thereof.

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

  In such applications, conventionally, molded products molded from flame-retardant polycarbonate resins have been painted and hard-coated, but from the viewpoints of increased environmental awareness, recyclability, and economic efficiency, Application as a product without painting or hard coating is strongly desired.

  On the other hand, electronic and electronic equipment casings are required to have various design properties such as glossiness, variety of coloring, metallic feeling, and matte feeling in order to increase commercial value. In particular, the matte feeling can produce a high-class feeling and is an important design element that is very popular with consumers in the fields of liquid crystal televisions, notebook computers, tablets, printers, projectors and the like.

  However, since the polycarbonate resin has a very low surface hardness and is easily scratched, it could not be used without coating or hard coating. On the other hand, as a method of improving the surface hardness of the polycarbonate resin, a method of blending polymethyl methacrylate (for example, see Patent Document 1), a method of blending an antiplasticizer (for example, see Patent Document 2), A method of blending a glass-based filler (see, for example, Patent Document 3) has been proposed. However, the method of blending polymethylmethacrylate has a dull feeling and the molded product surface peels off. Phenomenon and appearance defects such as flow marks are likely to occur, the method of blending with an antiplasticizer is easy to color, the matte feeling is not obtained, the flame retardancy is reduced, the gas at the time of molding There were many drawbacks. Also, the method of blending a glass filler also has a drawback that a molded product having a good appearance cannot be obtained unless appropriate molding conditions are selected.

  Furthermore, when used in electrical and electronic equipment casings, in addition to the surface hardness and matte feeling as described above, mechanical properties such as rigidity and impact resistance, when fitting products, or fixing parts with screws However, the above-mentioned method cannot satisfy these required physical properties and cannot be practically used as a housing material.

JP-A-7-90167 JP 2007-326938 JP 2011-98545 A

  The present invention was devised in view of the above problems of the prior art, and is a polycarbonate resin composition excellent in flame retardancy, surface hardness, matte feeling, rigidity, impact resistance, and self-tapping properties, and molding the same. An object of the present invention is to provide a molded article and a manufacturing method thereof.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that in a resin composition comprising a polycarbonate resin and a phosphorus flame retardant, a polymethyl methacrylate resin, a fluoropolymer, a plate silicate compound, a specific Each of the above graft copolymers contains a specific amount, and at that time, the polymethyl methacrylate resin and the plate silicate compound are contained in a specific ratio. It functions as an appearance improver, has excellent flame retardancy, surface hardness, matte feeling, rigidity, impact resistance, is excellent in self-tapping properties, and is a matte flame retardant polycarbonate resin material that fully exhibits a high-class feeling. As a result, the present invention has been completed.
The present invention provides the following polycarbonate resin composition, a molded article comprising the same, and a method for producing the same.

[1] Polymethyl methacrylate resin (B) 5 to 60 parts by mass, phosphorus flame retardant (C) 5 to 40 parts by mass, fluoropolymer (D) 0.001 to 100 parts by mass of polycarbonate resin (A) ~ 2 parts by mass, 5-60 parts by mass of a plate-like silicate compound (E), and a rubbery polymer obtained by graft polymerization of at least one (meth) acrylate compound capable of graft copolymerization. Containing 4 to 20 parts by mass of the graft copolymer (F),
The mass ratio ((B) / (E)) of the content of the polymethyl methacrylate resin (B) and the content of the plate silicate compound (E) is 4/1 to 1/4. A polycarbonate resin composition.
[2] The polycarbonate resin composition according to [1], further containing 0.0001 to 2 parts by mass of carbon black (G) with respect to 100 parts by mass of the polycarbonate resin (A).

[3] The polycarbonate resin composition according to the above [1] or [2], wherein the phosphorus flame retardant (C) is a phosphate ester compound 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, p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group.)
[4] The polycarbonate resin composition according to any one of [1] to [3], wherein the plate-like silicate compound (E) is talc or mica.

[5] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [4].
[6] The molded product according to [5], wherein the molded product has a textured surface.
[7] The molded body according to the above [5] or [6], wherein the molded body is an electronic / electric equipment casing.

  ADVANTAGE OF THE INVENTION According to this invention, it is possible to provide the polycarbonate resin composition which is excellent also in a flame retardance, surface hardness, a matte feeling, rigidity, an impact resistance, and self-tapping property, a molded object consisting thereof, and a manufacturing method of a molded object It is.

