JP5101810B2 - Flame retardant aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition and a casing of an electronic device comprising the same. More specifically, by using carbon fiber and graphite together, it has high rigidity, conductivity, low anisotropy, and good dimensional stability, and especially has high flame retardancy compared to when carbon fiber / graphite is used alone. The present invention relates to a flame retardant aromatic polycarbonate resin composition.

  Thermoplastic resins are widely used in all industries because of their ease of production and molding. In particular, aromatic polycarbonate resins generally exhibit excellent electrical insulation, heat resistance, and impact resistance, and are therefore used for storing and transporting electronic components such as semiconductors and electronic circuit boards, various electronic devices, and precision devices. Often used for containers. In recent years, with the miniaturization and high functionality of electronic components, thermoplastic resins are required to have the characteristics of having both dimensional stability and high conductivity and rigidity of thermoplastic resin molded products. Further, since miniaturization and high functionality of electronic components lead to heat generation of electronic components, there is a demand for high flame retardancy for thermoplastic resins used in electronic components. However, until now, none has obtained a resin composition having both low anisotropy, dimensional stability, high conductivity and rigidity, and flame retardancy.

  The addition of carbon black is one typical method for imparting electrical conductivity to a thermoplastic resin. For example, the carbon black comprises a specific ratio of aromatic polycarbonate, polyalkylene terephthalate, and carbon black having a specific DBP oil absorption amount. Resin compositions with improved properties are known (see Non-Patent Document 1 and Patent Document 1). Certainly, the conductivity can be easily imparted by adding carbon black. However, since the carbon black itself is flammable, it is difficult to make it flame retardant.

  Addition of graphite is also known as a technique for imparting rigidity and conductive performance to thermoplastic resins, and resin compositions having high flame retardancy without using halogen flame retardants and phosphorus flame retardants are known. (See Patent Document 2). However, with the addition of graphite, conductivity can be obtained only up to the antistatic region, and high conductivity has not been achieved.

  Also, a resin composition in which anisotropy is improved by blending two types of carbon fibers mainly having different fiber diameters with a thermoplastic resin is known (see Patent Document 3). Conductive fillers such as carbon fibers, metal fibers or metal flakes, metal-coated fibers such as conductive titanium oxide, or metal-coated flakes such as conductive mica have been conventionally used in consideration of improving mechanical properties. However, it is difficult to say that this document discloses sufficient knowledge about the flame retardancy, and particularly excellent flame retardancy is achieved without blending a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. It did not disclose effective knowledge to obtain.

  It is known that carbon fiber and graphite, which is a conductive filler, are used in combination with excellent dimensional accuracy and high rigidity and conductivity (see Patent Document 4). However, it is difficult to say that this document discloses sufficient knowledge about the flame retardancy, and particularly excellent flame retardancy is achieved without blending a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. It did not disclose effective knowledge to obtain.

Journal of Japan Adhesion Association Vol. 23, no. 3, 103-111 pages (1987) JP 2001-323150 A JP 2005-91927 A JP 2000-119405 A Japanese Patent Laid-Open No. 10-237316

  As mentioned above, it has high rigidity, conductivity, low anisotropy and good dimensional stability, and high flame retardancy without using chlorine, bromine and phosphorus flame retardants. Although a flame retardant resin composition is required, no method for obtaining such a resin composition is disclosed at present. Therefore, an object of the present invention is to provide such a flame retardant resin composition.

  As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventor used carbon fiber and graphite, particularly graphite having a specific particle diameter, and at the same time, an organometallic salt compound, particularly an alkali organic sulfonate (earth) As a result of further investigations, the inventors reached the present invention by finding that, when a metal salt is contained, good flame retardancy is achieved and high rigidity, conductivity, low anisotropy and good dimensional stability are obtained.

  That is, the gist of the present invention is to blend carbon fiber and graphite, particularly graphite having a specific particle diameter, and an organometallic salt compound, especially an organic sulfonate alkali (earth) metal salt, in a specific ratio, into a thermoplastic resin. This synergistic effect achieves good flame retardancy, high rigidity, electrical conductivity, low anisotropy and good dimensional stability. Carbon fiber and graphite give the resin an appropriate reinforcing effect and heat stabilizing effect. It is expected that decomposition and carbonization by the organometallic salt compound will effectively work as an improvement in flame retardancy.

  According to the present invention, the problems are as follows: (1) (A) aromatic polycarbonate resin (component A) 100 parts by weight, (B) carbon fiber (component B) 5 to 100 parts by weight, (C) graphite (component C) This is achieved by a flame retardant aromatic polycarbonate resin composition (Configuration 1) comprising 5 to 100 parts by weight and (D) metal salt (component D) 0.001 to 1 part by weight.

  One of the preferred embodiments of the present invention is (2) a flame retardant resin composition having the above constitution (1), wherein the flame retardant resin composition is produced by using graphite having 80% by weight or more of flaky graphite ( Configuration 2). The effect of the present invention is more effectively exhibited when the graphite is all flake graphite (that is, Flaque Graphite).

