JP5144872B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, by adding a fluorine-containing organometallic salt with reduced fluoride ions, the effect of preventing the molten dripping (hereinafter sometimes referred to as “drip”) is improved, and the aromatic polycarbonate is superior in flame retardancy. The present invention relates to a resin composition. Furthermore, the present invention provides an aromatic polycarbonate resin composition containing a fluorine-containing organometallic salt, a method for producing the aromatic polycarbonate resin composition in which the drip is prevented, and the drip is prevented in the resin composition. Related to the method.

  Aromatic polycarbonate resins are used as various molded article materials, taking advantage of their transparency and impact resistance, and are used in a wide range of fields. Further, in applications using this aromatic polycarbonate resin material, in recent years, attention has been paid to flame retardancy at the time of fire, and a resin composition having high flame retardancy in addition to the above-described properties is required. As a method for imparting flame retardancy to an aromatic polycarbonate resin, a flame retardant aromatic polycarbonate resin composition to which a halogen compound or a phosphorus compound has been added has been proposed, and OA equipment has a strong demand for flame retardancy. In addition, silicon flame retardants have been proposed.

  Many techniques have already been proposed for flame-retarding aromatic polycarbonate resins. For example, a method for making an aromatic polycarbonate resin flame-retardant by adding an organic metal salt has been proposed (see Patent Documents 1 and 2). However, the applications for which flame retardant aromatic polycarbonate resin materials are required are extremely diversified, and further flame retardant improvement techniques are desired.

  In recent years, in order to improve flame retardancy, it is not a method of changing the type of flame retardant or increasing the amount of flame retardant, but a method of adjusting the quality of conventionally known flame retardant to an appropriate range and improving flame retardancy Has also been proposed. For example, in an aromatic polycarbonate resin composition containing a fluorine-containing organometallic salt compound typified by an alkali metal salt of perfluoroalkylsulfonic acid, (i) the pH of the compound in an aqueous solution or dispersion is in the range of 5-9. (Ii) a method for reducing the alcohol-insoluble content of the compound (see Patent Document 4). However, all of these proposals are interesting in that the factors that reduce the flame retardancy are clarified, but the difference from the conventional commercially available fluorine-containing organometallic salt compounds is not sufficiently clear, and actually the effect of improving flame retardancy. Was not expressed. In addition, although the manufacturing method which makes the fluoride ion in perfluoroalkylsulfonic acid alkali metal salt about 1 ppm is well-known (refer patent document 5), perfluoroalkylsulfonic acid alkali metal salt obtained by this manufacturing method and There is no known combination with aromatic polycarbonate resins.

Japanese Patent Publication No.54-32456 Japanese Patent Publication No. 60-19335 JP 2001-31855 A JP 2001-115004 A Japanese Patent Laid-Open No. 1-268671

  An object of the present invention is to provide a flame retardant aromatic polycarbonate resin composition. More specifically, an object of the present invention is to provide a flame retardant aromatic polycarbonate resin composition containing a fluorine-containing organometallic salt compound, which has improved flame retardancy.

  As a result of intensive investigations aimed at achieving the above object, the present inventors have further reduced the proportion of fluoride ions contained in a trace amount in the fluorine-containing organometallic salt compound, whereby a polycarbonate containing the compound is contained. It has been found that the drip prevention effect during resin combustion is improved. This finding is that the ratio of the fluorine-containing organometallic salt compound to the aromatic polycarbonate resin composition is a small ratio of less than 1% by weight, and the ratio of fluoride ions in the compound is also a very small ratio of less than 100 ppm. In view of the fact, that is, considering that the ratio of the fluoride ion to the aromatic polycarbonate resin is extremely small, it is extremely surprising. Based on this finding, the inventors have further studied and completed the present invention.

  The present invention includes (1) 100 parts by weight of an aromatic polycarbonate resin (component A) and a fluorine-containing organometallic salt compound in which the content of fluoride ions measured by ion chromatography is 0.2 to 20 ppm by weight. (B component) It concerns on the aromatic polycarbonate resin composition which consists of 0.005-0.6 weight part. According to this configuration (1), an anti-drip effect is improved, and an aromatic polycarbonate resin composition having more excellent flame retardancy is provided. The reason why the anti-drip effect is improved by using a fluorine-containing organometallic salt in which the fluoride ion is reduced to a specific amount or less is considered as follows, although not fully elucidated. In other words, although it is a very small amount, fluoride ions act to violently decompose the carbonate bond during the combustion, and accordingly, it is considered that the melt viscosity of the resin during the combustion is lowered to induce the drip. . Moreover, since the reaction expands in a chain manner, it is considered that the effect of having the specific ratio or less appears remarkably. Such a decomposition reaction is inferred from the behavior that, when the resin composition is molded at a high temperature, for example, the molecular weight of the aromatic polycarbonate resin decreases more as the fluoride ion amount increases.

  One of the preferred embodiments of the present invention is (2) the aromatic polycarbonate resin composition according to (1), wherein the component B is an alkali metal salt of perfluoroalkylsulfonic acid. According to this configuration (2), an aromatic polycarbonate resin composition having better flame retardancy is provided. On the other hand, the alkali metal salt of perfluoroalkylsulfonic acid is inevitably mixed with fluoride ions to some extent on the basis of its production method. It succeeded in further improving the flame retardance of the aromatic polycarbonate resin composition containing this.

