JP2007126499A - Aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition comprising graphite that contains a silane compound and/or a silicone compound and exhibits excellent thermal stability. <P>SOLUTION: The aromatic polycarbonate resin composition comprises (A) 60-90 pts.wt. of an aromatic polycarbonate resin (component A) and (B) 10-40 pts.wt. of graphite (component B), and (C) 0.001-5 pts.wt., relative to 100 pts.wt. of the total of the components A and B, of the silane compound and/or the silicone compound (component C) bearing an amino group and/or an epoxy group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition with significantly improved thermal stability. More specifically, the present invention relates to an aromatic polycarbonate resin composition that is excellent in mechanical strength, low anisotropy, antistatic performance, and has a good appearance reinforced with graphite.

  Thermoplastic resins are widely used in all industries because of their ease of production and molding. In particular, aromatic polycarbonate resins generally exhibit excellent electrical insulation, heat resistance, and impact resistance, and are therefore used for storing and transporting electronic components such as semiconductors and electronic circuit boards, various electronic devices, and precision devices. Often used for containers. In recent years, electronic components have been reduced in size and functionality, and the thermoplastic resin is required to have antistatic performance in order to prevent electrical failure to the equipment caused by charging of the thermoplastic resin molded product or equipment malfunction due to dust adhesion. It has been.

In order to prevent such electrical failure and dust adsorption, the thermoplastic resin is given some conductivity by some means, and its volume specific resistance value is set as a so-called antistatic region 10. ^It needs to be about ¹⁰ to 10 ¹² Ω · m. In order to obtain a resin composition having such a resistance value, a method of adding an organic antistatic agent or a conductive resin, carbon black, carbon fiber or scaly graphite, metal fiber or metal flake, conductive property to the resin composition A method of adding metal-coated fibers such as titanium oxide or metal-coated flakes such as conductive mica has been used.

  For example, an antistatic resin composition obtained by blending a sulfonic acid phosphonium salt with an aromatic polycarbonate resin is known (see Patent Document 1). However, when an organic antistatic agent or a conductive resin is used, it is not practical because a large amount of addition is required to obtain a desired resistance value. In particular, an aromatic polyester-based resin typified by an aromatic polycarbonate resin is not preferable because it is easily decomposed by an ionic substance and requires a high processing temperature.

The addition of carbon black is one typical method for imparting electrical conductivity to a thermoplastic resin. For example, the carbon black comprises a specific ratio of aromatic polycarbonate, polyalkylene terephthalate, and carbon black having a specific DBP oil absorption amount. Resin compositions with improved properties are known (see Non-Patent Document 1 and Patent Document 2). Certainly, the addition of carbon black can easily provide conductivity, but in fact it has strong conductivity and is a powder, so increasing the dispersibility increases the electrical conduction state. It is difficult to increase in a stepwise manner, and when the added amount exceeds a certain level, the conductivity rapidly increases. Therefore, by using carbon black, it is difficult to stably produce a resin composition having a weak conductivity of about 10 ¹⁰ to 10 ¹² Ω · m or a molded body thereof. Furthermore, since carbon black itself is flammable, it is difficult to make it flame retardant.

  Also, a resin composition in which anisotropy is improved by blending two types of carbon fibers mainly having different fiber diameters with a thermoplastic resin is known (see Patent Document 3). Conductive fillers such as carbon fibers, metal fibers or metal flakes, metal-coated fibers such as conductive titanium oxide, or metal-coated flakes such as conductive mica have been conventionally used in consideration of improving mechanical properties. However, these fillers also have low electric resistance, and the blending amount must be in a small range in order to obtain a desired resistance value. Accordingly, a slight variation in the blending amount greatly affects the resistance value, and the resistance value variation among lots tends to increase.

  Addition of graphite is also known as a technique for imparting rigidity and antistatic performance to thermoplastic resins. For example, resin compositions comprising a specific ratio of aromatic polycarbonate, flaky graphite having a specific particle size and trimethyl phosphate are known. Yes (see Patent Document 4). However, it is difficult to say that this document discloses sufficient knowledge regarding the thermal stability, and does not disclose effective knowledge for obtaining excellent thermal stability.