  One of the preferred embodiments of the present invention is (3) the flame retardant resin composition (Configuration 3) of the above configuration (1) or (2), wherein the graphite of component C has an average particle size of 1 μm to 350 μm. is there. It is considered that such a specific particle size gives the resin an appropriate reinforcing effect and thermal stability effect.

  One of the preferred embodiments of the present invention is (4) the flame retardant resin composition having the above-mentioned constitutions (1) to (3), wherein the metal salt of component D is an alkali (earth) metal salt of an organic sulfonate ( Configuration 4). It is expected that the decomposition and carbonization by the alkali (earth) metal salt of organic sulfonate will work effectively as an improvement in flame retardancy.

  One of the preferred embodiments of the present invention comprises (E) 0.1 to 5 parts by weight of a fluorine-containing anti-dripping agent (E component) with respect to 100 parts by weight of the thermoplastic resin of component (A). It is a flame retardant resin composition (Configuration 5) having the above configurations (1) to (4). By blending such a fluorine-containing anti-drip agent, better flame retardancy can be obtained without affecting conductivity. The effective action of such a fluorine-containing anti-drip agent is also considered to be because the carbon fiber and the C component having a specific particle diameter give the resin an appropriate reinforcing effect and heat stabilizing effect.

  One of the preferred embodiments of the present invention is (6) a molded article for electronic parts formed from the flame-retardant aromatic polycarbonate resin composition having the constitutions (1) to (5). In particular, it is suitable for molded products of electronic devices that require electrical conductivity, flame retardancy, and dimensional accuracy due to the recent miniaturization and higher functionality of electronic components. Examples of such electronic devices include mobile phones, digital cameras, mobile terminals, and notebook computers.

Details of the present invention will be described below.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin used as the component A in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl). ) Propane (commonly called bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropyl Pyridene) diphenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) Examples include fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. A preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, and bisphenol A is particularly preferred from the viewpoint of impact resistance, and is widely used.

In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.
For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition, etc. have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  As the carbonate precursor, carbonyl halide, carbonic acid diester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing the aromatic polycarbonate resin by the interfacial polymerization method using the dihydric phenol and the carbonate precursor, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The aromatic polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, a polyester copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. Carbonate resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  The branched polycarbonate resin can impart anti-drip performance and the like to the reinforced aromatic polycarbonate resin composition of the present invention. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.1% in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 01 to 1 mol%, preferably 0.05 to 0.9 mol%, particularly preferably 0.05 to 0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. Those having a ratio of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

The aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and other straight-chain saturated aliphatic dicarboxylic acids, and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.
Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

The reaction by the interfacial polymerization method is usually a reaction between a dihydric phenol and phosgene, and is reacted in the presence of an acid binder and an organic solvent. As the acid binder, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.

In addition, catalysts such as tertiary amines and quaternary ammonium salts can be used for promoting the reaction, and monofunctional phenols such as phenol, p-tert-butylphenol, p-cumylphenol, etc. as molecular weight regulators. Are preferably used. Furthermore, examples of monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and triacontylphenol. These monofunctional phenols having a relatively long chain alkyl group are effective when improvement in fluidity and hydrolysis resistance is required.
The reaction temperature is usually 0 to 40 ° C., the reaction time is several minutes to 5 hours, and the pH during the reaction is usually preferably maintained at 10 or higher.

  The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonic acid diester. The dihydric phenol and the carbonic acid diester are mixed in the presence of an inert gas and reacted at 120 to 350 ° C. under reduced pressure. . The degree of vacuum is changed stepwise, and finally the phenols produced at 133 Pa or less are removed from the system. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, boron and aluminum hydroxides, Alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, alkoxide of alkali metal or alkaline earth metal, organic acid salt of alkali metal or alkaline earth metal, zinc compound, boron compound, silicon compound, germanium compound, Examples thereof include catalysts usually used for esterification and transesterification of organic tin compounds, lead compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds and the like. A catalyst may be used independently and may be used in combination of 2 or more types. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. Selected by range.

  In the polymerization reaction, in order to reduce phenolic end groups, for example, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate, 2-ethoxycarbonylphenyl phenyl carbonate, etc. Compounds can be added.

Further, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm with respect to the aromatic polycarbonate resin after polymerization. Preferred examples of the deactivator include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.
Details of other reaction formats are well known in various documents and patent publications.

In producing the aromatic polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 10,000 to 50,000, more preferably 14,000. It is -30,000, More preferably, it is 14,000-24,000.
With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 10,000, good mechanical properties cannot be obtained. On the other hand, a resin composition obtained from an aromatic polycarbonate resin having a viscosity average molecular weight exceeding 50,000 is inferior in versatility in that it is inferior in fluidity during injection molding.

  The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, an aromatic polycarbonate resin having a viscosity average molecular weight exceeding the range (50,000) improves the entropy elasticity of the resin. As a result, good moldability is exhibited in gas assist molding and foam molding which may be used when molding a reinforced resin material into a structural member. Such improvement in moldability is even better than that of the branched polycarbonate. As a more preferred embodiment, the A component is an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-1-1), and an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000. An aromatic polycarbonate resin (A-1 component) (hereinafter referred to as “high molecular weight component-containing aromatic polycarbonate resin”) having a viscosity average molecular weight of 16,000 to 35,000. May also be used.

