JP2006028389A - Aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition compounded with a fluorine-containing metal salt compound and fibrillated PTFE and having decreased aggregation of the fibrillated PTFE and problems caused by the aggregation. <P>SOLUTION: The aromatic polycarbonate resin composition is composed of (A component) 100 pts. wt. of an aromatic polycarbonate resin, (B component) 0.005-0.6 pt. wt. of a fluorine-containing organic metal salt compound and (C component) 0.001-1 pt. wt. of polytetrafluoroethylene having fibril-forming property. The fluoride ion content of the component B is 0.2-20 ppm by weight determined by ion chromatography. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention comprises a fluorine-containing organometallic salt compound represented by an alkali metal salt of perfluoroalkylsulfonic acid, and polytetrafluoroethylene having a fibril-forming ability (hereinafter sometimes simply referred to as “fibrillated PTFE”). The present invention relates to an aromatic polycarbonate resin composition to be contained. More specifically, the present invention relates to an aromatic polycarbonate resin composition in which aggregation of fibrillated PTFE during molding and an inconvenience derived therefrom are improved by using a fluorine-containing organometallic salt compound with reduced fluoride ions.

  Aromatic polycarbonate resins have excellent transparency, flame retardancy, and impact resistance, and are used in a wide range of fields. An aromatic polycarbonate resin composition in which a fluorine-containing organic metal salt compound typified by an alkali metal salt of perfluoroalkylsulfonic acid is blended with an aromatic polycarbonate resin is well known. The fluorine-containing organometallic salt compound imparts improved flame retardancy and antistatic properties to the aromatic polycarbonate resin composition. On the other hand, an aromatic polycarbonate resin composition in which fibrillated PTFE is blended with an aromatic polycarbonate resin is also well known. Fibrilized PTFE improves the melt viscosity characteristics of the resin composition. As a result, dripping prevention during combustion, molding defects represented by flow marks during molding, weld line reduction and weld strength improvement, gas assist It exhibits effects such as stabilization during molding, stabilization during foam molding, and improvement in blow moldability. The fluorine-containing organometallic salt compound and fibrillated PTFE are often combined and blended into an aromatic polycarbonate resin composition. Many of the combined purposes are flame retardant improvements.

  On the other hand, fibrillated PTFE has a high cohesive strength and such properties often cause various disadvantages. A typical example of such inconvenience is uneven color of the molded product. In addition, the effect expected for the fibrillated PTFE may not be sufficiently exhibited. In an aromatic polycarbonate resin composition in which a fluorinated organometallic salt compound and fibrillated PTFE are combined, aggregation of fibrillated PTFE tends to occur due to an excessive heat history. In particular, when a titanium dioxide pigment is included, the color unevenness of the molded product tends to be remarkable. In recent years, the thickness or size of molded products has been reduced, and the opportunity for excessive heat history to be added to resin materials is increasing. Therefore, the opportunity for improvement of the disadvantages associated with the aggregation of the fibrillated PTFE is increasing.

  Conventionally, in an aromatic polycarbonate resin composition containing a fluorine-containing organometallic salt compound represented by an alkali metal salt of perfluoroalkylsulfonic acid, (i) the pH of the compound in an aqueous solution or dispersion is 5-9. A method for adjusting the range (see Patent Document 1) and a method (ii) for reducing the alcohol-insoluble content of the compound (see Patent Document 2) are known. However, these documents do not disclose any knowledge about improvement of inconvenience due to aggregation of fibrillated PTFE. Moreover, the resin composition which consists of an aromatic polycarbonate, a fluorine-containing organometallic salt compound, and fibrillated PTFE is well-known (refer patent documents 3-5). A resin composition obtained by further combining titanium oxide with such a resin composition is also known (see Patent Documents 6 to 10).

JP 2001-031855 A JP 2001-115004 A JP 2001-270983 A JP 2002-060612 A Japanese Patent Laid-Open No. 2003-082218 JP 2002-372609 A JP 2003-183491 A JP 2003-226805 A JP 2003-213114 A JP 2003-342462 A

  An object of the present invention is to reduce aggregation of fibrillated PTFE and disadvantages associated therewith in an aromatic polycarbonate resin composition containing a fluorine-containing metal salt compound and fibrillated PTFE.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have further reduced the ratio of fluoride ions contained in a trace amount in the fluorine-containing organometallic salt compound, so that the fibrillated PTFE can be molded. It has been found that aggregation can be suppressed. 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 object of the present invention is (1) 100 parts by weight of an aromatic polycarbonate resin (component A), 0.005 to 0.6 parts by weight of a fluorine-containing organometallic salt compound (component B), and polytetrafluoroethylene having a fibril-forming ability. In the aromatic polycarbonate resin composition comprising 0.001 to 1 part by weight of fluoroethylene (C component), the B component has a fluoride ion content measured by ion chromatography of 0.2 to 20 ppm by weight. It is achieved by an aromatic polycarbonate resin composition characterized by being.