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

[Overview]
The polycarbonate resin composition of the present invention comprises 5 to 60 parts by mass of a polymethyl methacrylate resin (B), 5 to 40 parts by mass of a phosphorus-based flame retardant (C), and 100% by mass of the polycarbonate resin (A). (D) 0.001 to 2 parts by mass, 5 to 60 parts by mass of a plate-like silicate compound (E), and a rubbery polymer, and at least one (meth) acrylic ester compound capable of graft copolymerization 4 to 20 parts by mass of a graft copolymer (F) obtained by graft polymerization, and a mass ratio of the content of the polymethyl methacrylate resin (B) and the content of the plate silicate compound (E) ( (B) / (E)) is 4/1 to 1/4.

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

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by a general formula: — [— O—X ² —O—C (═O) —] —. 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 (A), For example, the polycarbonate resin 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 resin (A) may be linear or branched. Furthermore, the polycarbonate resin (A) 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 the monomers used as the raw material for the polycarbonate resin (A), as an example of the aromatic dihydroxy compound,
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 polycarbonate resin (A), 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 (A) The manufacturing method of polycarbonate resin (A) 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 o-hydroxybenzoic 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 (A) The molecular weight of the polycarbonate resin (A) 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 16,000 or more, more preferably 17,000 or more, and usually 40,000 or less, preferably 30,000 or less, more preferably 24,000 or less. By setting the viscosity average molecular weight to be equal to or higher than the lower limit of the above range, the mechanical strength of the polycarbonate resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. On the other hand, by setting the viscosity average molecular weight to be equal to or lower than the upper limit of the above range, the polycarbonate resin composition of the present invention can be suppressed and improved in fluidity, and the molding processability can be improved and the molding process can be easily performed. Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

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

  The terminal hydroxyl group concentration of the polycarbonate resin (A) 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 (A) is not limited to an embodiment including only one type of polycarbonate resin, and includes an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. 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.

  In addition, the polycarbonate resin (A) may contain a polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. 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 (A) 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.

[Polymethylmethacrylate resin (B)]
The polymethyl methacrylate resin (B) used in the present invention is a resin containing a methyl methacrylate monomer unit, and may contain another monomer unit that can be copolymerized as necessary.
Examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, α-methylstyrene and paramethylstyrene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; methacrylic acid; methacrylic acid Methacrylic acid ester monomers such as ethyl, butyl methacrylate, glycidyl methacrylate and hydroxyethyl methacrylate; Acrylic acid; Acrylic acid ester monomers such as methyl acrylate, butyl acrylate, glycidyl acrylate and hydroxyethyl acrylate Is mentioned. These may be used alone or in combination of two or more.
The proportion of the methyl methacrylate monomer unit is preferably 50% by mass or more from the viewpoint of heat resistance, etc. in 100% by mass of the total monomer units of the polymethyl methacrylate resin (B). The proportion of body units is preferably 50% by mass or less.

  The method for producing the polymethyl methacrylate resin (B) is not particularly limited. Various known methods such as suspension polymerization, bulk polymerization, and emulsion polymerization can be applied. The molecular weight of the polymethyl methacrylate resin (B) is not particularly limited, but a mass average molecular weight of 100,000 to 300,000 is preferable.

  In the present invention, the content of the polymethyl methacrylate resin (B) is 5 to 60 parts by mass, preferably 10 parts by mass or more, more preferably 12 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Preferably, it is 50 mass parts or less, More preferably, it is 45 mass parts or less. If the content of the polymethyl methacrylate resin (B) is too small, the improvement in hardness is small, and the appearance (texture appearance) when a molded article having a textured surface is molded using a non-mirror surface mold is deteriorated. If the amount is too large, the flame retardancy deteriorates.

[Phosphorus flame retardant (C)]
The polycarbonate resin composition of the present invention contains 5 to 40 parts by mass of the phosphorus-based flame retardant (C) with respect to 100 parts by mass of the polycarbonate resin (A). Thus, the flame retardance of the polycarbonate resin composition of this invention can be improved by containing a phosphorus flame retardant.

  The phosphorus-based flame retardant (C) is a compound containing phosphorus in the molecule and may be a low molecule, an oligomer, or a polymer. From the viewpoint of thermal stability, for example, the following The phosphate compound represented by the general formula (1) and the phosphazene compounds represented by the following general formulas (2) and (3) are particularly preferable.