  In such a high molecular weight component-containing aromatic polycarbonate resin (A-1 component), the molecular weight of the A-1-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably. 100,000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-1-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing aromatic polycarbonate resin (component A-1) is obtained by mixing the components A-1-1 and A-1-2 at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. Can do. Preferably, in 100% by weight of the A-1 component, the A-1-1 component is 2 to 40% by weight, more preferably the A-1-1 component is 3 to 30% by weight, and still more preferably The A-1-1 component is 4 to 20% by weight, and particularly preferably the A-1-1 component is 5 to 20% by weight.

  As the preparation method of the component A-1, (1) a method in which the components A-1-1 and A-1-2 are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by the production method (production method of (2)), a separately produced A-1-1 component and / or Examples thereof include a method of mixing the A-1-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a specific viscosity (η _SP ) calculated by the following formula. ,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The viscosity average molecular weight of the aromatic polycarbonate resin in the aromatic polycarbonate resin composition of the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

(B component: carbon fiber)
Examples of the carbon fiber of the present invention include carbon fibers such as metal-coated carbon fibers, carbon milled fibers, and vapor-grown carbon fibers, and carbon nanotubes. The carbon nanotube may be any one of a fiber diameter of 0.003 to 0.1 μm, a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable. Among these, carbon fibers, particularly metal-coated carbon fibers, are preferred in that they are excellent in mechanical strength and can impart good electrical conductivity. Good electrical conductivity has become one of important characteristics required for resin materials in recent digital precision equipment (represented by, for example, a digital still camera).

  As the carbon fiber, any of cellulose, polyacrylonitrile, pitch and the like can be used. Also obtained by a method in which a raw material composition composed of a polymer and a solvent with aromatic methylene bonds of aromatic sulfonic acids or their salts and a solvent is spun or molded and then carbonized without passing through an infusibilization step represented by a method such as carbonization. It is also possible to use those that have been used. Furthermore, any of general-purpose type, medium elastic modulus type, and high elastic modulus type can be used. Among these, polyacrylonitrile-based high elastic modulus type is particularly preferable.

  Moreover, although the average fiber diameter of carbon fiber is not specifically limited, Usually, it is 3-15 micrometers, Preferably it is 5-13 micrometers. A carbon fiber having an average fiber diameter in such a range can exhibit good mechanical strength and fatigue characteristics without impairing the appearance of the molded product. Moreover, the preferable fiber length of carbon fiber is 60-500 micrometers as a number average fiber length in a reinforced aromatic polycarbonate resin composition, Preferably it is 80-400 micrometers, Most preferably, it is a thing of 100-300 micrometers. The number average fiber length is a value calculated by an image analyzer from an optical microscope observation from the carbon fiber residue collected by high temperature ashing of the molded product, dissolution with a solvent, and decomposition with a chemical. is there. Further, when calculating such a value, a value having a length equal to or shorter than the fiber length is a value obtained by a method not counting.

  Further, the surface of the carbon fiber is preferably oxidized for the purpose of improving the adhesion with the matrix resin and improving the mechanical strength. Although the oxidation treatment method is not particularly limited, for example, (1) a method in which a fibrous carbon filler is treated with an acid or alkali or a salt thereof, or an oxidizing gas, (2) a fiber that can be converted into a fibrous carbon filler, or A method of firing the fibrous carbon filler at a temperature of 700 ° C. or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) after the fibrous carbon filler is oxidized and then in the presence of the inert gas. The method of heat-treating with is suitably exemplified.

  The metal-coated carbon fiber is obtained by coating the surface of the carbon fiber with a metal layer. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. As the method of metal coating, various methods described above for the surface coating with different materials in the glass filler can be employed. Of these, the plating method is preferably used. In addition, in the case of such metal-coated carbon fiber, as the original carbon fiber, those mentioned as the above carbon fiber can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm. More preferably, it is 0.2-0.35 micrometer.

  Such carbon fibers and metal-coated carbon fibers are preferably subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, a fibrous carbon filler treated with a urethane resin or an epoxy resin is suitable in the present invention because of its excellent mechanical strength.

  The amount of carbon fiber (component B) in the present invention is 5 to 100 parts by weight based on 100 parts by weight of component A, preferably 6 to 50 parts by weight, and more preferably 7 to 40 parts by weight. If the amount is less than 5 parts by weight, the properties expected for the blending of the filler, such as rigidity, strength, and dimensional stability, tend to be insufficient. On the other hand, when the amount exceeds 100 parts by weight, the toughness of the entire composition is insufficient, which is not preferable for practical use.

(C component: graphite)
As the graphite used as the component C in the present invention, any of natural graphite made of graphite by mineral name and various artificial graphites can be used. As natural graphite, any of earth-like graphite, scale-like graphite (Vein Graphite also called massive graphite), and scale-like graphite (Flake Graphite) can be used. Artificial graphite is obtained by heat-treating amorphous carbon and artificially aligning irregularly arranged fine graphite crystals. In addition to artificial graphite used for general carbon materials, Kish graphite, cracked graphite, And pyrolytic graphite. Artificial graphite used for general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as a main raw material.