  One of the preferred embodiments of the present invention is (3) a smooth flat plate having a thickness of 2 mm made of the resin composition and having an arithmetic average roughness (Ra) of 0.03 μm, and the haze measured by JIS K7105 is 0.00. It is an aromatic polycarbonate resin composition of said (1)-(2) satisfying that it is 3-20%. In the aromatic polycarbonate resin composition, polytetrafluoroethylene (PTFE) having fibril forming ability is commonly used as an anti-drip agent. However, the blending of PTFE lowers transparency, which is one of the characteristics of the aromatic polycarbonate resin. On the other hand, perfluoroalkylsulfonic acid alkali metal salts achieve flame retardancy with a small amount of blending, and thus can impart flame retardancy while maintaining transparency to some extent. Therefore, according to the present invention, the anti-drip effect of the aromatic polycarbonate resin composition can be enhanced by blending the specific fluorine-containing organometallic salt compound. Therefore, blending of PTFE from the resin composition conventionally blended with PTFE is possible. Can be made unnecessary or reduced. As a result, according to the configuration (3), an aromatic polycarbonate resin composition having better transparency while maintaining flame retardancy is provided.

  Furthermore, one of the preferred embodiments of the present invention is (4) a molded article formed from the aromatic polycarbonate resin composition of (1) to (3).

  The present invention also relates to (5) a method for producing an aromatic polycarbonate resin composition flame-retarded with a fluorine-containing organometallic salt compound, the melting and dropping of which is prevented in a vertical combustion test of UL standard 94, The production method comprises a fluorine-containing organometallic salt compound (100% by weight of an aromatic polycarbonate resin (component A)) in which the fluoride ion content measured by ion chromatography is 0.2 to 20 ppm by weight. B component) It is based on the manufacturing method of the aromatic polycarbonate resin composition characterized by mix | blending 0.005-0.6 weight part.

  In the aromatic polycarbonate resin composition, when the combustion rank in the vertical combustion test of UL standard 94 cannot be achieved by the occurrence of drip, the blending of PTFE having fibril forming ability conventionally used as an anti-drip agent as described above, and Prescriptions such as increasing the viscosity of aromatic polycarbonate resins have been taken. However, any of these formulations may impair other required properties. Furthermore, although increasing the amount of flame retardant is one of the simplest prescriptions, the addition of the flame retardant does not affect the characteristics of the aromatic polycarbonate resin in the first place. There is basically a demand for this.

  On the other hand, according to the present invention, by adding a specific fluorine-containing organic metal salt, the conventional fluorine-containing organic metal salt has a drip-preventing effect on a resin composition in which a drip has occurred at a predetermined thickness. Can be given. That is, the method for producing an aromatic polycarbonate resin composition having a drip prevention effect according to the configuration (5) provides a novel method different from the conventional method.

  In addition, the present invention provides (6) melting in a UL standard 94 vertical combustion test of a resin composition in which 0.005 to 0.6 parts by weight of a fluorine-containing organometallic salt is blended with 100 parts by weight of an aromatic polycarbonate resin (component A). A method for preventing dripping, wherein a fluorine-containing organometallic salt compound (component B) having a fluoride ion content of 0.2 to 20 ppm by weight as measured by ion chromatography is used as the metal salt. The present invention relates to a method for preventing melt dripping.

  Similar to the configuration (5), according to the configuration (6), an aromatic polycarbonate resin composition containing a conventional fluorine-containing organic metal salt, that is, a fluorine-containing organic metal salt having a fluoride ion content exceeding 20 ppm. However, when the target specimen thickness does not have a drip-preventing effect, the fluorine-containing organic metal salt having the specific fluoride ion content of the present invention is used to prevent drip. An effect can be imparted, and the present invention provides an unprecedented method of imparting a drip prevention effect by blending a specific fluorine-containing organometallic salt as in the present invention.

  Furthermore, one of the preferred embodiments of the present invention is (7) further containing 0.005 to 2 parts by weight of a fatty acid ester compound (C-1 component) as a release agent (C component) per 100 parts by weight of A component. (7a) the aromatic polycarbonate resin composition of (1) to (3), (7b) the molded product of (4), (7c) the production method of (5), and (7d) ( This is a method for preventing the melt dripping of 6). The blending of the fatty acid ester compound is preferable in terms of achieving good releasability while maintaining transparency, but it is also true that the flame retardancy may be greatly impaired by blending a small amount of the fatty acid ester compound. It is. According to this configuration (7) (including 7a to 7d, the same applies hereinafter), an aromatic polycarbonate resin composition that exhibits the effect of the fatty acid ester compound while maintaining good flame retardancy, its molded article, A method for producing a resin composition and a method for preventing its melting and dropping are provided.

  One of the preferred embodiments of the present invention is (8) Further, per 100 parts by weight of component A, as a flame retardant (component D), a phosphate compound (component D-1), a silicone compound (component D-2), and bromination (8a) of (1) to (3) and (7a), comprising 0.01 to 5 parts by weight of at least one compound selected from polycarbonate (including oligomer) (component D-3) (8b) the molded product of (4) and (7b), (8c) the production method of (5) and (7c), and (8d) of (6) and (7d). This is a method for preventing melt dripping.

  The combined use of the flame retardants of D-1 to D-3 and the fluorine-containing organic metal salt imparts good flame retardancy while maintaining the transparency, heat resistance, impact resistance, etc. of the aromatic polycarbonate resin. Therefore, it is a conventionally known flame retardant formulation. Since the resin composition having such a formulation maintains various balances of properties at its limit, a great improvement in flame retardancy in substantially the same composition has great technical significance. Therefore, the use of the specific fluorine-containing organometallic salt of the present invention is more meaningful in combination with these flame retardants. Therefore, according to the configuration (8), an aromatic polycarbonate resin composition having better flame retardancy while balancing various characteristics, a molded product thereof, a method for producing the resin composition, and a molten dripping thereof A method for preventing the problem is provided.

  One preferred embodiment of the present invention is (9) further comprising 0.1 to 50 parts by weight of a carbon filler (E-1 component) as a filler (E component) per 100 parts by weight of the A component. 9a) the aromatic polycarbonate resin composition of (1) to (3), (7a) and (8a), (9b) the molded product of (4), (7b) and (8b), (9c) ( 5), (7c) and (8c) production method, and (9d) (6d) (7d) and (8d) are methods for preventing melt dripping. According to the configuration (9), an aromatic polycarbonate resin composition having good flame retardancy even in a carbon filler which is disadvantageous in terms of combustibility, a molded product thereof, a method for producing the resin composition, and A method for preventing the melt dripping is provided.