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

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

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

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

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

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

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

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

In the cyclic phosphazene compound represented by the general formula (2), R ⁵ and R ⁶ may be the same or different and each represents an aryl group or an alkylaryl group. Examples of such an aryl group or alkylaryl group include a phenyl group, a naphthyl group, a methylphenyl group, and a benzyl group. Among them, cyclic phenoxyphosphazene in which R ⁵ and R ⁶ are phenyl groups is particularly preferable.
Examples of such a cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene, octachlorocyclohexane, and a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. Examples include compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as cyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group. .

  Moreover, in general formula (2), although t represents the integer of 3-25, the compound whose t is an integer of 3-8 is preferable especially, and the mixture of the compound from which t differs may be sufficient. Among them, a mixture of compounds in which t = 3 is 50% by mass or more, t = 4 is 10 to 40% by mass, and t = 5 or more is 30% by mass or less is preferable.

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

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

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

Further, the phosphazene compound may be a crosslinked phosphazene compound partially crosslinked. By having such a crosslinked structure, the heat resistance tends to be improved.
As such a crosslinked phosphazene compound, a crosslinked structure represented by the following general formula (4), for example, a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (that is, bisphenol S residue), 2,2- ( 4,4′-diphenylene) isopropylidene group-crosslinked structure, 4,4′-oxydiphenylene group-crosslinked structure, 4,4′-thiodiphenylene group-crosslinked structure, etc. And compounds having a crosslinked structure of 4,4′-diphenylene group.

[In Formula (4), X ³ is —C (CH ₃ ) ₂ —, —SO ₂ —, —S—, or —O—, and v is 0 or 1. ]

In addition, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ⁵ and R ⁶ are phenyl groups in the general formula (2) with a crosslinking group represented by the general formula (4). Alternatively, a crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ⁷ and R ⁸ are phenyl groups in the general formula (3) with a crosslinking group represented by the general formula (4) is flame retardant. From the above point, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound with a crosslinking group represented by the general formula (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 compound is a crosslinked phenoxy obtained by crosslinking the cyclic phenoxyphosphazene compound represented by the general formula (2) and the cyclic phenoxyphosphazene compound represented by the general formula (3) with a crosslinking group. In view of flame retardancy and mechanical properties, at least one selected from the group consisting of phosphazene compounds is preferable.

  The content of the phosphorus-based flame retardant (C) is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 40 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). Or less, preferably 35 parts by weight or less, more preferably 30 parts by weight or less. When the blending amount of the phosphorus-based flame retardant is less than 5 parts by mass, the flame retardancy is insufficient, and when it exceeds 40 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[Fluoropolymer (D)]
The polycarbonate resin composition of the present invention contains 0.001 to 2 parts by mass of the fluoropolymer (D) with respect to 100 parts by mass of the polycarbonate resin (A). One type of fluoropolymer (D) may be used, or two or more types may be used in any combination and in any ratio.

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

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

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

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

  The content of the fluoropolymer (D) is 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the polycarbonate resin (A). Especially preferably, it is 0.1 mass part or more, and is 2 mass parts or less, Preferably it is 1.5 mass parts or less, More preferably, it is 1 mass part or less. When the content of the fluoropolymer (D) is less than the lower limit of the above range, the flame retardancy effect due to the anti-dripping agent becomes insufficient, and when the content exceeds the upper limit of the above range, the polycarbonate resin composition There is a possibility that the appearance defect or the mechanical strength of the molded product formed from the above will be deteriorated.

[Plate-like silicate compound (E)]
The silicate compound is a compound containing a chemical composition of SiO ₂ units as a chemical composition. In the present invention, a plate-like plate silicate compound (E) is used. Specific examples include talc, mica, magnesium silicate, aluminum silicate, calcium silicate, kaolin, diatomaceous earth, and smectite, which may be natural products or synthesized products. Further, it may be a fired product or an unfired product, and may be a hydrate or an anhydrous product.
As the plate-like silicate compound (E), talc and mica are excellent in improving the flame retardancy of the resin composition, and are also excellent in hardness, warpage prevention effect, heat resistance and mechanical strength improvement effect. Talc is particularly preferable.