  Among these, preferred graphite of the present invention is flake graphite. The resin composition blended with such flaky graphite has good electrical conductivity and good flame retardancy due to good thermal stability. If the thermal stability is poor, the resin is significantly decomposed during combustion, and it is difficult to obtain good flame retardancy. The ratio of the flaky graphite is preferably 80% by weight or more, more preferably 90% by weight or more in the C component, and particularly preferably substantially the entire amount of the C component is the flaky graphite.

  The graphite of the present invention may contain expanded graphite that is thermally expandable by processing the scale-like graphite as represented by acid treatment, or graphite that has been expanded. However, such expanded graphite may be insufficient in terms of thermal stability, and expanded graphite often does not provide good flame retardancy, so expanded graphite and expanded graphite are C In 100% by weight of the component, it is preferably 20% by weight or less, more preferably 10% by weight or less.

    The average particle diameter of graphite in the composition of the present invention is in the range of 1 to 350 μm. The particle size is preferably 5 to 70 μm, more preferably 7 to 40 μm, and still more preferably 7 to 35 μm. By satisfying such a range, good flame retardancy is achieved. On the other hand, when the average particle size is less than 1 μm, the effect of improving the dimensional accuracy is likely to be reduced. It is not preferable. Such floating of the surface is a problem because the graphite may fall off from the surface of the molded product and may be damaged by continuity with the electronic component. In addition, the above preferable average particle diameter has an advantage that the appearance of the molded product is improved and good slidability is easily obtained. This particle size was measured by the following method.

  That is, for example, the obtained resin composition is dissolved in a solvent such as methylene chloride, chloroform, or tetrahydrofuran, and then filtered through a filter such as a glass filter to obtain a residue. The obtained residue is put into soapy water and the aggregated graphite is deagglomerated by ultrasonic vibration. Thereafter, the particle diameter can be measured by a microtrack laser diffraction method in which the particle is irradiated with light and the size of the particle diameter is measured from the amount of scattered light and the pattern scattered by each particle diameter.

  The fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. The volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.

  Further, the surface of graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. It may be given. The compounding quantity of C component is 5-100 weight part on the basis of 100 weight part A component, Preferably it is 15-70 weight part, More preferably, it is 20-45 weight part. If it is less than 5 parts by weight, it is difficult to obtain good antistatic properties and rigidity, and if it exceeds 100 parts by weight, the thermal stability is lowered.

(D component: organometallic salt compound)
The organometallic salt compound which is component D in the present invention is preferably an organic sulfonic acid alkali (earth) metal salt having 1 to 50 carbon atoms, preferably 1 to 40 carbon atoms. The alkali (earth) metal salt of the organic sulfonate includes a fluorine-substituted alkyl sulfone such as a metal salt of a perfluoroalkyl sulfonic acid having 1 to 10, preferably 2 to 8 carbon atoms and an alkali metal or an alkaline earth metal. Metal salts of acids and metal salts of aromatic sulfonic acids having 7 to 50 carbon atoms, preferably 7 to 40 carbon atoms, and alkali metal or alkaline earth metal salts are included.

  Examples of the alkali metal constituting the metal salt of the present invention include lithium, sodium, potassium, rubidium and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium and barium. More preferred is an alkali metal. Among such alkali metals, potassium and sodium are preferable from the viewpoint of flame retardancy and thermal stability, and potassium is particularly preferable. Such potassium salts and sulfonic acid alkali metal salts comprising other alkali metals can be used in combination.

  Specific examples of alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, perfluoro Sodium butanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, perfluorooctanesulfonate Cesium, cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perf Oro hexane sulfonate rubidium, and these may be used in combination of at least one or two. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8. Of these, potassium perfluorobutanesulfonate is particularly preferred.

The alkali (earth) metal salt of perfluoroalkylsulfonic acid composed of an alkali metal is usually mixed with not less than fluoride ions (F ⁻ ). The presence of such fluoride ions can be a factor that lowers the flame retardancy, so it is preferably reduced as much as possible. The ratio of such fluoride ions can be measured by ion chromatography. The content of fluoride ions is preferably 100 ppm or less, more preferably 40 ppm or less, and particularly preferably 10 ppm or less. Moreover, it is suitable that it is 0.2 ppm or more in terms of production efficiency. Such a perfluoroalkylsulfonic acid alkali (earth) metal salt with a reduced amount of fluoride ions is produced by using a known production method, and when producing a fluorine-containing organic sulfonic acid alkali (earth) metal salt. Of reducing the amount of fluoride ions contained in the raw materials, methods of removing hydrogen fluoride obtained by the reaction by gas generated during the reaction or heating, and alkali fluorine-containing organic sulfonate (earth) A metal salt can be produced by a method of reducing the amount of fluoride ions using a purification method such as recrystallization and reprecipitation. In particular, since the metal salt is relatively easily soluble in water, ion-exchanged water, particularly water having an electric resistance value of 18 MΩ · cm or more, that is, an electric conductivity of about 0.55 μS / cm or less, and from room temperature is used. It is preferable to produce by a process of dissolving at high temperature and washing, then cooling and recrystallization.