Journal of Japan Adhesion Association Vol. 23, no. 3, 103-111 pages (1987) Japanese Patent Laid-Open No. 2002-20608 JP 2001-323150 A JP 2000-119405 A Japanese Patent Laid-Open No. 2001-200353

  As described above, there is a demand for an aromatic polycarbonate resin composition having excellent antistatic performance, mechanical strength, thermal stability and appearance, but no method for obtaining such a resin composition is disclosed. Is the current situation. Accordingly, an object of the present invention is to provide such an aromatic polycarbonate resin composition.

  As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventor uses graphite having a specific particle size and simultaneously contains a silane compound and / or a silicone compound having an amino group and / or an epoxy group. As a result of finding that good thermal stability can be achieved and further investigations, the present invention has been achieved.

  That is, the gist of the present invention is that excellent thermal stability is obtained by blending a specific particle ratio of graphite having a specific particle size and a silane compound and / or a silicone compound having an amino group and / or an epoxy group into a thermoplastic resin. To achieve sex.

  According to the present invention, the above-mentioned problems are as follows: (1) (A) aromatic polycarbonate resin (component A) 60 to 90 parts by weight, (B) graphite (component B) 10 to 40 parts by weight, (C) An aromatic polycarbonate resin composition (Configuration 1) comprising 0.001 to 5 parts by weight of a silane compound and / or a silicone compound (component C) having an amino group and / or an epoxy group.

  One of the preferred embodiments of the present invention is (2) an aromatic polycarbonate resin composition having the above-described constitution (1), characterized in that it is produced by using graphite in which 80% by weight or more is scaly graphite. Configuration 2). The effect of the present invention is more effectively exhibited in scaly graphite (that is, Flaque Graphite).

  One of the preferred embodiments of the present invention is that (3) the aromatic polycarbonate resin composition of the above constitution (1) or (2) wherein the B component graphite is graphite having an average particle diameter of 5 to 300 μm (constitution 3). ).

（ここで式中、Ｘは炭素数１〜１０のアルコキシ基を表し、Ｙはアミノ基またはエポキシ基を含む基を表す。） One of the preferred embodiments of the present invention is that (4) the aromatic polycarbonate resin composition of the above constitutions (1) to (3) (constitution 4), wherein the C component is a silane compound represented by the following formula (1). ).

(In the formula, X represents an alkoxy group having 1 to 10 carbon atoms, and Y represents a group containing an amino group or an epoxy group.)

（ここで式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれアミノ基またはエポキシ基を含む、炭素数１〜１０のアルキル基、炭素数２〜１０のエーテル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基、炭素数７〜２０のアラルキルオキシ基及びメチル基からなる群より選ばれる基を表す。ただし、Ｒ_１、Ｒ_２、およびＲ_３のすべてがメチル基である場合は除く。また、ｍ、ｎは０≦ｍ≦１００、０≦ｎ≦１００の整数を表す。ただし、ｍ、ｎ共に０の場合およびＲ_２のみがアミノ基またはエポキシ基を含む基でありかつｎが０の場合は除く。） One of the preferred embodiments of the present invention is that (5) the aromatic polycarbonate resin composition of the above constitutions (1) to (3) (constitution 5), wherein the component C is a silicone compound represented by the following formula (2): ).

(Wherein R ₁ , R ₂ , and R ₃ are each an alkyl group having 1 to 10 carbon atoms, an ether group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, each containing an amino group or an epoxy group. Alkoxy group, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryloxy group having 6 to 10 carbon atoms Represents a group selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms and a methyl group, except when all of R ₁ , R ₂ , and R ₃ are methyl groups, and m, n Represents an integer of 0 ≦ m ≦ 100 and 0 ≦ n ≦ 100, except when both m and n are 0, and when only R ₂ is a group containing an amino group or an epoxy group and n is 0. )

One of the preferable embodiments of the present invention is that (6) the C component includes any one of R ₁ , R ₂ , and R ₃ containing an amino group or an epoxy group, or an alkyl group having 1 to 10 carbon atoms or a carbon number It is an aromatic polycarbonate resin composition (Structure 6) of said structure (1)-(3) which is a silicone compound represented by said Formula (2) which is 2-10 ether groups.

  One of the preferred embodiments of the present invention is (7) a molded article for electronic equipment formed from the flame retardant resin composition having the above-mentioned constitutions (1) to (6). In particular, it is suitable for a molded product of a portable electronic device that has a high risk of adverse effects on electronic components due to charging during use. Examples of such electronic devices include mobile phones, digital cameras, mobile terminals, and notebook computers. Furthermore, the flame retardant resin composition of the present invention is particularly suitable for molded products mainly composed of a polycarbonate resin, since it has excellent dimensional stability and relatively excellent sliding characteristics due to the blending of graphite. It is suitably used for a member that slides during use, such as a lens barrel.