  The average particle diameter of the plate silicate compound (E) is preferably 0.5 to 100 μm, more preferably 1 to 50 μm, and particularly preferably 2 to 10 μm. If it is less than 0.5 μm, handling becomes difficult, and if it exceeds 100 μm, the impact resistance tends to decrease.

  The plate-like silicate compound (E) may be subjected to surface treatment with various surface treatment agents such as a silane treatment agent in order to enhance the adhesion with the resin. Although it does not specifically limit as a surface treating agent, Although a conventionally well-known thing can be used, epoxy group containing silane coupling agents, such as an epoxy silane, and amino group containing silane coupling agents, such as amino silane, are resin. It is preferable because the physical properties are hardly lowered. In addition, polyoxyethylene silane or the like can be used. The surface treatment method is not particularly limited, and a normal treatment method can be used.

  There is no particular limitation on the method of treating the plate silicate compound (E) with the surface treating agent, and it can be carried out by a usual method. For example, it can be carried out by adding a surface treatment agent to the plate-like silicate compound (E) and stirring or mixing in a solution or while heating.

  These plate silicate compounds (E) may be used alone or in combination of two or more different average particle diameters, types, surface treatment agents, and the like.

  Content of plate-like silicate compound (E) is 5-60 mass parts with respect to 100 mass parts of polycarbonate resin (A), Preferably it is 10-50 mass parts, More preferably, it is 12-45 mass parts. When the content is less than 5 parts by mass, the molded article obtained has a poor flame retardancy improving effect and tends to be inferior in heat resistance and mechanical strength improving effect. On the other hand, when the amount exceeds 60 parts by mass, impact resistance, thermal stability, and surface properties of the obtained molded product are lowered, and workability tends to be lowered, such as difficulty in kneading with a resin during melt kneading.

  In the present invention, the content of the polymethyl methacrylate resin (B) and the plate-like silicate compound (E) is such that the mass ratio (B) / (E) is 4/1 to 1/4. And If it falls below this range, mechanical properties such as impact resistance will deteriorate, and the surface appearance will worsen. If it exceeds this range, flame retardancy and surface appearance will deteriorate. The mass ratio (B) / (E) is preferably 3/1 to 1/2, and more preferably 2/1 to 1 / 1.35.

[Graft copolymer (F)]
The polycarbonate resin composition of the present invention contains a graft copolymer (F) obtained by graft-polymerizing a rubbery polymer with at least one (meth) acrylic acid ester compound capable of graft copolymerization.
As a method for producing a graft copolymer obtained by graft-copolymerizing a rubber polymer with a (meth) acrylic acid ester compound that can be graft-copolymerized therewith, any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. A production method may be used, and emulsion polymerization is particularly preferable.
The copolymerization method may be single-stage or multistage grafting, but multistage graft copolymerization is preferred.

The rubbery polymer 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 rubbery polymer include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate-2-ethylhexyl acrylate copolymer, and polyorganosiloxane rubber. Such as silicone rubber, butadiene-acrylic composite rubber, composite rubber made of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-α- such as ethylene-octene rubber Examples thereof include olefin rubber, ethylene-acrylic rubber, and fluorine rubber. These may be used alone or in admixture of two or more.
Of these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, polyorganosiloxane rubber, and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance, and butadiene series such as polybutadiene rubber and styrene-butadiene rubber. More preferred are rubbers and polyorganosiloxane rubbers.

Examples of the (meth) acrylic acid ester compound that can be graft copolymerized with the rubber polymer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Preferable examples include octyl acrylate and phenyl (meth) acrylate.
A (meth) acrylic acid ester compound may be used individually by 1 type, or may mix and use 2 or more types.

  Furthermore, other graft copolymerizable monomers other than (meth) acrylic acid ester compounds can be used in combination, and specific examples of such monomers include aromatic vinyl compounds, vinyl cyanide compounds, (Meth) acrylic acid compounds, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, phthalic acid, itaconic acid, etc. Α, β-unsaturated carboxylic acid compounds and anhydrides thereof (for example, maleic anhydride and the like). These monomer components may be used alone or in combination of two or more.