  Specific examples of the aromatic (earth) metal salt of an aromatic sulfonate include, for example, disodium diphenyl sulfide-4,4′-disulfonate, dipotassium diphenyl sulfide-4,4′-disulfonate, potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate Poly (1,3-phenylene oxide) polysulfonic acid polysodium, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid poly Lithium, poly (2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, naphthalene-2 , 6-disulfonic acid dipotassium, biphenyl-3,3'-disulfonic acid calcium, diphenylsulfone-3-sulfonic acid sodium, diphenylsulfone-3-sulfonic acid potassium, diphenylsulfone-3,3'-disulfonic acid dipotassium, diphenylsulfone -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate. Among these aromatic sulfonate alkali (earth) metal salts, potassium salts are particularly preferable.

  The amount of component D is 0.001 to 1 part by weight, preferably 0.01 to 0.3 part by weight, more preferably 0.03 to 0.2 part by weight, based on 100 parts by weight of component A. is there. If it is less than 0.001 part by weight, the flame retardancy is not achieved, and if it exceeds 1 part by weight, the thermal stability is lowered and the flame retardancy is also lowered.

(E component: fluorine-containing anti-dripping agent)
Examples of the fluorine-containing anti-dripping agent as the E component include a fluorine-containing polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexa Fluoropropylene copolymer, etc.), partially fluorinated polymers as disclosed in US Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

  PTFE having a fibril-forming ability has a very high molecular weight, and tends to bind PTFE to each other by an external action such as shearing force to form a fiber. The molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in the number average molecular weight determined from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there.

  Examples of commercially available PTFE having such fibril forming ability include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Commercially available PTFE aqueous dispersions include Asahi IC Fluoropolymers' full-on AD-1, AD-936, Daikin Kogyo's full-on D-1 and D-2, Mitsui Dupont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Corporation.

As a mixed form of PTFE, (1) a method in which an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-aggregated mixture (Japanese Patent Application Laid-Open No. 60-258263; (Method described in JP-A-63-154744), (2) A method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (method described in JP-A-4-272957), (3) A method in which an aqueous dispersion of PTFE and an organic polymer particle solution are uniformly mixed, and each medium is simultaneously removed from the mixture (described in JP-A-06-220210, JP-A-08-188653, etc.) And (4) a method of polymerizing monomers forming an organic polymer in an aqueous dispersion of PTFE (a method described in JP-A-9-95583), and (5) A method in which an aqueous dispersion of TFE and an organic polymer dispersion are uniformly mixed, and a vinyl monomer is further polymerized in the mixture dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3000” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  As a ratio of PTFE in the mixed form, 1 to 60% by weight of PTFE is preferable in 100% by weight of the PTFE mixture, and more preferably 5 to 55% by weight. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

  The amount of component E is preferably 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight, still more preferably 0.1 to 0.7 parts by weight, based on 100 parts by weight of component A. Parts by weight. In such a range, it is possible to achieve both a sufficient melt dripping preventing effect and good appearance and flow characteristics. In addition, the ratio of the said E component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

<Other additives>
(I) Phosphorus stabilizer It is preferable that the flame retardant resin composition of the present invention further contains a phosphorus stabilizer. Such a phosphorus-based stabilizer greatly improves the thermal stability of the flame-retardant resin composition during production or molding. As a result, mechanical properties, antistatic properties, flame retardancy and molding stability are improved. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.

  Other phosphite compounds include, for example, trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyl diaryl phosphites such as monobutyl diphenyl phosphite, triphenyl phosphite. Triaryl phosphites such as phyto and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite , Bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Erythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di Illustrative are cyclic phosphites such as -tert-butylphenyl) phosphite.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. An example of the tertiary phosphine is triphenylphosphine.

  The amount of the phosphorus stabilizer is preferably 0.0001 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the component A. Part. Further, it is preferable that 50% by weight or more of the phosphorus-based stabilizer is a trialkyl phosphate and / or an acid phosphate compound, and particularly 50% or more of the 100% by weight is a trialkyl phosphate. preferable.

(Ii) Hindered phenol stabilizer The flame retardant resin composition of the present invention further contains a hindered phenol stabilizer, so that, for example, the hue deteriorates during molding or the hue deteriorates during long-term use. The effect is further exhibited. Examples of the hindered phenol-based stabilizer include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel). Propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N , N-dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′- Methylene bis (4-ethyl-6-tert-butylphenol), 4,4′-methylene bis (2,6- Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol) 2,2′- Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert- Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) -5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1,- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3-methyl) -6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4′-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Nbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di- tert-butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate and tetrakis [methylene-3- (3 ′, 5′-di-tert -Butyl-4-hydroxyphenyl) propionate] methane and the like. All of these are readily available. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.

  Other antioxidants than the hindered phenol stabilizers can also be used. Examples of such other antioxidants include lactone stabilizers represented by reaction products of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Are described in JP-A-7-233160), and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthio And sulfur-containing stabilizers such as propionate. The said hindered phenol type stabilizer can be used individually or in combination of 2 or more types.

  The amount of the hindered phenol stabilizer and the other antioxidant is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of component A. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

(Iii) Release agent The flame retardant resin composition of the present invention may contain a release agent. As the release agent, for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), Examples include silicone compounds, fluorine compounds (fluorine oil typified by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. The amount of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 0.8 parts by weight, based on 100 parts by weight of component A.