Hereinafter, the details of the present invention will be described.
(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 resins, copolymerized polycarbonate resins copolymerized with bifunctional alcohols (including alicyclics), and polyester carbonate resins copolymerized with such bifunctional carboxylic acids and difunctional alcohols are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

  Since the branched polycarbonate resin can synergistically improve the drip prevention ability of the flame retardant aromatic polycarbonate resin composition of the present invention, its use is preferable. 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 ratio of the polyfunctional compound in the branched polycarbonate resin is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, more preferably 0.01 to 0.8 mol in the total amount of the aromatic polycarbonate resin. The mol%, particularly preferably 0.05 to 0.4 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also preferably in the above-mentioned range in the total amount of the aromatic polycarbonate resin. Such a branched structure amount 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 ⁻⁸ to 1 × 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent, relative to 1 mol of dihydric phenol as a raw material. 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.
The details of the reaction formats other than those described above are also well known in books and patent publications.

  In producing the flame retardant 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. It is 14,000-30,000, More preferably, it is 14,000-24,000.

  Aromatic polycarbonate resins having a viscosity average molecular weight of less than 10,000 may not provide practically expected impact resistance, etc., and may not have sufficient drip-preventing ability, resulting in poor flame retardancy. Cheap. 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. Moreover, the transparency that is a feature of the present invention may not be fully utilized due to an increase in the molding temperature.

  The aromatic polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, the aromatic polycarbonate resin having a viscosity average molecular weight exceeding the above range (50,000) exhibits the drip prevention ability of the flame retardant aromatic polycarbonate resin composition of the present invention by improving the entropy elasticity of the resin. Furthermore, it can be improved synergistically. This improvement effect is even better than the branched polycarbonate. As more preferred embodiments, the A component is an aromatic polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-3-1), and the aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000. An aromatic polycarbonate resin (A3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter referred to as “high molecular weight component-containing aromatic polycarbonate resin”). Can also be used.

  In such a high molecular weight component-containing aromatic polycarbonate resin (A3 component), the molecular weight of the A-3-1 component is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000. 000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-3-2 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 (A3 component) can be obtained by mixing the A-3-1 component and the A-3-2 component at various ratios and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in A100 component 100 weight%, A-3-1 component is 2 to 40 weight%, More preferably, A3-1 component is 3 to 30 weight%, More preferably, A- The 3-1 component is 4 to 20% by weight, and the A-3-1 component is particularly preferably 5 to 20% by weight.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component 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 such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 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

Moreover, the calculation method of the said viscosity average molecular weight is applied also to the viscosity average molecular weight measurement of the resin composition of this invention and the molded article shape | molded from this resin composition. That is, in the present invention, these viscosity average molecular weights are obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution obtained by dissolving 0.7 g of a molded product in 100 ml of methylene chloride into the above formula.

(B component: fluorinated organometallic salt)
The component B in the present invention contains a fluoride ion (F ⁻ ) content of 0.2 to 20 ppm, preferably 0.2 to 10 ppm, more preferably 0.2 to 5 ppm as measured by ion chromatography. It is a fluorine organometallic salt compound.

  The fluorine-containing organic metal salt in the present invention refers to a metal salt compound composed of an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. As a more preferred specific example, Examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organic metal salts can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. 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.

  The metal constituting the metal salt of the present invention is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include beryllium, magnesium, and calcium. Strontium and barium. More preferred is an alkali metal. Accordingly, a preferred B component of the present invention is a perfluoroalkylsulfonic acid alkali metal salt. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Specific examples of such B component, particularly preferred alkali metal perfluoroalkyl sulfonates include potassium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluorohexane sulfonate, potassium perfluorooctane sulfonate, penta Sodium fluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctanesulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, perfluorobutanesulfone Cesium acid, cesium perfluorooctane sulfonate, cesium perfluorohexane sulfonate, perfluorobutane sulfonate Rubidium, and perfluorohexane sulfonic acid rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

The fluoride ion content measured by ion chromatography in the present invention is a value measured by the following method. That is, a precisely weighed fluorine-containing organometallic salt sample is dissolved in ultrapure water (for reagents) to prepare a 0.2 wt% aqueous solution. After sufficiently dissolving, the aqueous solution is filtered (for example, using an OnGuard-H cartridge manufactured by DIONEX), and a predetermined amount is extracted from the filtered aqueous solution to obtain a measurement solution. The measurement solution is measured using an ion chromatograph measurement device. For this measurement, for example, an ion chromatograph DX-100 manufactured by DIONEX was used, the column was ASA-SC for anion analysis, the detector was an electric conductivity meter, and the eluent was 1.8 mmol Na with respect to 1 liter of pure water. A mixed aqueous solution in which ₂ CO ₃ and 1.7 mmol of NaHCO ₃ are dissolved, and the eluent flow rate is 1.5 ml / min. The content of fluoride ions present in the sample can be determined based on the obtained fluoride ion intensity, and the content of fluoride ions in the component B of the present invention is calculated. The concentration of the prepared aqueous solution described here was 0.2% by weight, but can be appropriately changed depending on the type of the fluorine-containing organometallic salt and the amount of fluoride ions. The ratio of fluoride ions in the aromatic polycarbonate resin composition can be obtained by dissolving a certain amount of sample in methylene chloride, adding a certain amount of ultrapure water, mixing and stirring, What is necessary is just to extract a fixed quantity what filtered the obtained water layer with the OnGuard-H cartridge by DIONEX, and use it as a measurement solution.