The graft copolymer (F) obtained by graft-polymerizing at least one (meth) acrylate compound to a rubber polymer is a core / shell type graft copolymer type in terms of impact resistance and surface appearance. Those are preferred. Among these, at least one rubber component selected from a polybutadiene-containing rubber, a polybutyl acrylate-containing rubber, a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl acrylate rubber (Interpenetrating Polymer Network (IPN) type) composite rubber is used. A core / shell type graft copolymer comprising a shell layer formed by graft copolymerization of (meth) acrylic acid ester around the core layer is particularly preferred.
In such a core / shell type graft copolymer, the rubber component is preferably contained in an amount of 40% by mass or more, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

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

  By containing the polycarbonate resin (A), the phosphorus-based flame retardant (B), the fluoropolymer (D), and the graft copolymer (F) in the specified amounts in the present invention, surprisingly, the flame retardancy is reduced. The impact resistance, in particular, the impact resistance during high temperature molding and the impact resistance in a low temperature environment can be improved.

  The content of the graft copolymer (F) is 4 to 20 parts by mass with respect to 100 parts by mass of the polycarbonate resin (A). When the content is less than 4 parts by mass, the impact resistance improvement effect becomes insufficient, and when the content exceeds 20 parts by mass, the appearance defect, heat resistance, and flame retardancy of the molded product molded from the polycarbonate resin composition are reduced. Arise. The content is preferably 5 parts by mass or more, more preferably 7 parts by mass or more, and preferably 17 parts by mass or less, more preferably 15 parts by mass or less, with respect to 100 parts by mass of the polycarbonate resin (A). is there.

  As described above, the polymethyl methacrylate resin (B), the phosphorus flame retardant (C), the fluoropolymer (D), the plate-like silicate compound (E), and the graft copolymer (F) are respectively described above. By containing a specific amount of polymethylmethacrylate resin (B) and plate silicate compound (E) in a ratio of 4/1 to 1/4, surprisingly, plate silicate A matte flame retardant that functions as an appearance improver for molded products, has excellent flame retardancy, surface hardness, matte feeling, rigidity, impact resistance, is excellent in self-tapping properties, and has a high-class feeling. Polycarbonate resin material.

[Carbon black]
The resin composition of the present invention preferably contains carbon black from the viewpoint of improving the high-quality feeling of the molded product. There are no restrictions on the production method of carbon black to be used, the raw material species, etc., and any conventionally known ones such as oil furnace black, channel black, acetylene black, ketjen black and the like can be used. Among these, oil furnace black is preferable from the viewpoint of colorability and cost.

  The average particle size of the carbon black to be used may be appropriately selected and determined, and among these, 5 to 60 nm is preferable, 7 to 55 nm is more preferable, and 10 to 50 nm is particularly preferable. By setting the average particle diameter within the above range, the aggregation of carbon black is suppressed and the appearance tends to be improved. The average particle diameter of carbon black can be obtained using a transmission electron microscope.

Nitrogen adsorption specific surface area of the carbon black used in the present invention 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 can be measured according to JIS K6217 (unit: m ² / g).

The DBP absorption of carbon black ^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 amount can be measured according to JIS K6217 (unit ^cm 3 / 100g). 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.

  The carbon black used in the present invention 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.

  The content of carbon black is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and still more preferably 0.001 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A). Moreover, Preferably it is 2 mass parts or less, More preferably, it is 1 mass part or less. When the carbon black is less than the lower limit of the above range, the appearance and jetness may be inferior, and when the carbon black content exceeds the upper limit of the above range, the heat stability of the polycarbonate resin composition of the present invention May be reduced.

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

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF Japan, 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 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 ″-(me Citylene-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-t rt- pentylphenyl acrylate.

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

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

[Release agent]
It is also preferable to contain a release agent. Preferable 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 15,000, polysiloxane silicone oils, 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. Here, the term “aliphatic” is used as a term including alicyclic compounds.

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

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

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

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

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

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

  In addition, 1 type may contain the 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 parts by mass or more, preferably 0.01 parts by mass or more, and usually 2 parts by mass or less, preferably 1 with respect to 100 parts by mass of the polycarbonate resin (A). It is below mass parts. When the content of the release agent is less than the lower limit of the range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the range, hydrolysis resistance And mold contamination during injection molding may occur.

[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 the polycarbonate resin (A) and the polymethyl methacrylate resin (B), various resin additives, and the like. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

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

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

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

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

  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 Japan “Ubinur 400”, BASF Japan “Ubinur M-40”, BASF Japan “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531” "Siasorb UV24", "ADEKA STAB 1413", "ADEKA STAB LA-51" manufactured by ADEKA, and the like.