  Among such release agents, saturated fatty acid esters, particularly partial esters and / or full esters of higher fatty acids and polyhydric alcohols are preferred. Full esters are particularly preferred. Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms. Specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid). ), Heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid and other saturated aliphatic carboxylic acids, as well as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaene Mention may be made of unsaturated aliphatic carboxylic acids such as acids and cetoleic acid. Among these, the aliphatic carboxylic acid preferably has 10 to 22 carbon atoms, and more preferably has 14 to 20 carbon atoms. In particular, saturated aliphatic carboxylic acids having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid are preferred. The aliphatic carboxylic acid such as stearic acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Also in the saturated fatty acid ester, ester compounds obtained from stearic acid or palmitic acid which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

  On the other hand, as a polyhydric alcohol which is a structural unit of saturated fatty acid ester, a C3-C32 thing is more preferable. Specific examples of such polyhydric alcohols include glycerin, diglycerin, polyglycerin (for example, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol, and the like.

The acid value in the saturated fatty acid ester of the present invention is preferably 20 or less (can take substantially 0), more preferably 2 to 15, and still more preferably 4 to 15. The hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.
Content of a mold release agent is 0.005-3 weight part on the basis of 100 weight part A component, Preferably it is 0.01-1 weight part.

(Iv) Ultraviolet Absorber The flame retardant resin composition of the present invention may be required to have good light resistance, and in such a case, the incorporation of an ultraviolet absorber is effective.
Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2-methoxy Phenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-methoxy-2′-carboxybenzophenone and the like.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specifically, the ultraviolet absorber is, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4, 4-hydroxyphenyltriazine). 6-diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) ) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  Specifically, in the case of the cyclic imino ester, the ultraviolet absorber is, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2′-m-phenylenebis (3,1). -Benzoxazin-4-one), 2,2'-p, p'-diphenylenebis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The

  Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. The blending amount of the ultraviolet absorber and light stabilizer is 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight, still more preferably 0.05 to 0. 5 parts by weight.

(V) Other Flame Retardant The aromatic resin composition of the present invention achieves good flame retardancy without substantially containing a chlorine flame retardant, a bromine flame retardant, and a phosphorus flame retardant. However, the addition of such a flame retardant does not inhibit the flame retardant effect. However, in order to make better use of the characteristics of the present invention, it is preferable that the flame retardant resin composition of the present invention does not substantially contain a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. On the other hand, in order to further improve the flame retardancy by utilizing the features of the present invention, for example, a silicone flame retardant can be further blended.

  Such a silicone flame retardant is a compound having a siloxane bond and improves the flame retardancy by a chemical reaction during combustion, and various compounds conventionally proposed as flame retardants for resins can be used. The silicone compound binds itself when burned or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to a resin such as polycarbonate by a reduction reaction during the formation of the structure. It is considered a thing. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone-based flame retardant of the present invention is represented by D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _{m D n Q q, M m T} p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone-based flame retardant are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and a more preferable structure is M _m D _n or M _m D _n T _p .

  Here, the coefficients m, n, p, and q in the above formula are integers of 1 or more that indicate the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency. When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

Furthermore, the silicone flame retardant of the present invention may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and decyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group and tolyl group. Groups and aralkyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. Especially as an alkyl group, C1-C4 alkyl groups, such as a methyl group, an ethyl group, a propyl group, are preferable.
Such a silicone flame retardant is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 6 parts by weight, based on 100 parts by weight of the component A.

（ここで式中、Ｘは加水分解性基を表し、Ｙは反応性有機官能基を表す。） (Vi: silane compound or silicone compound)
In the present invention, a silane compound represented by the following formula (1) can also be used.

(Wherein, X represents a hydrolyzable group and Y represents a reactive organic functional group.)

As a specific example of the silane compound, KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) is preferable, and is a silane compound represented by the following formula (2).

（ここで式中、Ｒ_１、Ｒ_２、Ｒ_３は反応性基またはメチル基を表す。また、ｍ、ｎは０≦ｍ≦１００、０≦ｎ≦１００の整数を表す。ただし、ｍ、ｎ共に０の場合は除く。） Moreover, the silicone compound represented by following formula (3) can also be used for this invention.

(Wherein R ₁ , R ₂ and R ₃ represent a reactive group or a methyl group. M and n represent integers of 0 ≦ m ≦ 100 and 0 ≦ n ≦ 100, provided that m, (except when n is 0)

( ここで式中、Ｒは NH₂-C₂H₄-NH-C₃H₆である。また、ｍ、ｎは０≦ｍ≦１００、０≦ｎ≦１００の整数を表す。ただし、ｍ、ｎ共に０の場合は除く。)

As specific examples of the silicone compound, SF8417 (manufactured by Toray Dow Corning) and BY16-855D (manufactured by Toray Dow Corning) are preferable, and are represented by the following formulas (4) and (5), respectively.

(Wherein R is NH ₂ —C ₂ H ₄ —NH—C ₃ H ₆ , and m and n represent integers of 0 ≦ m ≦ 100 and 0 ≦ n ≦ 100, where m , N is excluded when 0.)