  The production method of component B of the present invention uses a known production method, a method for reducing the amount of fluoride ions contained in a raw material when producing a fluorine-containing organic metal salt, and a fluorination obtained by reaction. Producing by a method that removes hydrogen and the like by a gas generated during the reaction or heating, and a method of reducing the amount of fluoride ions by using a purification method such as recrystallization and reprecipitation for producing a fluorine-containing organometallic salt. Can do. In particular, since the B component is relatively soluble in water, ion-exchanged water, particularly water having an electric resistance 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.

  Perfluoroalkylsulfonic acid alkali metal salt, which is a preferred component B in the present invention, is usually obtained by using perfluoroalkylsulfonic acid or perfluoroalkylsulfonyl fluoride as a basic compound such as alkali metal carbonate or hydroxide. It is performed by the method of neutralizing with. When perfluoroalkyl sulfonic acid is used, it is often in a liquid state and is difficult to purify. Therefore, it contains a relatively large amount of fluoride ions mixed in the production of the sulfonic acid. On the other hand, when perfluoroalkylsulfonyl fluoride is used, fluoride ions are generated by the neutralization reaction.

  When perfluoroalkylsulfonic acid is used, fluoride ions can be reduced by the method of performing the neutralization reaction disclosed in JP-A-1-268671 in an acidic region having a pH of 3 or less. According to such a method, a perfluoroalkylsulfonic acid alkali metal salt with reduced fluoride ions can be obtained without further purification steps. On the other hand, when perfluoroalkylsulfonyl fluoride is used as a raw material, it is preferable to reduce the fluoride ion to a predetermined amount by recrystallization as described above after the production of the metal salt. Moreover, when using perfluoroalkylsulfonic acid as a raw material, it is preferable to further include a purification step by recrystallization. More specifically, by a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, and a method of neutralizing perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. The perfluoroalkylsulfonic acid alkali metal salt produced (preferably by the latter method) is ion-exchanged water (particularly preferably having an electric resistance of 18 MΩ · cm or more) 2 to 10 times the metal salt. 1) to 40 to 90 ° C. (more preferably 60 to 85 ° C.) and dissolved for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. C., more preferably in the range of 10 to 35.degree. C., and the precipitated crystals are removed by filtration, whereby a perfluoroalkylsulfonic acid alkali which is a preferred B component of the present invention. It is preferable to produce the Shokushio.

  The blending ratio of the B component in the present invention is 0.005 to 0.6 parts by weight, preferably 0.005 to 0.2 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin of the A component. Preferably it is 0.008-0.13 weight part. The better the range, the better the flame retardancy and the more transparent the material.

(C component: mold release agent)
A release agent can be blended in the aromatic polycarbonate resin composition of the present invention as necessary. In this invention, since it has favorable flame retardance, even when it is a case where the mold release agent which tends to have a bad influence with respect to a flame retardance is mix | blended, favorable flame retardance can be achieved. Known release agents can be used. 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), silicone compound, fluorine compound (E.g., fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. The release agent is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (component A).

  Among them, fatty acid ester (C-1 component) is preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid 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, And saturated aliphatic carboxylic acids such as docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and setoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  Since the above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil), these aliphatic carboxylic acids. The acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the C-1 component of the present invention, an aliphatic carboxylic acid produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the C component of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of component C is more preferably in the range of 0.1-30. 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.

  The amount of component C (preferably component C-1) is 0.005 to 2 parts by weight, preferably 0.01 to 1 part by weight, preferably 0.05 to 0.5 parts by weight per 100 parts by weight of component A. Part. In such a range, the aromatic polycarbonate resin composition has good releasability and flame retardancy, and particularly has good transparency in the C-1 component.

(D component: flame retardant)
A flame retardant other than the component B can be blended in the aromatic polycarbonate resin composition of the present invention as necessary. Such flame retardants include brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (including oligomers), brominated polyacrylates, halogenated flame retardants such as chlorinated polyethylene, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomers. Organophosphorus flame retardants such as compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, alkali (earth) metal sulfonates, borate metal salt flame retardants, and stannic acid other than the component B of the present invention Examples thereof include organic metal salt flame retardants such as metal salt flame retardants, and silicone flame retardants. Among these, as described above, at least one compound selected from a phosphate compound (D-1 component), a silicone compound (D-2 component), and a brominated polycarbonate (including oligomer) (D-3 component) is preferable. And B component of the present invention.

(D-1 component: phosphate compound)
Various phosphate compounds known as conventional flame retardants can be used as the D-1 component phosphate compound used as a flame retardant other than the B component of the present invention, but it is particularly preferably represented by the following general formula (i). One or more phosphate compounds may be mentioned.

（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導されるものが挙げられ、ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していないフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導されるものである。）

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And those derived from (4-hydroxyphenyl) sulfide, where n is an integer from 0 to 5, or in the case of a mixture of phosphate esters having different numbers of n, is an average value from 0 to 5, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol substituted or unsubstituted with one or more halogen atoms .)

  Specific examples of the phosphate compound substituted with a halogen atom include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like. The

  Specific examples of the phosphate compound not substituted with a halogen atom include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenyl bis (diphenyl phosphate), and phosphate ester oligomers mainly composed of bisphenol A bis (diphenyl phosphate). It indicates that a small amount of other components having different degrees of polymerization may be included, and more preferably, the component of n = 1 in the formula (i) is 85% by weight or more, more preferably 89% by weight or more, and still more preferably 90% by weight. % Is contained ).

(D-2 component: silicone compound)
The D-2 component silicone compound used as a flame retardant other than the B component of the present invention improves flame retardancy by a chemical reaction during combustion, and has been proposed as a flame retardant for aromatic polycarbonate resins. Various compounds can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. 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 .

Structure of the silicone compound of the D-2 component of the present invention, specifically, _D n as rational _{formula, 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 compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are 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. .

  Further, the D-2 component silicone compound 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.

  Furthermore, it is preferable that D-2 component contains an aryl group at the point which can provide the aromatic polycarbonate resin composition excellent in the flame retardance and transparency. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (ii) is preferably 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（ｉｉ）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（１）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (ii), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (1), n is 2; In these cases, different types of X can be taken.)