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 resin, copolymer polycarbonate resin copolymerized with bifunctional alcohol (including alicyclic), and polyester carbonate resin copolymerized with such bifunctional carboxylic acid and bifunctional alcohol are included. Moreover, the mixture which mixed 2 or more types of the obtained aromatic polycarbonate resin may be sufficient.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The average particle size of graphite in the composition of the present invention is in the range of 5 to 300 μm. The particle size is preferably 5 to 70 μm, more preferably 7 to 40 μm, and still more preferably 7 to 35 μm. By satisfying such a range, good flame retardancy is achieved. On the other hand, if the average particle size is less than 5 μm, the effect of improving the dimensional accuracy tends to be lowered, and if the average particle size exceeds 300 μm, the impact resistance is slightly lowered and so-called graphite floats on the surface of the molded product. It is not preferable. Such surface floating is a problem because graphite may fall off from the surface of the molded product and may be connected to an electronic component to damage the component. In addition, the above preferable average particle diameter has an advantage that the appearance of the molded product is improved and good slidability is easily obtained. This particle size was measured by the following method.

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

The fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98% by weight or more. The volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1% by weight or less.
Further, the surface of graphite is subjected to surface treatment such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment in order to increase the affinity with the thermoplastic resin as long as the characteristics of the composition of the present invention are not impaired. It may be given. The amount of component B is 10 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 10 to 30 parts by weight, based on 100 parts by weight of the total of component A and component B. If it is less than 10 parts by weight, it is difficult to obtain good antistatic properties and rigidity, and if it exceeds 40 parts by weight, the thermal stability is lowered.

（ここで式中、Ｘは炭素数１〜１０のアルコキシ基を表し、Ｙはアミノ基またはエポキシ基を含む基を表す。） <C component: silane compound or silicone compound>
The silane compound as the component C of the present invention is preferably a silane compound represented by the following formula (1).

(In the formula, X represents an alkoxy group having 1 to 10 carbon atoms, and Y represents a group containing an amino group or an epoxy group.)

As a specific example of the silane compound, KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd.) is preferable, and is a silane compound represented by the following formula (3).

（ここで式中、Ｒ_１、Ｒ_２、およびＲ_３は、それぞれアミノ基またはエポキシ基を含む、炭素数１〜１０のアルキル基、炭素数２〜１０のエーテル基、炭素数１〜１０のアルコキシ基、炭素数６〜２０のシクロアルキル基、炭素数６〜２０のシクロアルコキシ基、炭素数６〜１０のアリール基、炭素数７〜２０のアラルキル基、炭素数６〜１０のアリールオキシ基、炭素数７〜２０のアラルキルオキシ基及びメチル基からなる群より選ばれる基を表す。ただし、Ｒ_１、Ｒ_２、およびＲ_３のすべてがメチル基である場合は除く。また、ｍ、ｎは０≦ｍ≦１００、０≦ｎ≦１００の整数を表す。ただし、ｍ、ｎ共に０の場合およびＲ_２のみがアミノ基またはエポキシ基を含む基でありかつｎが０の場合は除く。） The silicone compound as component C of the present invention is preferably a compound represented by the following formula (2).

(Wherein R ₁ , R ₂ , and R ₃ are each an alkyl group having 1 to 10 carbon atoms, an ether group having 2 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, each containing an amino group or an epoxy group. Alkoxy group, cycloalkyl group having 6 to 20 carbon atoms, cycloalkoxy group having 6 to 20 carbon atoms, aryl group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aryloxy group having 6 to 10 carbon atoms Represents a group selected from the group consisting of an aralkyloxy group having 7 to 20 carbon atoms and a methyl group, except when all of R ₁ , R ₂ , and R ₃ are methyl groups, and m, n Represents an integer of 0 ≦ m ≦ 100 and 0 ≦ n ≦ 100, except when both m and n are 0, and when only R ₂ is a group containing an amino group or an epoxy group and n is 0. )

Among these, the silicone compound represented by the above formula (2), wherein R ₁ , R ₂ , and R ₃ are an alkyl group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms, including an amino group or an epoxy group. Is preferred.