  That is, according to the configuration (1), a resin composition in which aggregation during molding of fibrillated PTFE is suppressed is provided. The reason why the aggregation is suppressed by using the fluorine-containing organometallic salt compound in which the fluoride ion is reduced to a specific amount or less is estimated as follows. The melting point of fibrillated PTFE (around 325 ° C.) is close to the molding temperature of the aromatic polycarbonate resin (excluding a special case, it is approximately in the range of 280 to 340 ° C.). Therefore, during the molding process, the mobility of the fibrillated PTFE itself is high in the molten matrix resin. This tends to cause shrinkage of the fibrillated PTFE itself. Further, since the matrix resin itself is flowing, the PTFEs are in contact with each other. These results are considered to cause aggregation.

  On the other hand, fluoride ions act to break carbonate bonds during molding. Stress is acting on the polycarbonate matrix that constrains the fibrillated PTFE. Such degradation is believed to relieve the stress and, as a result, the fibrillated PTFE tends to shrink. 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 preferable aspects of the present invention is (2) the aromatic polycarbonate resin composition having the constitution (1), wherein the component B is an alkali metal perfluoroalkylsulfonic acid. According to this configuration (2), an aromatic polycarbonate resin composition having better flame retardancy is provided. For the combined use of fibrillated PTFE and perfluoroalkylsulfonic acid alkali metal salt, improvement in flame retardancy is most expected. On the other hand, the alkali metal salt of perfluoroalkylsulfonic acid is unavoidably mixed with fluoride ions to some extent based on its production method. In the present invention, by preventing such contamination, aggregation of the PTFE in the aromatic polycarbonate resin composition containing the metal salt and fibrillated PTFE is suppressed. As a result, the present invention provides an aromatic polycarbonate resin composition excellent in appearance and flame retardancy.

  One of the preferred embodiments of the present invention is that (3) the resin composition further comprises 0.01 parts by weight or more and less than 3 parts by weight of a titanium dioxide pigment (component D) based on 100 parts by weight of the component A. It is an aromatic polycarbonate resin composition of said structure (1)-(2) formed. Appearance inconvenience due to agglomeration during molding of fibrillated PTFE tends to be particularly noticeable as uneven color of the molded product when it contains a titanium dioxide pigment. According to the configuration (3), an aromatic polycarbonate resin composition with improved color unevenness is provided.

  Although the reason why the color unevenness becomes remarkable due to the presence of the titanium dioxide pigment is not clear, it is presumed as follows. The first is considered to be derived from the strong coloring power and hiding power of the titanium dioxide pigment itself. That is, since it has a strong coloring power, when non-uniform dispersion occurs, the non-uniformity is likely to appear in the appearance. Second, it is considered that fibrillated PTFE and titanium dioxide pigment have a relatively strong affinity under molding processing conditions. Titanium dioxide dispersed in the resin matrix due to such affinity is expected to be biased around the fibrillated PTFE. In such a biased state, the fibrillated PTFE itself is further aggregated, so that it is considered that the dispersion of the titanium diacid pigment is uneven.

  One of the preferred embodiments of the present invention is (4) a molded article formed from the aromatic polycarbonate resin composition having the constitutions (1) to (3). According to the configuration (4), inconvenience due to aggregation of the fibrillated PTFE is improved, and as a result, a molded article having a good appearance, moldability, and mechanical strength is stably produced.

  Furthermore, according to another aspect of the present invention, the object is (5) 100 parts by weight of an aromatic polycarbonate resin (component A), 0.005 to 0.6 parts by weight of a fluorine-containing organometallic salt compound (component B), And a polytetrafluoroethylene (C component) having a fibril forming ability of 0.001 to 1 part by weight, and a method for producing an aromatic polycarbonate resin composition in which aggregation of the C component during molding is suppressed. And a fluorine-containing organometallic salt compound having a fluoride ion content of 0.2 to 20 ppm by weight as measured by an ion chromatography method as the component B. Achieved by the method.

  Furthermore, according to a preferred embodiment of the present invention, the object is as follows: (6) 100 parts by weight of an aromatic polycarbonate resin (component A), 0.005 to 0.6 parts by weight of a fluorine-containing organometallic salt compound (component B), fibrils Polytetrafluoroethylene (C component) having 0.001 to 1 part by weight having a forming ability and 0.01 part by weight or more and less than 3 parts by weight of titanium dioxide pigment (D component). A process for producing an aromatic polycarbonate resin composition with improved unevenness, wherein the content of fluoride ions measured by ion chromatography as the B component is 0.2 to 20 ppm by weight. This is achieved by a method for producing an aromatic polycarbonate resin composition characterized by using a salt compound.