  The D-2 component of the present invention may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, a vinyl group, and a mercapto group. Examples thereof include a group and a methacryloxy group.

  The silicone compound having a Si—H group in the D-2 component of the present invention is preferably exemplified by a silicone compound containing at least one structural unit represented by the following general formulas (iii) and (iv).

（式（ｉｉｉ）および式（ｉｖ）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（ｖ）で示される化合物を示す。α１〜α３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（ｉｉｉ）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (iii) and formula (iv), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (v): Α1 to α3 each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (iii) represents a plurality of different repeating units. Can be taken.)

（式（ｖ）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α４〜α８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（４）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (v), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α 4 to α 8 each independently represents 0 or 1. m 2 represents 0. Alternatively, it represents an integer of 1 or more, and the repeating unit in the case where m2 is 2 or more in formula (4) can take a plurality of different repeating units.

  In the component D-2 of the present invention, examples of the silicone compound having an alkoxy group include at least one compound selected from compounds represented by the general formula (vi) and the general formula (vii).

（式（ｖｉ）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In the formula (vi), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（ｖｉｉ）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In formula (vii), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. And at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.)

(D-3 component: brominated polycarbonate)
In the brominated polycarbonate (component D-3) used in the present invention, the structural unit represented by the following general formula (viii) is at least 60 mol%, preferably at least 80 mol%, particularly preferably all structural units. It is a brominated polycarbonate compound substantially composed of a structural unit represented by the following general formula (viii).

（式（ｖｉｉｉ）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）

(In the formula (viii), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —).

In the formula (viii), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate of component D-3 has few remaining chloroformate group ends, and the amount of terminal chlorine is preferably 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the aromatic polycarbonate resin composition becomes better, and a resin composition excellent in hue and molding processability is provided.

The D-3 component brominated polycarbonate preferably has few remaining hydroxyl groups. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by ¹ H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the resin composition is further improved.

  The specific viscosity of the D-3 component brominated polycarbonate is preferably in the range of 0.015-0.1, more preferably in the range of 0.015-0.08. The specific viscosity of the brominated polycarbonate is calculated according to the formula for calculating the specific viscosity used in calculating the viscosity average molecular weight of the aromatic polycarbonate resin which is the component A of the present invention.

The D-1 component to D-3 component are each preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, still more preferably 0 to 100 parts by weight of the A component. 0.02 to 2 parts by weight. By such a suitable composition ratio, an aromatic polycarbonate resin composition having an excellent synergistic effect with the component B and having good flame retardancy is provided.
(Other flame retardants)
As the organic metal salt flame retardant other than the component B of the present invention, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. For example, an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth of an aliphatic sulfonic acid Examples thereof include metal salts, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids (all of which do not contain a fluorine atom).

  Preferable examples of such aliphatic sulfonic acid metal salts include alkali (earth) metal salts of alkyl sulfonates, and these can be used alone or in combination of two or more (here, The notation of alkali (earth) metal salt is used to include both alkali metal salts and alkaline earth metal salts). Preferred examples of the alkane sulfonic acid used for the alkali (earth) metal salt of the alkyl sulfonate include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, and heptane. Examples thereof include sulfonic acid and octanesulfonic acid, and these can be used alone or in combination of two or more.

  The aromatic sulfonic acid used in the aromatic (earth) metal salt of aromatic sulfonate includes monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, monomeric or polymeric sulfonic acid. Aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid, Examples include at least one acid selected from the group consisting of sulfonic acids of aromatic sulfoxides and condensates of methylene type bonds of aromatic sulfonic acids, and these are used alone or in combination of two or more. be able to.

  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 Α, α, α-trifluoroacetophenone sodium 4-sulfonate, dipotassium benzophenone-3,3′-disulfonate, Nene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, naphthalene Examples thereof include a formalin condensate of sodium sulfonate and a formalin condensate of sodium anthracene sulfonate.

  On the other hand, the alkali (earth) metal salt of sulfate ester may include, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Alcohol sulfates include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol mono, di, tri, tetrasulfate, and lauric acid monoglyceride. And sulfuric acid ester of palmitic acid monoglyceride, stearic acid monoglyceride sulfate and the like. The alkali (earth) metal salts of these sulfates are preferably alkali (earth) metal salts of lauryl sulfate.

  Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N Examples include-(N'-benzylaminocarbonyl) sulfanilimide and alkali (earth) metal salts of N- (phenylcarboxyl) sulfanilimide.

  In the combined use with the component B of the present invention, an aromatic (earth) metal salt of an aromatic sulfonate is preferable, and a potassium salt is particularly preferable. When blending such an alkali (earth) sulfonate metal salt, the amount is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight per 100 parts by weight of component A.

(E component: filler)
Various kinds of known fillers can be blended in the aromatic polycarbonate resin composition of the present invention as a reinforcing filler. Such fillers include, for example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake. , Carbon beads, carbon milled fibers, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, ceramic particles, ceramic fibers, ceramic balloons, graphite, and various whiskers (potassium titanate whiskers) , Aluminum borate whisker, basic magnesium sulfate, etc.). These reinforcing fillers may be used alone or in combination of two or more.

  Among these, a carbon filler (E-1 component) is preferable in that the effect of the present invention is more exhibited. Examples of the carbon filler include carbon fibers (fiber diameter is 0.1 μm or more, including vapor phase growth method), carbon flakes, carbon beads, carbon milled fiber, vapor growth ultrafine carbon fiber (fiber diameter is 0.1 μm). Less), carbon nanotubes (fiber diameter is less than 0.1 μm, hollow), fullerene, and the like. Among these, carbon fiber is preferable in terms of the reinforcing effect. More preferably, the carbon fiber has a fiber diameter of 1 to 20 μm.