  Of the compounds (3), (4), and (5), the compound represented by (3) is most preferable.

(Vii filler)
In the flame-retardant resin composition of the present invention, various fillers other than the B and C components can be blended as reinforcing fillers within the range where the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, fullerene, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, metal oxide particles And metal oxide fibers, metal oxide balloons, and various whiskers (such as potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.

In addition, the flame retardant resin composition of the present invention may contain a small amount of additives known per se for imparting various functions to the molded article and improving the properties. These additives are used in usual amounts as long as the object of the present invention is not impaired.
Examples of such additives include sliding agents (for example, PTFE particles other than the E component), colorants (for example, pigments and dyes such as carbon black and titanium oxide), fluorescent dyes, and inorganic phosphors (for example, aluminate as a base crystal). Phosphors), antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), photochromic agents, etc. Is mentioned.

(Manufacture of flame retardant resin composition)
Arbitrary methods are employ | adopted in order to manufacture the flame-retardant resin composition of this invention. For example, the components A to E and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then an extrusion granulator as necessary. Or a briquetting machine or the like, and granulating the preliminary mixture, followed by melt-kneading with a melt-kneader represented by a vent type twin-screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then mixed with the component A or directly supplied to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like. Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

(Molding)
A molded article comprising the aromatic polycarbonate resin composition of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, an aromatic polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various irregular extrusion molded articles, a sheet | seat, and a film. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The aromatic polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding, blow molding or the like.

(surface treatment)
Further, the molded article of the present invention can be subjected to various surface treatments. As the surface treatment, various surface treatments such as a hard coat, a water / oil repellent coat, a hydrophilic coat, an antistatic coat, an ultraviolet absorption coat, an infrared absorption coat, and metalizing (evaporation) can be performed. Examples of the surface treatment method include liquid deposition, vapor deposition, thermal spraying, and plating. As the vapor deposition method, either a physical vapor deposition method or a chemical vapor deposition method can be used. Examples of physical vapor deposition include vacuum vapor deposition, sputtering, and ion plating. Examples of the chemical vapor deposition (CVD) method include a thermal CVD method, a plasma CVD method, and a photo CVD method.

  The aromatic polycarbonate resin composition of the present invention has high rigidity, conductivity, low anisotropy and good dimensional stability by using carbon fiber and graphite having a specific particle diameter, and particularly an alkali organic sulfonate. (Earth) By using a metal salt, it has good flame retardancy even if it does not substantially contain chlorine-based flame retardant, bromine-based flame retardant, and phosphorus-based flame retardant. A flame retardant resin composition and a molded product thereof (particularly preferably a molded housing product) are provided by combining an inhibitor.

  The aromatic polycarbonate resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and particularly for applications that require efficient heat dissipation from electrical and electronic equipment. It satisfies the corresponding good characteristics.

  Such applications include, for example, personal computers, notebook computers, game machines (home game machines, arcade game machines, pachinko machines, slot machines, etc.), display devices (LCD, organic EL, electronic paper, plasma display, projectors, etc.) The power transmission component (represented by the housing of the dielectric coil power transmission device) is exemplified. Examples of such applications include printers, copiers, scanners, and fax machines (including these multifunction machines). Examples of such applications include precision equipment such as VTR cameras, optical film cameras, digital still cameras, camera lens units, security devices, and mobile phones. In particular, the flame-retardant resin composition of the present invention is suitably used for a housing, a cover, and a frame of a digital image information processing apparatus such as a camera barrel or a digital camera.

  In addition, the flame-retardant resin composition of the present invention is a medical device such as a massage machine or a high oxygen treatment device; a home electric appliance such as an image recorder (such as a so-called DVD recorder), an audio device, and an electronic musical instrument; It is also suitable for parts such as gaming machines such as machines; and home robots equipped with precision sensors.

In addition, the flame-retardant resin composition of the present invention includes various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, electronic It can be used for a container for conveying parts (IC magazine case, silicon wafer container, glass substrate storage container, carrier tape, etc.).
Therefore, the resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and the industrial effect exerted by the resin composition is extremely large.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.
(I) Flame retardance Using a test piece having a shape conforming to UL standard 94 and having a thickness of 0.8 mm, a combustion test was performed by a method according to the vertical combustion test of UL standard 94. The maximum number of burning seconds in a set of 5 specimens was recorded. After the molding, the test piece was stored for 48 hours in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and then a combustion test was performed.
(Ii) Rigidity (flexural modulus)
The flexural modulus (MPa) was measured according to ISO178. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(Iii) Surface resistivity: 50 mm in width, 90 mm in length, 2 mm thick part of a three-stage plate having a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), 1 mm (length 25 mm) from the gate side The plate was stored for one week in an environment at a temperature of 23 ° C. and a relative humidity of 50%, and the condition was adjusted. Then, the test piece was taken with a digital insulation meter (DSM-8103, manufactured by Toa Denpa Kogyo Co., Ltd.). The surface resistivity was determined. It shows that electroconductivity is excellent, so that the numerical value of surface resistivity is small.
(Iv) Anisotropy: A flat plate having a short side of 50 mm, a long side of 100 mm, and a thickness of 4 mm having a film gate having a thickness of 1.5 mm on one short side was molded and conditioned at 23 ° C., 50% RH for 24 hours. Thereafter, the flow direction and the perpendicular direction dimension of the flow of the flat plate were measured using a three-dimensional measuring machine (MICROPAK 550 manufactured by Mitoyo Seisakusho Co., Ltd.), and the molding shrinkage in the flow direction and the perpendicular direction was determined. The ratio of the molding shrinkage ratio obtained here in the direction perpendicular to the flow direction (shrinkage ratio in the flow direction / shrinkage ratio in the perpendicular direction) was obtained as anisotropy. The anisotropy value is preferably closer to 1.
The following were used as raw materials.

