JP4705392B2 - Flame retardant resin composition - Google Patents

Description

  The present invention relates to a flame retardant resin composition. More specifically, the flame retardancy has excellent antistatic performance, rigidity, thermal stability and appearance, and high flame retardancy without the use of chlorine, bromine and phosphorus flame retardants The present invention relates to a resin composition.

  Thermoplastic resins are widely used in all industries because of their ease of production and molding. In particular, aromatic polycarbonate resins generally exhibit excellent electrical insulation, heat resistance, and impact resistance, and are therefore used for storing and transporting electronic components such as semiconductors and electronic circuit boards, various electronic devices, and precision devices. Often used for containers. In recent years, 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. Further, since miniaturization and high functionality of electronic components lead to heat generation of electronic components, there is a demand for high flame retardancy for thermoplastic resins used in electronic components.

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, so that the decomposition is further promoted.

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 about the flame retardancy, and particularly excellent flame retardancy is achieved without blending a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. It did not disclose effective knowledge to obtain.

  On the other hand, a number of techniques for making a resin composition flame-retardant by blending expansive graphite as a flame retardant with a thermoplastic resin have been reported. For example, a resin composition comprising a thermoplastic resin, thermally expandable graphite and red phosphorus (see Patent Document 5), a thermoplastic resin, neutralized thermally expandable graphite, and ammonium polyphosphate having a specific weight reduction temperature. A resin composition (see Patent Document 6), a thermoplastic resin, and a thermally expandable graphite in which a guest compound composed of an organic molecule having a functional group easily coordinated to an alkali (earth) metal is inserted between graphite layers. Resin composition (refer to Patent Document 7), thermoplastic resin, thermally expandable graphite and resin composition comprising a specific ratio of specific cyclic phosphorus compound (refer to Patent Document 8), and polycarbonate resin, phosphorus compound, neutralized In addition, a resin composition comprising a thermally expandable graphite and an inorganic filler (see Patent Document 9) is known.

  However, such heat-expandable graphite tends to lower the thermal stability of the resin composition due to an interlayer treatment agent typified by concentrated nitric acid, and a resin composition that is more excellent in thermal stability and flame retardancy. There were cases where it was required. Furthermore, in recent years, it has been demanded that the burden on the environment is reduced by the material. Therefore, there is a demand for a material having good flame retardancy without adding a chlorine-based flame retardant, a bromine-based flame retardant, and a phosphorus-based flame retardant. In this respect, the knowledge of the above-mentioned document does not disclose knowledge sufficient to satisfy such a requirement.

  In addition, when producing a resin composition in which conductive carbon black or graphite is blended with a polycarbonate resin with an extruder, it is possible to blend polytetrafluoroethylene having a fibril forming ability in order to enhance the supply capability of the premix. It is publicly known (see Patent Document 10).

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 JP-A-8-73649 JP-A-8-217910 JP-A-10-183011 Japanese Patent Laid-Open No. 11-217508 Japanese Patent No. 2000-63619 Japanese Patent Laid-Open No. 3-91556

  As mentioned above, it has excellent antistatic performance, rigidity, thermal stability and appearance, and has high flame retardancy without using chlorine-based flame retardant, bromine-based flame retardant and phosphorus-based flame retardant Although there is a demand for a resin composition, there is currently no disclosure of a method for obtaining such a resin composition. Therefore, an object of the present invention is to provide such a flame retardant resin composition.

  As a result of intensive studies in view of the above-mentioned problems of the prior art, the present inventor has good flame retardancy when using graphite having a specific particle size and simultaneously containing an alkali (earth) metal salt of an organic sulfonate. As a result of finding out that it can be achieved and conducting further studies, the present invention has been achieved.

  That is, the gist of the present invention is that a good flame retardancy is obtained by such a synergistic effect by blending a thermoplastic resin with graphite having a specific particle size and an alkali (earth) metal sulfonate in a specific ratio. To achieve. It is expected that graphite with a specific particle size will give an appropriate reinforcing effect and thermal stability effect to the resin, and that decomposition and carbonization by alkali metal sulfonate (earth) metal salt will work effectively as an improvement in flame retardancy. The

  According to the present invention, the above problems are (1) (A) 100 parts by weight of a thermoplastic resin (component A), (B) 5 to 100 parts by weight of graphite (component B) having an average particle diameter of 5 μm to 300 μm, ( C) An organic sulfonate alkali (earth) metal salt (component C) is achieved by a flame retardant resin composition comprising 0.001 to 1 part by weight.