( ここで式中、Ｒは NH₂-C₂H₄-NH-C₃H₆である。また、ｍ、ｎは０≦ｍ≦１００、１≦ｎ≦１００の整数を表す。)

Specific examples of the silicone compound include SF8417 (manufactured by Dow Corning Toray) and BY16-855D (manufactured by Dow Corning Toray), which are represented by the following formulas (4) and (5).

(Wherein, R is NH ₂ —C ₂ H ₄ —NH—C ₃ H ₆ , and m and n represent integers of 0 ≦ m ≦ 100 and 1 ≦ n ≦ 100.)

Of the formulas (3), (4) and (5), the compound represented by (3) is most preferred.
The amount of component C is 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the total of component A and component B. .

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

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

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

The acid value in the saturated fatty acid ester of the present invention is preferably 20 or less (can take substantially 0), more preferably 2 to 15, and still more preferably 4 to 15. The hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K0070.
Content of a mold release agent is 0.005-3 weight part on the basis of 100 weight part A component, Preferably it is 0.01-1 weight part.

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

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

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

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

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

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

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

(Iii) Flame Retardant Various compounds known as flame retardants may be blended in the aromatic polycarbonate resin composition of the present invention. The compounding of the compound used as a flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

  Examples of such flame retardants include (i) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (ii) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

(Iii-1) Organometallic salt-based flame retardant An organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing 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 ion of the organometallic salt flame retardant 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, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. 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.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, 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 0.1 to 3 hours, more preferably 0.5 to 2.5 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. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The blending amount of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, based on the total of 100 parts by weight of the component A and the component B. Preferably it is 0.008-0.13 weight part. The more preferable range is, the effects (for example, flame retardancy and antistatic properties) expected by the blending of the fluorine-containing organic metal salt are exhibited, and the adverse effect on the light resistance of the polycarbonate resin composition is reduced.

  In addition, as an organic metal salt flame retardant other than the above-mentioned fluorine-containing organic metal salt compound, a metal salt of an organic sulfonic acid not containing a fluorine atom is suitable. Examples of the metal salt include an alkali metal salt of an aliphatic sulfonic acid, an alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of an aromatic sulfonic acid, and an alkaline earth metal salt of an aromatic sulfonic acid (any Also does not contain a fluorine atom).

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

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

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

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

  Among the above, preferable metal salts of organic sulfonic acids not containing fluorine atoms are aromatic (earth) metal salts of aromatic sulfonates, and potassium salts are particularly preferable. When blending such an alkali (earth) sulfonic acid metal salt, the content is 0.001 to 1 part by weight, more preferably 0.005 based on the total of 100 parts by weight of component A and component B. It is -0.5 weight part, More preferably, it is 0.01-0.1 weight part.

(Iii-2) Silicone Flame Retardant The silicone compound used as the silicone flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins 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 silicone compound used in the silicone-based flame retardant 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 formulas are integers of 1 or more representing 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 and hue.
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. .

  The 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.

（式中、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。） Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (6) is 10 to 70% by weight (more preferably 15 to 60% by weight).

(In the formula, X independently represents an OH group and a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in the formula, when n is 2 or more, You can take different kinds of X.)

  The silicone compound used as the silicone-based flame retardant 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, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.

（式（７）および式（８）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（９）で示される化合物を示す。α^１〜α^３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（７）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。） As a silicone compound which has Si-H group, the silicone compound containing at least 1 or more types of the structural unit shown by the following general formula (7) and (8) is illustrated suitably.

(In formula (7) and formula (8), 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 (9). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer greater than or equal to 1. Further, in formula (7), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式中、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。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ_２は０もしくは１以上の整数を表わす。さらに式中においてｍ_２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 the formula, 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 in the formula, when m ₂ is 2 or more, the repeating unit can take a plurality of different repeating units.

（式中、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。） Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from the compounds represented by the general formula (10) and the general formula (11).

(In the formula, 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 and an 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 an aryl group or an aralkyl group. Δ ¹ , δ ² , and δ ³ represent an alkoxy group having 1 to 4 carbon atoms.)

（式中、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 the formula, 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 an aryl group having 6 to 12 carbon atoms Represents an aralkyl group, 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.

  When blending such a silicone-based flame retardant, the content thereof is 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, still more preferably, based on a total of 100 parts by weight of component A and component B. Is 1.2 to 5 parts by weight.