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 anti-drip ability of the 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 within 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 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the raw material dihydric phenol. Selected by range.

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

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

  In producing the aromatic polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the aromatic polycarbonate resin is not particularly limited, but is preferably 10,000 to 50,000, more preferably 14,000. It is -30,000, More preferably, it is 14,000-24,000.

  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. In addition, since the molding process temperature tends to be increased, color unevenness is likely to occur.

  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) further synergizes the anti-drip ability of the aromatic polycarbonate resin composition of the present invention by improving the entropy elasticity of the resin. Can be improved. 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 (A-3 component) (hereinafter referred to as “high molecular weight component-containing aromatic polycarbonate resin”) having a viscosity average molecular weight of 16,000 to 35,000. May also be used.

  In such a high molecular weight component-containing aromatic polycarbonate resin (A-3 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 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 (A-3 component) is 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. Can do. Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight, more preferably the A-3-1 component is 3 to 30% by weight, and still more preferably The A-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 the three components, and (3) an aromatic polycarbonate resin obtained by the 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 the drop time of methylene chloride, t is the drop time of the sample solution]
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

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

(B component: fluorinated organometallic salt compound)
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 organometallic salt compound in the present invention refers to a metal salt compound composed of an anionic component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cationic component composed of a metal ion. And 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 organometallic salt compounds 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 compound sample is dissolved in ultrapure water (for reagent) 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 is used, the column is ASA-SC for anion analysis, the detector is an electric conductivity meter, and the eluent is 1.8 mmol of Na per 1 L 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 compound 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.

  A well-known manufacturing method is used for manufacture of B component of this invention. As such a production method, (i) a method for reducing the amount of fluoride ions contained in a raw material when producing a fluorine-containing organometallic salt compound, (ii) hydrogen fluoride obtained by the reaction, etc. during the reaction Preferred is a method of removing by generated gas or heating, and (iii) a method of reducing the amount of fluoride ions of the compound by using a purification method such as recrystallization and reprecipitation in the production of a fluorine-containing organometallic salt compound. Is exemplified. In particular, component B is relatively easy to dissolve in water. Therefore, ion-exchanged water, particularly water having an electric resistance value of 18 MΩ · cm or more, that is, water satisfying an electric conductivity of about 0.55 μS / cm or less, is dissolved at a temperature higher than room temperature, and then washed. A method of manufacturing by a step of cooling and recrystallization is preferable as a method of manufacturing the B component.

  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, it is purified as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more.

  The solution in which the metal salt is dissolved is stirred at the above temperature for 0.05 to 3 hours, more preferably for 0.1 to 2 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. As a result, a purified perfluoroalkylsulfonic acid alkali metal salt, which is a suitable component B, is produced. It is even better to wash the alkali metal salt with ion-exchanged water or a polar solvent (especially alcohol is preferred). By this operation, fluoride ions can be further reduced.

  The above purification operation is summarized as follows. That is, a preferable method for producing the component B includes (i) a step of preparing an alkali metal salt of perfluoroalkylsulfonic acid, and (ii) a range of 40 to 90 ° C. in the ion-exchanged water of 2 to 10 times by weight of the metal salt. (Iii) a step of stirring the liquid in which the metal salt is dissolved at such a temperature for 0.05 to 3 hours, (iv) a step of cooling the liquid to a range of 0 to 40 ° C., and (v ) It consists of a step of taking out the precipitated crystals. More preferably, (vi) a step of washing the extracted crystals with ion-exchanged water or a polar solvent is added.

  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 more preferable range is, the effects expected by blending the fluorine-containing organic metal salt (for example, flame retardancy and antistatic property) are exhibited, and the disadvantages due to the aggregation of fibrillated PTFE are suppressed.

(C component: polytetrafluoroethylene having fibril-forming ability)
Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE of component C has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise. .

  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. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of such commercially available fibrillated PTFE 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 fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Examples of commercially available fibrillated PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

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

  The content of the fibrillated PTFE (component C) in the aromatic polycarbonate resin composition is preferably in the range of 0.001 to 1 part by weight, more preferably 0.05 to 0. It is in the range of 7 parts by weight, more preferably 0.1 to 0.5 parts by weight.

(D component: Titanium dioxide pigment)
As the titanium dioxide pigment of component D used in the present invention, those usually used for various coloring applications can be used, and they are widely known per se. There is also a titanium dioxide pigment composed of 100% by weight of TiO ₂ (in the present invention, the titanium dioxide component of the titanium dioxide pigment is expressed as “TiO ₂ ”, and the entire pigment including the surface treatment agent is expressed as “titanium dioxide pigment”. write). However, surface treatment is usually performed with oxides of various metals such as aluminum, silicon, titanium, zirconium, antimony, tin, and zinc. Also in the present invention, the content of TiO _{2 in} 100% by weight of the metal oxide in the titanium dioxide pigment is about 89 to 98% by weight, and it is preferable that the surface treatment of the metal oxide is performed. For example, an inorganic surface treatment agent having an Al ₂ O ₃ content ratio of 0.5 to 4.5% by weight is preferable.