Each component indicated by symbols in Tables 1 and 2 is as follows.
(A component)
PC: Linear polycarbonate resin powder having a viscosity average molecular weight of 22400 (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
(B component)
CF: Carbon fiber [Besfight manufactured by Toho Rayon Co., Ltd. HTA-C6-U, PAN system, urethane bundling, diameter 7 μm]
(C component)
C-1: Scale-like graphite (average particle size 3.3 μm, fixed carbon amount 80.0%, volatile content 3.0%, ash content 17.0%) [Nishimura Graphite Co., Ltd. ultra fine graphite (trade name) ]
C-2: flake graphite (average particle size 10 μm, fixed carbon content 99.0%, volatile content 0.6%, ash content 0.4%) [Nishimura Graphite Co., Ltd. PB-99 (trade name)]
C-3: flake graphite (average particle size 25 μm, fixed carbon content 99.0%, volatile content 0.6%, ash content 0.4%) [PA-99 (trade name) manufactured by Nishimura Graphite Co., Ltd.]
C-4: flake graphite (average particle size 350 μm, fixed carbon content 98.0%, volatile content 1.5%, ash content 0.5%) [5098 (trade name) manufactured by Nishimura Graphite Co., Ltd.]
(D component)
FR: potassium perfluorobutane sulfonate (manufactured by Dainippon Ink & Chemicals, Inc., MegaFuck F-114P)
(E component)
PTFE: Polytetrafluoroethylene having a fibril forming ability (“Polyflon MPA FA500” (trade name) manufactured by Daikin Industries, Ltd.)
(Other ingredients)
PEW: Polyethylene wax (High wax 405MP manufactured by Mitsui Chemicals, Inc.)
SL: Fatty acid ester mainly composed of stearyl stearate and glycerin tristearate (Riquemar SL900 manufactured by Riken Vitamin Co., Ltd.)
AS: Aminosilane compound [KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.]

[Examples 1-8, Comparative Examples 1-6]
After mixing an aromatic polycarbonate resin, carbon fiber, scaly graphite, an organic sulfonate alkali (earth) metal salt, and a fluorine-containing anti-dripping agent in the blending amounts shown in Tables 1 and 2 in a blender, a vent type 2 Pellets were obtained by melt-kneading using a shaft extruder. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX-30XSST (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions are a discharge rate of 16 kg / h, a screw rotation speed of 220 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 280 ° C. from the first supply port to the second supply port and 290 ° C. from the second supply port to the die part. did. Carbon fiber is supplied from the second supply port using the side feeder of the extruder, and graphite is supplied first together with other polycarbonate resin, organic sulfonate alkali (earth) metal salt, and fluorine-containing anti-dripping agent. It was supplied to the extruder through the mouth. The first supply port here is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port.

  The obtained pellets were dried at 120 ° C. for 5 hours with a hot air circulation dryer, and then a test piece for evaluation was molded at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. using an injection molding machine. The evaluation results are shown in Tables 1 and 2.

  As apparent from the above table, it can be seen that the flame retardant resin composition of the present invention has good flame retardancy.

Claims (7)

(A) aromatic polycarbonate resin (component A) 100 parts by weight, (B) carbon fiber (component B) 5 to 100 parts by weight, (C) graphite (C component) 5 to 80% by weight or more being scaly graphite 100 parts by weight, (D) an organic metal salt compound component (D) 0.001 parts by weight, and an amino silane compound flame retardant aromatic polycarbonate resin composition comprising a.   The flame retardant aromatic polycarbonate resin composition according to claim 1, wherein the graphite (C component) is graphite having an average particle diameter of 1 μm to 350 μm.   The flame retardant aromatic polycarbonate resin composition according to claim 1 or 2, wherein the organic metal salt compound (component D) is an alkali (earth) metal salt of an organic sulfonate.   The organometallic salt compound (component D) is one or more selected from the group consisting of alkali (earth) metal salts of perfluoroalkyl sulfonic acids and alkali (earth) metals of aromatic sulfonic acids. The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3.   The flame-retardant fragrance according to any one of claims 1 to 4, comprising 0.1 to 5 parts by weight of (E) a fluorine-containing anti-dripping agent (E component) with respect to 100 parts by weight of component A. Group polycarbonate resin composition.   The aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein a flame retardant level V-2 of UL94 standard is achieved in a molded product having a thickness of 0.8 mm.   The molded article for electronic components formed from the flame-retardant aromatic polycarbonate resin composition of any one of the said Claims 1-6.