（式中、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。） (Iii-3) Halogen Flame Retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (l2) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. It is a brominated polycarbonate compound composed of the structural unit represented by (l2).

(In the formula, 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 (l2), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.
The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 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 polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a polycarbonate resin composition that is superior in molding processability is provided.

The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. 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 polycarbonate resin composition is further improved.

The specific viscosity of the 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 above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.
When blending such a halogenated flame retardant, the content thereof is 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, and still more preferably 1 based on the total of 100 parts by weight of component A and component B. ~ 18 parts by weight.

(Iv) Filler In the flame-retardant resin composition of the present invention, various fillers other than the component B can be blended as reinforcing fillers within the range where the effects of the present invention are exhibited. For example, calcium carbonate, glass fiber, glass bead, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon bead, carbon milled fiber, vapor grown ultrafine carbon fiber (fiber diameter is 0.1 μm or more), carbon nanotube (Fiber diameter is less than 0.1 μm, hollow), fullerene, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, metal oxide particles, metal oxide fibers, Examples include metal oxide balloons and various whiskers (such as potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more.

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

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

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

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

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

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

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

  The aromatic polycarbonate resin composition of the present invention has an aromatic polycarbonate resin composition having good thermal stability by using a silane compound and / or a silicone compound having an amino group and / or an epoxy group, and its A molded article (particularly preferably a housing molded article) is provided.

  The aromatic polycarbonate resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and in particular, uses that require antistatic performance for molded articles that dislike dust and the like of electrical and electronic equipment and It satisfies satisfactory characteristics corresponding to applications that require efficient heat dissipation from the equipment.

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

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

In addition, the aromatic polycarbonate resin composition of the present invention includes various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, electronic Containers for parts transportation (IC magazine cases, silicon wafer containers, glass substrate storage containers, carrier tapes, etc.), antistatic or antistatic parts (e.g., charging rolls for electrophotographic photosensitive devices), and various mechanical parts (gear, It can be used for turntables, rotors, screws, etc. (including mechanical parts for micromachines).
Therefore, the resin composition of the present invention is extremely useful for various industrial uses such as the field of OA equipment and the field of electrical and electronic equipment, and the industrial effect exerted by the resin composition is extremely large.

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

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. The following items were evaluated.
(I) Thermal Stability Evaluation Molding Machine Made by TOSHIBA MACHINE IS25EP, cylinder temperature 300 ° C., mold temperature 80 ° C., retained in the molding machine for 10 minutes and then molded. The viscosity average molecular weight of the obtained molded product was measured, and the thermal stability was evaluated by the difference (ΔM) from the viscosity average molecular weight of the molded product molded without staying.
(Ii) Rigidity (flexural modulus)
The flexural modulus (MPa) was measured according to ISO178. The shape of the test piece was 80 mm long × 10 mm wide × 4 mm thick.
(Iii) Appearance evaluation Molding with a weight of about 90 g including 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 The product was injection molded. The case where there was no roughness on any step on the surface of such a three-stage plate was evaluated as ◯, and the case where roughness was found on any step was evaluated as x.
(Iv) Antistatic performance (charged half-life before drying treatment)
Using a 2 mm thick part of the above-mentioned three-stage plate, the plate was stored for one week in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The charged voltage half-life (seconds) of the test piece was determined according to -0110). The smaller the value of the charged voltage half-life, the better the antistatic performance.
(V) Flame retardancy Using a test piece having a shape conforming to UL standard 94 and having a thickness described in Table 1, 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. 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.
The following were used as raw materials.
Each component indicated by symbols in Tables 1 and 2 is as follows.