TiO _{2 in the} component D may be either anatase type or rutile type in crystal form, and they can be mixed and used as necessary. A rutile type is more preferable in terms of initial mechanical properties and long-term weather resistance. A rutile type crystal may contain an anatase type crystal. Furthermore TiO ₂ production process is sulfuric acid method, chlorine method, but those which have been prepared by various other methods can be used, the chlorine method is more preferred. Further, the titanium dioxide pigment of the present invention is not particularly limited in its shape, but is preferably in the form of particles. The average particle diameter of the titanium dioxide pigment is preferably 0.01 to 0.4 μm, more preferably 0.1 to 0.3 μm, and still more preferably 0.15 to 0.25 μm. Such an average particle diameter is calculated by measuring the number of individual single particles and observing the number average thereof through observation with an electron microscope.

The coating with various metal oxides on the surface of TiO ₂ can be performed by various commonly used methods. For example, it is manufactured from the following steps 1) to 8). That is, 1) untreated TiO ₂ after dry pulverization is made into an aqueous slurry, 2) the slurry is wet pulverized and atomized, 3) a fine particle slurry is collected, and 4) a metal salt is soluble in the fine particle slurry. Add compound 5) Neutralize and coat TiO ₂ surface with metal hydrated oxide 6) Remove by-products, adjust slurry pH, filter, and clean with pure water 7) Washed Examples thereof include a method of drying the cake, and 8) crushing the dried product with a jet mill or the like. In addition to this method, for example, a method of reacting TiO ₂ particles with an active metal compound in a gas phase can be mentioned. Further, in the coating of the metal oxide surface treatment agent on the TiO ₂ surface, firing after the surface treatment, surface treatment again after the surface treatment, and firing after the surface treatment and surface treatment again are performed. Is possible. As the surface treatment with the metal oxide, either a high-density treatment or a low-density (porous) treatment can be selected.

In the titanium dioxide pigment of component D, the content of TiO _{2 in} 100% by weight of the metal oxide is preferably 97% by weight or less, more preferably 96% by weight or less. The titanium dioxide pigment of component D preferably has a TiO ₂ content of 90% by weight or more, more preferably 91% by weight or more. The titanium dioxide pigment of component D preferably has an Al ₂ O ₃ content of 4% by weight or less.

  The D component titanium dioxide pigment may be surface-treated with an organic compound. As such a surface treatment agent, various treatment agents such as polyol, amine, and silicon can be used. Examples of the polyol-based surface treatment agent include pentaerythritol, trimethylolethane, and trimethylolpropane. Examples of the amine-based surface treatment agent include triethanolamine acetate and trimethylolamine acetate. Examples of the silicon-based surface treatment agent include alkyl chlorosilanes (such as trimethylchlorosilane), alkylalkoxysilanes (such as methyltrimethoxysilane), and hydrogen polysiloxane. Examples of the hydrogen polysiloxane include alkyl hydrogen polysiloxane and alkylphenyl hydrogen polysiloxane. Such an alkyl group is preferably a methyl group or an ethyl group.

  An appropriate surface treatment of the organic compound is preferable because it makes it possible to improve dispersibility and improve hydrolysis resistance efficiently. The amount of the organic compound to be surface-treated is preferably 1% by weight or less per 100% by weight of D component, more preferably 0.6% by weight or less, and further preferably 0.4% by weight or less. On the other hand, the lower limit is 0.05% by weight or more. The surface treatment agent for the organic compound may cover the surface of the titanium dioxide pigment in the composition. Therefore, a method may be used in which the surface treatment agent is separately added when the raw material of the resin composition is melt-kneaded, and the surface treatment of the titanium dioxide pigment is performed in the melt-kneading step.

  Content of a titanium dioxide pigment (D component) is 0.01 weight part or more and less than 3 weight part on the basis of 100 weight part A component. In such a range, it is more preferably 0.05 parts by weight or more, still more preferably 0.1 parts by weight or more. On the other hand, in such a range, it is more preferably less than 2 parts by weight, still more preferably less than 1 part by weight. The color unevenness due to the influence of the titanium dioxide pigment becomes noticeable at 0.01 parts by weight or more. If it is 3 parts by weight or more, the hiding power increases, so that the color unevenness is not conspicuous.