  The E component is preferably in the range of 0.1 to 50 parts by weight per 100 parts by weight of the A component. In particular, the E-1 component is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 1.5 to 20 parts by weight per 100 parts by weight of the A component.

(Other additives)
(Anti-dripping agent)
In addition to the aromatic polycarbonate resin composition of the present invention, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), an anti-drip agent (polytetrafluoroethylene having fibril-forming ability, etc.) and the like are separately blended. Can be used in combination with flame retardants.

  Since the aromatic polycarbonate resin composition of the present invention has an excellent drip-preventing effect, the resin composition containing polytetrafluoroethylene (PTFE) having a fibril-forming ability further has a UL standard 94 V-0 rank in a thin wall. By achieving or reducing the PTFE, the appearance and transparency of the resin composition can be improved.

  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, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd.

  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 then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Examples of commercially available PTFE in a mixed form 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.

(Radical generator)
The aromatic polycarbonate resin composition of the present invention can contain a radical generator. Preferred radical generators include 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, organic peroxides such as dicumyl peroxide, 2,3-dimethyl-2,3- Diphenylbutane (Dicumyl) and the like can be mentioned, and these are commercially available under the trade names such as Perhexin 25B, Parkmill D, and NOFMER BC manufactured by NOF Corporation. In particular, those that generate as little radicals as possible at the time of melt kneading and that generate stable radicals to some extent at the time of combustion are preferred, so 2,3-dimethyl-2,3-diphenylbutane (dicumyl) is more preferred as a radical generator. be able to. Such a radical generator can further improve flame retardancy.

(Stabilizer)
(Phosphorus stabilizer)
The aromatic polycarbonate resin composition of the present invention preferably further contains a phosphorus stabilizer. Such phosphorus stabilizers improve thermal stability during production or molding, and improve mechanical properties, hue, and molding stability. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris ( Diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylpheny) ) Phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is 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.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment.

(Hindered phenol stabilizer)
The aromatic polycarbonate resin composition of the present invention can further contain a hindered phenol-based stabilizer, and such inclusion is particularly effective in preventing dry heat deterioration. Examples of such hindered phenol stabilizers include α-tocopherol, butylhydroxytoluene, sinapyl 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 ′ -Methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (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-thio Ethylenebis- [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, 1,3,3 5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) Isocyanurate, 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 phenolic antioxidant can be used individually or in combination of 2 or more types.

  At least one stabilizer selected from phosphorus stabilizers and hindered phenol stabilizers is 0.0001 to 1 part by weight, preferably 0.001 to 100 parts by weight of aromatic polycarbonate resin (component A). It is contained in a proportion of 0.1 part by weight, more preferably 0.005 to 0.1 part by weight. 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.

(UV absorber)
Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate 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- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  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.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-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.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (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

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred in terms of ultraviolet absorption, and cyclic iminoesters and cyanoacrylates are preferred in terms of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The compounding quantity of a ultraviolet absorber is 0.01-2 weight part with respect to 100 weight part of aromatic polycarbonate resin (A component), Preferably it is 0.03-2 weight part, More preferably, it is 0.02-1 weight part. More preferably, it is 0.05 to 0.5 parts by weight.

(Light stabilizer)
The polycarbonate resin composition of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis. (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1 , 2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2, 2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, and polymethylpropyl 3-oxy- [4- (2,2,6, - it may also include tetramethyl) piperidinyl] hindered amine light stabilizer represented by a siloxane.

The above light stabilizers may be used alone or in a mixture of two or more. The amount of the light stabilizer used is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, and 0.02 to 1 part by weight based on 100 parts by weight of the aromatic polycarbonate resin (component A). Further preferred.
That's right.

(Other resins and elastomers)
In the polycarbonate resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range where the object of the present invention is not impaired.

  Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyethylene, and polypropylene. And other resins such as polyolefin resin, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, and epoxy resin.

  As the elastomer, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, MBS (methyl methacrylate / sterene / butadiene) which is a core-shell type elastomer. Examples thereof include rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

  In addition, in the aromatic polycarbonate resin composition of the present invention, additives known per se can be blended in a small proportion for imparting various functions to the molded article and improving the characteristics. 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), colorants (for example, pigments and dyes such as carbon black and titanium oxide), light diffusing agents (for example, acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, carbonic acid Calcium particles), fluorescent brighteners, fluorescent dyes, inorganic phosphors (for example, phosphors having aluminate as a base crystal), antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, Examples thereof include photocatalytic antifouling agents (for example, fine particle titanium oxide and fine particle zinc oxide), impact modifiers typified by graft rubber, infrared absorbers (heat ray absorbers), and photochromic agents.

(Haze value)
The aromatic polycarbonate resin composition of the present invention is preferably a smooth plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm, and the haze measured by JIS K7105 is 0.00. It satisfies 3 to 20%, more preferably 0.3 to 5%, still more preferably 0.3 to 3%. The haze value is measured using a haze meter. Such a smooth flat plate is obtained by subjecting the pellets to predetermined drying, and then injection-molding the pellets into a cavity constituted by a mold surface having an arithmetic average roughness (Ra) of 0.03 μm. The arithmetic average roughness (Ra) of the mold surface can be measured using a surface roughness meter.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the aromatic polycarbonate resin composition of this invention. For example, component A, component B, and optionally other components are mixed thoroughly using a premixing means such as a V-type blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Examples thereof include granulation with a briquetting machine and the like, followed by melt kneading with a melt kneader typified by a vent type biaxial ruder, and pelletization with a device such as a pelletizer.