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

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N N” manufactured by BASF Japan Ltd. -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, “BASF Japan” Tinuvin 1577ED "," Tinuvin 400 "," Tinuvin 405 "," Tinuvin 460 "," Tinubin 477-DW "," Tinubin 479 ", etc. are mentioned.

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

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by BASF Japan, 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 ultraviolet absorber is less than the lower limit of the range, the effect of improving the weather resistance may be insufficient, and if the content of the ultraviolet absorber exceeds the upper limit of the 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 which manufactures 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), polymethyl methacrylate resin (B), phosphorus flame retardant (C), fluoropolymer (D), plate silicate compound (E), and graft copolymer ( F), and other components to be blended as necessary, for example, using various mixers such as a tumbler or Henschel mixer, and then mixed with a Banbury mixer, roll, Brabender, single screw kneading extruder, twin screw A method of melt-kneading with a mixer such as a kneading extruder or kneader can be mentioned.

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

  The polycarbonate resin composition of the present invention exhibits flame retardancy by the UL94 test at a thickness of 1.5 mm in the UL94 test (combustion test of plastic materials for equipment parts) defined by the US Underwriters Laboratories (UL). It becomes possible to achieve extremely high flame retardance of 5 VB.

[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 electric / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, and lighting equipment. Among these, it is particularly suitable for use in housings of electric / electronic devices and OA devices, and is particularly suitable for housings of various portable terminals, projectors, personal computers, printers, televisions, copying machines, and the like.

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

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated more concretely, this invention is limited to a following example and is not interpreted.
Each component used in Examples and Comparative Examples is as shown in Table 1 below.

(Examples 1-5, Comparative Examples 1-5)
[Production of resin composition pellets]
Each component described in Table 1 was blended at the ratio (mass ratio) described in Table 2 and Table 3 below, mixed for 20 minutes with a tumbler, and then a twin screw extruder manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. (TEX30HSST), kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, a barrel temperature of 280 ° C., the molten resin extruded in a strand shape is rapidly cooled in a water tank, and pelletized using a pelletizer, A pellet of a polycarbonate resin composition was obtained.

[Preparation of test piece]
After drying the pellets obtained by the above production method at 80 ° C. for 5 hours, using a SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a cylinder temperature of 260 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.5 mm was injection molded under the following conditions.
Moreover, after drying the pellet obtained by said manufacturing method at 80 degreeC for 5 hours, using a Sumitomo Heavy Industries, Ltd. injection molding machine (Cycap M-2, clamping force 75T), cylinder temperature 280 ISO multipurpose test piece, length 100mm, width 50mm, thickness 2mm flat plate test piece (surface is mirror surface), surface 100mm length, width 100mm, width 50 mm and 2 mm-thick flat test pieces (the surface was textured) were each injection molded.
Furthermore, after drying the pellet obtained by the said manufacturing method at 80 degreeC for 5 hours, cylinder temperature 260 degreeC, mold temperature 80 degreeC, molding cycle using the SE100DU type injection molding machine by Sumitomo Heavy Industries, Ltd. Injection molding was performed under conditions of 30 seconds, and a self-tap test piece having a cylindrical boss portion (dimension of the boss portion: inner diameter 2.1 mm / outer diameter 4.5 mm / height 10 mm) was formed.

[Flame retardance evaluation]
The flame resistance of each polycarbonate resin composition was evaluated by conditioning the obtained test specimen (1.5 mm thickness) for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was performed in accordance with the 94-5VB standard of the UL94 test (combustion test of plastic materials for equipment parts) defined by Underwriters Laboratories (UL). When all five samples were 5VB, “◯”, and when any one of the five samples did not satisfy 5VB, it was determined as “x” because 5VB was not satisfied.

[Elastic modulus evaluation]
Using the ISO multipurpose test piece obtained above, the flexural modulus (unit: MPa) was measured under the condition of 23 ° C. in accordance with ISO178.

[Surface appearance evaluation]
The surface appearance of the 20 plate-like test pieces (surface mirror surfaces) obtained above was visually observed and evaluated according to the following criteria.
++: No sample with flow mark or silver streak ++: Three or less samples with flow mark or silver streak-: Four or more samples with flow mark or silver streak -: 11 or more samples with flow marks or silver streaks

[surface hardness]
The flat test piece (mirror surface) obtained above was subjected to a scratch test five times in accordance with JIS K5400, and the pencil hardness was evaluated.