(Other ingredients)
(Release agent)
A release agent can be blended in the aromatic polycarbonate resin composition of the present invention as necessary. The resin composition of the present invention also has good flame retardancy. Therefore, although usually a mold release agent tends to have a bad influence with respect to a flame retardance, the resin composition of this invention can achieve favorable flame retardance. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (for example, polyethylene wax and 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine A compound (for example, fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like can be mentioned. 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 these, fatty acid esters are 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, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 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 is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 22 carbon atoms. Examples of the saturated aliphatic carboxylic acid in 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, docosanoic acid and the like are exemplified. Examples of unsaturated aliphatic carboxylic acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid. Among these, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable, and saturated aliphatic carboxylic acids are preferable, and stearic acid and palmitic acid are particularly preferable.

  Since the above 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 fatty acid ester of the present invention, aliphatic carboxylic acids 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 fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The compounding amount of the release agent (preferably fatty acid ester) 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. It is. In such a range, the aromatic polycarbonate resin composition has good release properties and flame retardancy, and particularly has a good hue and appearance in fatty acid esters.

(Flame retardants)
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 (i) halogenated flame retardants (for example, brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorinated polyethylenes), (ii) organic Phosphorus flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) organometallic salt flame retardants (for example, organic sulfonic acids other than component B) Alkali (earth) metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (iv) silicone flame retardants composed of silicone compounds. Among these, at least one compound selected from a phosphate compound (E-1 component), a silicone compound (E-2 component), and a brominated polycarbonate (including oligomer) (E-3 component) is preferably used in the present invention. The B component is used in combination.

(E-1 component: phosphate compound)
As the phosphate compound of the E-1 component used as the organophosphorus flame retardant of the present invention, various phosphate compounds known as conventional flame retardants can be used, and more particularly particularly represented by the following general formula (i). One or more phosphate compounds may be mentioned.

（但し前記式中の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 contained, and more preferably, the component of n = 1 in the formula (i) is 80% by weight or more, more preferably 85% by weight or more, and further preferably 90% by weight. % Is contained ).

(E-2 component: silicone compound)
The E-2 component silicone compound used as the silicone-based flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as a flame retardant for aromatic polycarbonate resin 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 .

Specifically, the structure of the E-2 component silicone compound of the present invention is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone 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. .

  Furthermore, the E-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 an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Furthermore, it is preferable that E-2 component contains an aryl group from 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（ｉｉ）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 (ii), n is 2). In these cases, different types of X can be taken.)

  The E-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 E-2 component of the present invention is preferably exemplified by a silicone compound containing at least one of the structural units 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（ｖ）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 (v) can take a plurality of different repeating units.

  In the E-2 component of the present invention, examples of the silicone compound having an alkoxy group include at least one compound selected from the 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.)

(E-3 component: brominated polycarbonate)
In the brominated polycarbonate (E-3 component) 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 the E-3 component has few remaining chloroformate group terminals, and the terminal chlorine content 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 E-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 E-3 component brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 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 components E-1 to E-3 are each preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and still more preferably 0 to 100 parts by weight of the component A. 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 -3,4'-dipotassium disulfonate, α, α, α-trifluoroacetophenone-4-sodium sulfonate, dipotassium benzophenone-3,3'-disulfonate, thiof 2,5-disulfonic acid disodium, thiophene-2,5-disulfonic acid dipotassium, thiophene-2,5-disulfonic acid calcium, benzothiophene sodium sulfonate, diphenyl sulfoxide-4- potassium sulfonate, naphthalene sulfone Examples thereof include a formalin condensate of sodium acid and a formalin condensate of sodium anthracene sulfonate.

  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 esters of palmitic acid monoglyceride and stearic acid monoglyceride sulfate. 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.

(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. A filler is 0.1-50 weight part per 100 weight part of A component, More preferably, it is 1-30 weight part, More preferably, it is 1.5-20 weight part.

  Examples of the carbon filler include carbon fiber (fiber diameter is 0.1 μm or more, including vapor phase growth method), carbon flakes, carbon beads, carbon milled fiber, vapor phase 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.

(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. Particularly preferred are those which generate as little radicals as possible during melt-kneading and generate stable radicals to some extent during combustion. Therefore, as a more preferred radical generator, 2,3-dimethyl-2,3-diphenylbutane (dicumyl) can be mentioned. Such a radical generator can further improve flame retardancy.

(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, and tertiary phosphine.

  Specific examples of the phosphite compound include 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.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizer can be used not only in one kind but also in a mixture of two or more kinds. 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 a phosphorus stabilizer and a hindered phenol stabilizer is 0.0001 to 1 part by weight, preferably 100 parts by weight of 100 parts by weight of an aromatic polycarbonate resin (component A). 0.001 to 0.1 parts by weight, more preferably 0.005 to 0.1 parts by weight. When the amount of the stabilizer is too smaller than the above range, it is difficult to obtain a good stabilizing effect. When the amount of the stabilizer 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. Further, the phenyl group of the exemplified compound 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 absorbing monomer and / or the light-stable monomer and a single amount of an alkyl (meth) acrylate or the like. 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

  Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorbing ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin (component A). Preferably 0.05 to 0.5 parts by weight is blended.