  As a method for supplying each component to the melt-kneader, (i) A component, B component and other components are each independently supplied to the melt-kneader; (ii) A component, B component and other components A method in which a part is premixed and then supplied to the melt-kneader independently of the remaining components, (iii) a method in which the component B is diluted and mixed with water or an organic solvent and supplied to the melt-kneader, and further (iv) Examples include a method in which the diluted mixture is premixed with other components and then supplied to the melt kneader. In addition, when there exists a liquid thing in the component to mix | blend (for example in said (iii) and (iv)), what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

  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, a polycarbonate resin composition can be extrusion-molded and it can also be made into shapes, such as various profile 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. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

(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 improves the drip prevention effect by blending a fluorine-containing organic metal salt (especially an alkali metal perfluoroalkylsulfonic acid salt) with a reduced fluoride ion content. It has excellent flame retardancy. Furthermore, the present invention produces an aromatic polycarbonate resin composition in which melting dripping is prevented in a vertical combustion test of UL standard 94 by blending a fluorine-containing organometallic salt with reduced fluoride ion content into an aromatic polycarbonate resin. It is a method to do. In addition, the present invention is a method for preventing melt dripping in a vertical combustion test of UL standard 94 of an aromatic polycarbonate resin composition containing a fluorine-containing organic metal salt, wherein the amount of fluoride ions is reduced as the metal salt It is the method characterized by using. Thus, there is no technology for improving the flame retardancy by reducing the amount of fluoride ions in the fluorine-containing organic metal salt in the conventional flame retarding technology.

  Aromatic polycarbonate resin compositions that have conventionally used fluorine-containing organometallic salts are based on a balance of various properties, and it is often difficult to change the components in the resin composition. As a result, it is difficult to improve the mechanical properties, transparency, hue, thermal stability, and long-term properties (humidity heat resistance, fatigue properties, etc.) by imparting superior flame retardancy or reducing flame retardants. There was a problem with it. According to the present invention, the flame retardant performance is improved by using the same flame retardant as that of the prior art, so that it is possible to solve such a problem. Therefore, 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 the industrial effect exerted by the composition is extremely large.

  The form of the present invention considered to be the best by the present inventors 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 Evaluation was performed by a vertical combustion test based on the UL standard 94 using test pieces having thicknesses shown in Table 1 prepared according to the UL standard.

[Examples 1 to 11 and Comparative Examples 1 to 7]
The resin composition which consists of a mixture ratio of Table 1 and Table 2 was created in the following ways. The description will be made according to the symbols in the following table. Each component of the ratio of Table 1 and Table 2 was measured, it mixed uniformly using the tumbler, and this mixture was thrown into the extruder and preparation of the resin composition was performed. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The screw configuration is the first stage kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) before the vent position. Thereafter, a second-stage kneading zone (consisting of a feed rotor × 1 and a return rotor × 1) was provided. Strands were extruded under conditions of cylinder temperature and die temperature of 280 ° C. and vent suction of 3000 Pa, cooled in a water bath, then cut into strands with a pelletizer, and pelletized. The obtained pellets were dried at 120 ° C. for 6 hours with a hot air circulating dryer, and a test piece was molded at an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y] at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. did.

The raw materials used in Table 1 are as follows.
(A component)
PC-1: Linear polycarbonate resin (a polycarbonate resin comprising bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such a polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 22,400.
PC-2: Linear polycarbonate resin (a polycarbonate resin composed of bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. Such a polycarbonate resin is produced without using an amine catalyst and is an aromatic polycarbonate resin. The ratio of the terminal hydroxyl group in the terminal was 10 mol%, and the viscosity average molecular weight was 15,500.
PC-3: Branched aromatic polycarbonate resin (Teflon IB2500 manufactured by Idemitsu Petrochemical Co., Ltd.)
PC-4: Linear polycarbonate resin (a polycarbonate resin composed of bisphenol A prepared by the phosgene method and p-tert-butylphenol as a terminal terminator. This polycarbonate resin is produced using an amine catalyst and has a viscosity average molecular weight. Was 121,500.

(B component)
B-1: Perfluorobutanesulfonic acid potassium salt having a fluoride ion amount of 1 ppm (production of B-1)
Dai Nippon Ink Co., Ltd. MegaFuck F-114P: 100 parts by weight, ion-exchanged water: 300 parts by weight were charged in a glass flask equipped with a thermometer and a stirrer, heated to 80 ° C., and under nitrogen flow 2 After stirring for an hour, the mixture was cooled to room temperature, and the precipitated crystals were collected by filtration. The crystals were washed with 100 parts by weight of ion-exchanged water, and the wet powder was dried with a hot air dryer at 80 ° C. under a nitrogen atmosphere for 24 hours. It is further washed with methanol and subsequently washed with ion-exchanged water, and then the wet powder is dried with hot air at 80 ° C. for 20 hours. The obtained powder is pulverized using a pulverizing mill and passed through a standard sieve No. 400. The desired product was obtained. The ion-exchanged water is ion-exchanged water having an electric resistance of 18 MΩ · cm or more (that is, electric conductivity of about 0.55 μS / cm or less) obtained through Yamato Scientific Co., Ltd. Auto Pure WQ500 type. The same applies to the case where “ion-exchanged water” is simply described.
B-2: Perfluorobutanesulfonic acid potassium salt having a fluoride ion content of 9 ppm (production of B-2)
Dai Nippon Ink Co., Ltd. MegaFuck F-114P: 100 parts by weight, ion-exchanged water: 300 parts by weight were charged in a glass flask equipped with a thermometer and a stirrer, heated to 80 ° C., and stirred for 2 hours. After continuing, it cooled to room temperature and the crystal | crystallization which precipitated was taken out by filtration. The crystals were washed with 100 parts by weight of ion-exchanged water, and the wet powder was dried in air at 80 ° C. for 20 hours with a hot air dryer. After further washing with ion-exchanged water, the wet powder was dried with hot air at 80 ° C. for 20 hours. The obtained powder was pulverized using a pulverizing mill and passed through a standard sieve No. 400 to obtain the desired product.
(Other than B component)
B-3: Perfluorobutanesulfonic acid potassium salt having a fluoride ion content of 40 ppm (Bayowet C4 manufactured by Bayer)
B-4: Perfluorobutanesulfonic acid potassium salt with 126 ppm fluoride ion (Dainippon Ink Co., Ltd. MegaFuck F-114P)

(C component: mold release agent)
(C-1 component)
SL: Fatty acid ester mainly composed of stearyl stearate and glycerin tristearate (Riquemar SL900 manufactured by Riken Vitamin Co., Ltd.)
VPG: Fatty acid ester mainly composed of pentaerythritol tetrastearate (Roxyol VPG861 manufactured by Cognis Japan Co., Ltd.)