[Wrinkle appearance evaluation]
The surface appearance of 20 flat test pieces (surface wrinkles) obtained as described above was visually observed and evaluated according to the following criteria.
++: No wrinkle transfer and glossy sample, 0 sheets +: No wrinkle transfer defect, glossy samples 3 or less-: Wrinkle transfer defects, glossy Samples of 4 or more and 10 or less ---: 11 or more samples with glossy transfer failure and glossiness

[Self-tapping evaluation]
When a B-tight screw with a nominal diameter of 2.6 mm and a length of 6 mm is tightened on the boss portion of the self-tap test piece obtained above under the condition of a torque of 0.5 N to confirm that there is no crack. Then, the screw was once loosened and once more tightened under the condition of a torque of 0.5 N was repeated a total of 5 times.
This test was carried out with three samples (N = 1 to 3), and in all the tests, those that had no cracks were judged to be acceptable. In addition, in each test (N = 1 to 3) for reference, those in which no cracking occurred 5 times are indicated as “5 times passed”, and for what has cracked, how many times it was cracked Was written.

From Examples 1 to 5 shown in Table 2, polycarbonate resin (A), polymethyl methacrylate resin (B), phosphorus flame retardant (C), fluoropolymer (D), plate silicate compound (E) And a predetermined amount of the graft copolymer (F), and the mass ratio (B) / (E) of the content of the polymethyl methacrylate resin (B) and the plate silicate compound (E) is 4/1 to The polycarbonate resin composition in the range of 1/4 shows extremely excellent flame retardancy that achieves 5 VB with a UL flame retardance of 1.5 mm, a high elastic modulus, and a good surface appearance and surface hardness. It can be seen that the grain appearance achieves better self-tapping.
On the other hand, it can be seen that the polycarbonate resin composition of Comparative Example in Table 3 that does not satisfy the requirements defined in the present invention has poor performance in any of these.
Therefore, from the above examples and comparative examples, the effects of excellent flame retardancy, surface hardness, matte feeling, rigidity, impact resistance and self-tapping properties can be obtained for the first time by the configuration of the present invention. Was confirmed.

  Since the polycarbonate resin composition of the present invention is excellent in flame retardancy, surface hardness, matte feeling, rigidity, impact resistance and self-tapping properties, it is particularly suitable for use in housings such as electric / electronic devices and OA devices. And industrial applicability is very high.

Claims (8)

Of the polycarbonate resin (A) 100 parts by mass of the mass-average molecular weight of from 100000 to 300000 of polymethyl methacrylate resin (B) 12 to 60 parts by weight, phosphorus-based flame retardant (C) 5 to 40 parts by weight, fluoro Polymer (D) 0.001 to 2 parts by mass, plate-like silicate compound (E) 5 to 60 parts by mass, and at least one (meth) acrylic acid ester that can be graft copolymerized with the rubbery polymer 4 to 20 parts by mass of a graft copolymer (F) obtained by graft polymerization of the compound, and the plate silicate compound (E) is talc or mica,
And wherein the content of the polymethyl methacrylate-based resin (B) and plate-shaped silicate compound (E) the mass ratio of the content of ((B) / (E)) is 2 / 1-1 / 4 A polycarbonate resin composition.   Furthermore, the polycarbonate resin composition of Claim 1 which contains 0.0001-2 mass parts of carbon black (G) with respect to 100 mass parts of polycarbonate resin (A). The polycarbonate resin composition according to claim 1 or 2, wherein the phosphorus-based flame retardant (C) is a phosphate ester compound 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, p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group.) The mass ratio ((B) / (E)) of the content of the polymethyl methacrylate resin (B) and the content of the plate silicate compound (E) is from 1/1 to 1/4. 4. The polycarbonate resin composition according to any one of 3.   The molded object formed by shape | molding the polycarbonate resin composition in any one of Claims 1-4.   The molded body according to claim 5, wherein the molded body has a textured surface.   The molded body according to claim 5 or 6, wherein the molded body is an electronic / electric equipment casing.   A method for producing a molded article, comprising subjecting the polycarbonate resin composition according to any one of claims 1 to 4 to injection molding using a non-specular mold.