(Light stabilizer)
In addition, the aromatic polycarbonate resin composition of the present invention includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 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 6,6-tetramethyl) piperidinyl] hindered amine light stabilizer typified by siloxane can also be included.

  The light stabilizers may be used alone or in a mixture of two or more. The light stabilizer is preferably 0.0005 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, still more preferably 0.02 to 1 part per 100 parts by weight of the aromatic polycarbonate resin (component A). Part by weight is blended.

(Other resins and elastomers)
In the aromatic polycarbonate resin composition of the present invention, other resins and elastomers can be used in a small proportion within a range in which 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.

  Such additives include sliding agents (eg PTFE particles), colorants (pigments and dyes other than titanium oxide), light diffusing agents (eg acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, and calcium carbonate particles). , Fluorescent brighteners, fluorescent dyes, inorganic phosphors (for example, phosphors with aluminate as the mother crystal), antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antibacterial agents Examples include soiling agents (excluding titanium oxide, for example, fine zinc oxide), impact modifiers typified by graft rubber, infrared absorbers (heat ray absorbers), and photochromic agents.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the aromatic polycarbonate resin composition of this invention. For example, the A component, the B component, the C component, and optionally other components are supplied to a melt kneader represented by a vent type twin screw extruder and melt kneaded. Usually, the strand extruded from the extruder die is cooled through a water tank, and the cooled strand is cut with a pelletizer to obtain pellets made of the resin composition. At the time of supply to the extruder, the raw materials can be premixed. Examples of the premixing means include a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. The raw material and its premixed mixture may be granulated by an extrusion granulator or a briquetting machine, if necessary.

  As a method for supplying each component to the melt kneader, (i) A component, B component, C component and other components are each independently supplied to the melt kneader, (ii) A component, B component, C A method in which a component and a part of another component are premixed and then supplied to the melt kneader independently of the remaining components, and (iii) a method in which the component B is diluted and mixed with water or an organic solvent and supplied to the melt kneader. Further, (iv) a method in which such a diluted mixture is premixed with other components and then supplied to a melt kneader is exemplified. 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.

  A preferred extruder has a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin. A pressure reducing pump such as a vacuum pump is preferably installed in the vent. By such installation, generated moisture and volatile gas are efficiently discharged outside 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 screens include wire meshes, screen changers, and sintered metal plates (such as disk filters). Examples of the melt-kneader include a banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more axes in addition to the 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. Since the aromatic polycarbonate resin composition of the present invention contains fibrillated PTFE, it has favorable characteristics in injection press molding, gas assist injection molding, and foam molding.

  Various shaped extrusion molded articles, sheets, films and the like can also be produced from the aromatic polycarbonate resin composition of the present invention by an extrusion method. In addition, an inflation method, a calendar method, a casting method, and the like may be applied to the formation of the sheet and the film. Furthermore, the aromatic polycarbonate resin composition of the present invention can be formed into a heat-shrinkable tube by applying a specific stretching operation. Moreover, you may manufacture a molded article by applying rotation molding, blow molding, etc. to the aromatic polycarbonate resin composition of this invention. Fibrilized PTFE often works favorably in extrusion molding and 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 contains, as an essential component, a fluorine-containing organometallic salt compound (especially an alkali metal perfluoroalkyl sulfonate) having a reduced fluoride ion content. Such a metal salt compound reduces aggregation of fibrillated PTFE and inconveniences (particularly color unevenness problem) in the polycarbonate resin composition containing fibrillated PTFE. Furthermore, the aromatic polycarbonate resin composition of the present invention also has excellent flame retardancy. Therefore, according to this invention, the manufacturing method of the said structure (5) and the manufacturing method of the said structure (6) are also provided. Thus, there has never been a technique for reducing aggregation of fibrillated PTFE and inconveniences derived therefrom by reducing the amount of fluoride ions in the fluorine-containing organometallic salt compound.

  Usually, the resin composition is based on a balance of various properties, and it is often difficult to change the components in the resin composition. For example, the color unevenness of the present invention can be suppressed by blending a filler having a relatively high shielding effect. However, such responses generally have a negative impact on other important properties (such as flame retardancy and mechanical strength). According to the present invention, the problem is solved by the fluorine-containing organometallic salt compound itself, so that inconvenience due to the blending of other components is avoided. In other words, a very ideal solution for the problem is proposed. In particular, in a composition containing a titanium dioxide pigment, if the color unevenness of the molded product during the molding process is improved without basically changing the composition, the influence is great. Therefore, the aromatic polycarbonate resin composition of the present invention is extremely useful for various industrial applications 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.
(1) Flame retardance Using a test piece having a shape conforming to UL standard 94 and having a thickness described in Tables 1 and 2, a combustion test was performed by a method conforming to the vertical combustion test of UL standard 94. The presence or absence of drip and the maximum number of burning seconds in a set of five test pieces were recorded. A sample in which even one drip occurred was not recorded as the maximum number of burning seconds. The test piece was manufactured by injection molding in a molding cycle of 2 minutes as described below. After molding, the test piece was stored for 48 hours in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%. A combustion test was performed after such storage.