(A component)
PC: Linear polycarbonate resin powder having a viscosity average molecular weight of 19700 (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX)
(B component)
B-1: Scale-like graphite (average particle size 3.3 μm, fixed carbon content 80.0%, volatile content 3.0%, ash content 17.0%) [Nishimura Graphite Co., Ltd. ultra fine powder (trade name) ]
B-2) Scale-like graphite (average particle size 10 μm, fixed carbon amount 99.0%, volatile content 0.6%, ash content 0.4%) [PB-99 (trade name) manufactured by Nishimura Graphite Co., Ltd.]
B-3) Scale-like graphite (average particle size 25 μm, fixed carbon content 99.0%, volatile content 0.6%, ash content 0.4%) [PA-99 (trade name) manufactured by Nishimura Graphite Co., Ltd.]
B-4) Scale-like graphite (average particle size 350 μm, fixed carbon amount 98.0%, volatile content 1.5%, ash content 0.5%) [5098 (trade name) manufactured by Nishimura Graphite Co., Ltd.]
(C component)
C-1: Aminosilane compound [KBM603 manufactured by Shin-Etsu Chemical Co., Ltd.]
C-2: Amino-modified silicone compound [SF8417 manufactured by Toray Dow Corning Co., Ltd.]
C-3: Epoxy-modified silicone compound [BY16-855D manufactured by Toray Dow Corning Co., Ltd.]
(Additives other than the present invention)
TMP: Trimethyl phosphate [Dahachi Chemical Industry Co., Ltd. TMP]
DC: α-olefin maleic anhydride copolymer wax [Diacarna-30 manufactured by Mitsubishi Chemical Corporation, acid value 75 mgKOH / g]
AY: Silane coupling agent [AY43-408 manufactured by Toray Dow Corning Co., Ltd.]
(Other ingredients)
FR: potassium perfluorobutane sulfonate (manufactured by Dainippon Ink & Chemicals, Inc., MegaFuck F-114P)
PTFE: Polytetrafluoroethylene having a fibril forming ability (“Polyflon MPA FA500” (trade name) manufactured by Daikin Industries, Ltd.)
SL: Fatty acid ester mainly composed of stearyl stearate and glycerin tristearate (Riquemar SL900 manufactured by Riken Vitamin Co., Ltd.)

[Examples 1-8, Comparative Examples 1-7]
Prepare a pre-mixture by uniformly mixing the aromatic polycarbonate resin, scaly graphite, amino group and / or epoxy group-containing silane compound or silicone compound, and other components with the composition shown in Table 1 and Table 2 using a tumbler. The mixture was prepared and supplied from a first supply port located at the screw root of the extruder. The obtained preliminary mixture is supplied to the first supply port (screw base) of a vent type twin screw extruder [TEX30XSST manufactured by Nippon Steel Works, Ltd.] having a diameter of 30 mmφ, and the cylinder temperature is 280 ° C., the screw rotation number is 170 rpm, and the discharge is performed. It was melt-extruded and pelletized at an amount of 13 kg / h and a vent vacuum of 3 kPa.
The obtained pellets were dried at 120 ° C. for 5 hours with a hot-air circulating dryer, and then a test piece for evaluation was molded using an injection molding machine at a cylinder temperature of 300 ° C. and a mold temperature of 80 ° C. The evaluation results are shown in Tables 1 and 2.

  As is apparent from the above table, it can be seen that the aromatic polycarbonate resin composition of the present invention has excellent thermal stability.

Claims (7)

  (A) 60 to 90 parts by weight of aromatic polycarbonate resin (component A) and (B) 10 to 40 parts by weight of graphite (component B), and (C) amino group and / or epoxy group An aromatic polycarbonate resin composition comprising 0.001 to 5 parts by weight of a silane compound and / or a silicone compound (component C).   2. The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin composition is manufactured using graphite having 80% by weight or more of flaky graphite.   The aromatic polycarbonate resin composition according to claim 1, wherein the graphite (component B) is graphite having an average particle diameter of 5 to 300 μm. The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the component C is a silane compound represented by the following formula (1).

(In the formula, X represents an alkoxy group having 1 to 10 carbon atoms, and Y represents a group containing an amino group or an epoxy group.) C component is a silicone compound represented by following formula (2), The aromatic polycarbonate resin composition of any one of Claims 1-3.

(Wherein R ₁ , R ₂ and R ₃ each comprise an amino group or an epoxy group,
An alkyl group having 1 to 10 carbon atoms, an ether group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, and 6 carbon atoms. Represents a group selected from the group consisting of an aryl group having 10 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, and a methyl group. However, the case where all of R ₁ , R ₂ , and R ₃ are methyl groups is excluded. M and n represent integers of 0 ≦ m ≦ 100 and 0 ≦ n ≦ 100. However, the case where both m and n are 0 and the case where only R ₂ is a group containing an amino group or an epoxy group and n is 0 are excluded. ) In the above formula (2), the C component is an alkyl group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms, in which any of R ₁ , R ₂ , and R ₃ includes an amino group or an epoxy group It is a silicone compound represented, The aromatic polycarbonate resin composition of any one of Claims 1-3.   The resin molded product formed by shape | molding the aromatic polycarbonate resin composition of any one of Claims 1-6.