(D component: other flame retardant)
(D-1 component)
FG15: Tris (2,4,6-tribromophenyl) phosphate (Fireguard FG-1500 manufactured by Teijin Chemicals Ltd.)
(D-2 component)
SiH: Silicone containing Si-H group and phenyl group (production of SiH)
A 1 L flask equipped with a stirrer, a cooling device, and a thermometer was charged with 301.9 g of water and 150 g of toluene, and cooled to an internal temperature of 5 ° C. A mixture of trimethylchlorosilane (21.7 g), methyldichlorosilane (23.0 g), dimethyldichlorosilane (12.9) and diphenyldichlorosilane (76.0) was charged into the dropping funnel and dropped into the flask over 2 hours while stirring. During this time, cooling was continued to maintain the internal temperature at 20 ° C. or lower. After completion of the dropwise addition, the mixture was further aged for 4 hours with stirring at an internal temperature of 20 ° C., then left to stand to remove the separated hydrochloric acid aqueous layer, added with 10% aqueous sodium carbonate solution, stirred for 5 minutes and then left to stand. The separated aqueous layer was removed. Then, it wash | cleaned 3 times with ion-exchange water, and it confirmed that the toluene layer became neutral. This toluene solution was heated to an internal temperature of 120 ° C. under reduced pressure to remove toluene and low-boiling substances, and then insoluble materials were removed by filtration to obtain a silicone compound SiH. This silicone compound SiH had an Si—H amount of 0.21 mol / 100 g, an aromatic group amount of 49% by weight, and an average degree of polymerization of 8.0.
(D-3 component)
FG75: Brominated polycarbonate oligomer (Fireguard FG-7500 manufactured by Teijin Chemicals Ltd.)
(Other D components)
KSS: Alkali metal sulfonic acid alkali metal salt mainly composed of potassium diphenylsulfone sulfonate (KSS manufactured by UCB Japan)

(E component)
(E-1 component)
CF: Carbon fiber chopped strand (Beast Fight HTA-C6-U manufactured by Toho Tenax Co., Ltd.)
(Other E components)
GF: Chopped strand of glass fiber (ECS 03 T-511 / F manufactured by Nippon Electric Glass Co., Ltd.)
MF: Glass fiber milled fiber (PFE-301S manufactured by Nittobo Co., Ltd.)

(Other ingredients)
PTFE: Fluorine resin having fibril forming ability (Polyflon MPA FA500 manufactured by Daikin Corporation)
TMP: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
DMP: Dimethylphenylphosphonate (manufactured by Nissan Chemical Industries, Ltd.)
IRG: Phosphite compound (Irgafos 168 manufactured by Ciba Specialty Chemicals)
EPQ: Phosphorus stabilizer mainly composed of phosphonite (Sandstab P-EPQ manufactured by Clariant Japan)
CBM: carbon black master (carbon black MA-100 manufactured by Mitsubishi Chemical Corporation), high wax 405MP manufactured by Mitsui Chemicals, Inc., and PC-2 (polycarbonate resin having a viscosity average molecular weight of 15,500) described above are weighted. (Pellets melt-mixed using a twin-screw extruder at a ratio of 20:10:70; therefore, the CBM is composed mainly of the A component and includes the C component and the E-1 component.)

  From the comparison between Examples and Comparative Examples in Tables 1 and 2, it can be seen that the aromatic polycarbonate resin composition of the present invention is excellent in flame retardancy due to its drip prevention effect.

Claims (6)

100 parts by weight of aromatic polycarbonate resin (component A), fluorine-containing organometallic salt having a fluoride ion content of 0.2 to 20 ppm by weight based on the total weight of component B measured by ion chromatography An aromatic polycarbonate resin composition comprising 0.005 to 0.6 parts by weight of a compound (component B) and 0.005 to 2 parts by weight of a release agent and containing no fluoropolymer.   The aromatic polycarbonate resin composition according to claim 1, wherein the component B is a perfluoroalkylsulfonic acid alkali metal salt.   2. A smooth flat plate having a thickness of 2 mm made of the resin composition and having an arithmetic average roughness (Ra) of 0.03 μm, wherein the haze measured by JIS K7105 is 0.3 to 20%. The aromatic polycarbonate resin composition according to claim 2.   The molded article formed from the aromatic polycarbonate resin composition of any one of the said Claims 1-3. A method for producing an aromatic polycarbonate resin composition flame-retarded with a fluorine-containing organometallic salt compound, in which melt dripping during a melt test is prevented in a vertical combustion test of UL standard 94, the production method comprising: Fluorine-containing fluorine ion content measured by ion chromatography method is 0.2 to 20 ppm by weight based on the total weight of component B with respect to 100 parts by weight of aromatic polycarbonate resin (component A) An aromatic polycarbonate resin composition comprising 0.005 to 0.6 parts by weight of an organometallic salt compound (component B) and 0.005 to 2 parts by weight of a release agent, and no fluoropolymer. Production method. A resin composition in which 0.005 to 0.6 parts by weight of a fluorine-containing organometallic salt and 0.005 to 2 parts by weight of a release agent are blended with 100 parts by weight of an aromatic polycarbonate resin (component A) and no fluoropolymer is blended. In which the content of fluoride ions measured by ion chromatography as the metal salt is 0 by weight based on the total weight of the B component. A method for preventing melting dripping during a melting test , which comprises using a fluorine-containing organometallic salt compound (component B) of 2 to 20 ppm.