(2) Light transmittance of molded article About the sample (Examples 1-2 and Comparative Examples 1-2) which does not contain a titanium dioxide pigment, the light transmittance of the molded article was observed. Such light transmittance is an index for confirming the aggregation state of fibrillated PTFE. That is, when fibrillated PTFE aggregates, the light transmittance increases. The total light transmittance of both the plate during molding (before residence) and the 10-minute residence molding (after residence) was measured. A value obtained by subtracting that before residence from the total light transmittance after residence was defined as ΔTt. It can be said that the aggregation of fibrillated PTFE progressed as the ΔTt increased. The measurement plate was a three-stage plate having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the gate side. A 2 mm portion of a three-stage plate was used for measuring the total light transmittance. The total light transmittance was measured according to JIS K7105 using a haze meter HR-100 (manufactured by Murakami Color Research Laboratory Co., Ltd.).

(3) Visual observation of aggregation state About the sample (Examples 1-2 and Comparative Examples 1-2) which does not contain a titanium dioxide pigment, the aggregation state of fibrillated PTFE was visually observed. The observation was performed using the same three-stage plate as in (2) above.

(4) L value of retention molded article About the sample (Examples 3-8 and Comparative Examples 3-7) containing a titanium dioxide pigment, the L value of the molded article at the time of 10 minutes residence molding was observed. A lower L value indicates that the titanium dioxide pigment is aggregated with the aggregation of the fibrillated PTFE. That is, the concealment effect by the titanium dioxide pigment is reduced by the aggregation of the pigment, and the blackness by the carbon black is emphasized instead. The measurement plate used was the same three-stage plate as in (2), and a 2 mm thick portion was measured. The color computer (TC-1800MK-II: Tokyo Denshoku Co., Ltd. product) was used for the measurement.

(5) Visual observation of uneven color The state of uneven color was visually observed about the sample (Examples 3-8 and Comparative Examples 3-7) containing a titanium dioxide pigment. The observation was performed using the same three-stage plate as in (2) above. In Table 2, “Yes” is indicated when the plate exhibits a non-uniform hue, ie, color unevenness is observed, and “None” is indicated when the plate exhibits a uniform hue, ie, no color unevenness is observed. .

(Examples 1-8 and Comparative Examples 1-7)
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. The strands were extruded under a cylinder and die temperature of 280 ° C. and a vent suction of 3000 Pa. The strands were cooled in a water bath, then cut with a pelletizer and pelletized. The obtained pellets were dried at 120 ° C. for 6 hours using a hot air circulation dryer. The pellets immediately after drying were formed into a three-stage plate and a test piece for combustion test using an injection molding machine (Toshiba Machine Co., Ltd. IS150EN-5Y). The molding conditions were a cylinder temperature described in the column of “test piece molding temperature” in Tables 1 and 2, and a mold temperature of 70 ° C. The molding cycle of the three-stage plate was 1 minute, and the molding cycle of the test piece for the combustion test was 40 seconds.

The raw materials used in Table 1 are as follows.
(A component)
PC-1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 22,500 (Panlite L-1225WP manufactured by Teijin Chemicals Ltd.)
PC-2: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 (Panlite L-1225WX manufactured by Teijin Chemicals Ltd.)
PC-3: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 30,000 (Panlite K-1300WP manufactured by Teijin Chemicals Ltd.)
PC-4: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 16,000 (CM-1000 manufactured by Teijin Chemicals Ltd.)

(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: 400 parts by weight were charged into a glass flask equipped with a thermometer and a stirrer, and then heated to 80 ° C. under nitrogen flow 0 The stirring was continued for 5 hours, and then the mixture was cooled to room temperature (23 ° C.), and the precipitated crystals were collected by filtration. The crystal was washed with 700 parts by weight of ion exchange water, and further washed with 600 parts by weight of methanol. Subsequently, after washing with 600 parts by weight of ion-exchanged water, the wet powder is dried with hot air at 80 ° C. for 20 hours in a nitrogen atmosphere, and the obtained powder is pulverized using a pulverizing mill and passed through a standard sieve No. 400. Got. 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 of simply describing “ion exchange water”.
B-2: Perfluorobutanesulfonic acid potassium salt having a fluoride ion amount of 8 ppm (production of B-2)
Dai Nippon Ink Co., Ltd. MegaFuck F-114P: 100 parts by weight, ion-exchanged water: 400 parts by weight were charged in a glass flask equipped with a thermometer and a stirrer, then heated to 80 ° C., and 0.5 hours After continuing the stirring, the crystals precipitated by cooling to room temperature were taken out by filtration. The crystals were washed with 700 parts by weight of ion exchange water, and the wet powder was dried with a hot air dryer at 80 ° C. for 20 hours. 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 (Megafac F-114P, manufactured by Dainippon Ink, Inc.)

(C component: fibrillated PTFE)
PTFE: Polytetrafluoroethylene having fibril-forming ability (Polyflon MPA FA500 manufactured by Daikin Industries, Ltd.)
B449: A mixture of polytetrafluoroethylene particles having fibril-forming ability and styrene-acrylonitrile copolymer particles (polytetrafluoroethylene content 50% by weight) (BLENDEX B449 manufactured by GE Specialty Chemicals)

(D component: Titanium dioxide pigment)
D-1: Titanium dioxide (Ishihara Sangyo Co., Ltd., Tyco PC-3, average particle size: 0.22 μm, Al ₂ O ₃ content: 2.0 wt%, TiO ₂ content: 91 wt%)

(Other ingredients)
SL: Fatty acid ester mainly composed of stearyl stearate and glycerin tristearate (Riquemar SL900 manufactured by Riken Vitamin Co., Ltd.)
FG70: Brominated polycarbonate oligomer (Fireguard FG-7000 manufactured by Teijin Chemicals Ltd.)
EW: Fatty acid ester containing pentaerythritol tetrastearate as a main component (Rikastar EW-400 manufactured by Riken Vitamin Co., Ltd.)
SiH: Silicone X-40 produced by the following method and containing a phenyl group X-40: Organosiloxane compound (X-40-9243 manufactured by Shin-Etsu Chemical Co., Ltd.) (Disclosed in Japanese Patent No. 082218)
MgSiO2: hydrous magnesium silicate reagent (composition formula: 2MgO · 3SiO ₂ · 5H ₂ O, manufactured by Wako Pure Chemical Industries, Ltd., pH = 11.2)
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)
CB: Carbon Black (Furnace Black # 970 manufactured by Mitsubishi Chemical Corporation)

  From the comparison between Examples and Comparative Examples in Tables 1 and 2, the aromatic polycarbonate resin composition of the present invention was obtained by aggregating fibrillated PTFE by using an alkali metal salt of a specific perfluoroalkanesulfonic acid, It can also be seen that the uneven color of the molded product due to the aggregation is improved.

Claims (6)

  100 parts by weight of aromatic polycarbonate resin (component A), 0.005 to 0.6 parts by weight of fluorine-containing organometallic salt compound (component B), and polytetrafluoroethylene (component C) 0.001 having fibril-forming ability An aromatic polycarbonate resin composition comprising 1 part by weight of an aromatic polycarbonate resin, wherein the B component has a fluoride ion content of 0.2 to 20 ppm as measured by ion chromatography. Composition.   The aromatic polycarbonate resin composition according to claim 1, wherein the component B is a perfluoroalkylsulfonic acid alkali metal salt.   The resin composition further comprises a titanium dioxide pigment (component D) in an amount of 0.01 to 3 parts by weight based on 100 parts by weight of the component A. 2. The aromatic polycarbonate resin composition according to item 1.   The molded article formed from the aromatic polycarbonate resin composition of any one of the said Claims 1-3.   100 parts by weight of aromatic polycarbonate resin (component A), 0.005 to 0.6 parts by weight of fluorine-containing organometallic salt compound (component B), and polytetrafluoroethylene (component C) 0.001 having fibril-forming ability A method for producing an aromatic polycarbonate resin composition comprising 1 part by weight, in which aggregation of component C during molding processing is suppressed, the content of fluoride ions measured by ion chromatography as component B A method for producing an aromatic polycarbonate resin composition comprising using a fluorine-containing organometallic salt compound having a weight ratio of 0.2 to 20 ppm.   Aromatic polycarbonate resin (component A) 100 parts by weight, fluorine-containing organometallic salt compound (component B) 0.005-0.6 parts by weight, fibril forming ability polytetrafluoroethylene (component C) 0.001-1 A method for producing an aromatic polycarbonate resin composition comprising parts by weight and a titanium dioxide pigment (component D) of 0.01 part by weight or more and less than 3 parts by weight, wherein the color unevenness of the molded product during the molding process is improved. And a fluorine-containing organometallic salt compound having a fluoride ion content of 0.2 to 20 ppm by weight as measured by an ion chromatography method as the component B. Method.