  One of the preferred embodiments of the present invention comprises (2) 0.01 to 5 parts by weight of a fluorine-containing anti-dripping agent (D component) with respect to 100 parts by weight of the thermoplastic resin of component (A). It is a flame retardant resin composition of the said structure (1) formed. By blending such a fluorine-containing anti-drip agent, even better flame retardancy can be obtained without affecting the antistatic performance. The reason why such a fluorine-containing anti-drip agent acts effectively is considered to be because a moderate reinforcing effect and a heat stabilizing effect are given to the resin by the B component having a specific particle diameter.

  One of the preferred embodiments of the present invention is that the flame retardant resin according to any one of the above constitutions (1) to (2), wherein (3) the thermoplastic resin of component A is 50% by weight or more of 100% by weight of the resin. It is a composition. Such a polycarbonate resin is excellent in flame retardancy and moldability, and is a particularly preferable thermoplastic resin in the present invention because the effect of the alkali (earth) metal salt of organic sulfonate is particularly effectively exhibited.

  One of the preferred embodiments of the present invention is that the flame retardant resin composition according to any one of the above constitutions (1) to (3), wherein (4) the B component graphite is 80% by weight or more of flaky graphite in 100% by weight. It is a thing. 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 (5) a molded article for electronic equipment formed from the flame retardant resin composition having the above-mentioned constitutions (1) to (4). 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.

Details of the present invention will be described below.
<A component: Thermoplastic resin>
The thermoplastic resin of component A of the present invention is not particularly limited. Such preferred thermoplastic resins include polycarbonate resin, polyethylene naphthalate resin, polyarylate resin, polyphenylene ether resin, polysulfone resin, polyether sulfone resin, cyclic polyolefin resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyamino Examples thereof include bismaleimide resins and polyether ether ketone resins. Among these, polycarbonate resin, polyethylene naphthalate resin, and polyarylate resin are preferable, and polycarbonate resin is particularly preferable. In addition, said suitable A component should just contain 50 weight% or more of a suitable thermoplastic resin in 100 weight% A component, Preferably it is 60 weight% or more, More preferably, it is 70 weight% or more. That is, a thermoplastic resin other than such a suitable thermoplastic resin may be contained in 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less in 100% by weight of the component A.

  The polycarbonate resin which is a particularly preferred component A of the present invention will be described. A typical polycarbonate resin (hereinafter, sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor. The reaction may be performed by an interfacial polycondensation method, a molten ester, or the like. Examples thereof include an exchange method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “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-phenylenediisopropylidene) Phenol, 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, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to the 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 of 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, the following (1) to (3) copolymer polycarbonates are particularly preferable.
(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 methods 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 and the like 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.

  On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol or the like can be mentioned.

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

  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. In addition, about the ratio of this branched structure, it is possible to calculate by 1H-NMR measurement.

  The component A polycarbonate resin is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a copolymer obtained by copolymerizing a bifunctional alcohol (including alicyclic). Polyester carbonate obtained by copolymerizing a polymerized polycarbonate and such a bifunctional carboxylic acid and a bifunctional alcohol together may be used. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

  The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, etc., linear saturated aliphatic dicarboxylic acid 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.

  Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.

  The component A polycarbonate resin may be a mixture of two or more of polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, polycarbonate-polyorganosiloxane copolymers, and the like. Good. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used.

  In the polymerization reaction of polycarbonate, the reaction by the interfacial polycondensation 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, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As the monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, as monofunctional phenols, long chain alkyl groups having 10 or more carbon atoms such as decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol are used. A monofunctional phenol substituted with a nucleus can be mentioned, and the phenol is effective in improving fluidity and hydrolysis resistance. Such end terminators may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is decompressed to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Further, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, relative to 1 mol of dihydric phenol as a raw material. It is.

  In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polycarbonate. Compounds such as phenylphenyl carbonate can be added.

  Furthermore, 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. Moreover, it is suitable to use in the ratio of 0.01-500 ppm with respect to the polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, Most preferably, it is a ratio of 0.01-100 ppm. Examples of preferable quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecyl benzyl sulfate.

  When the viscosity average molecular weight of the polycarbonate resin of component A is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process properties are lowered. Therefore, the range is from 10,000 to 50,000. Is preferable, the range of 12,000 to 30,000 is more preferable, and the range of 15,000 to 28,000 is more preferable.

  The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (50,000) has high entropy elasticity. As a result, good moldability is exhibited in gas assist molding, extrusion molding, blow molding, injection press molding and foam molding. Such improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, the polycarbonate resin of component A is a polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-3-1) and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 ( A polycarbonate resin (A-3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as “high molecular weight component-containing polycarbonate resin”). Can be mentioned.

  In such a high molecular weight component-containing polycarbonate resin (component A-3), the molecular weight of the component A-3-1 is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000. 000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-3-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 3 to 30% by weight and 70 to 97% by weight of the A-3-2 component, more preferably 4 to 20% by weight of the A-3-1 component and 80 to 96% by weight of the A-3-2 component. In particular, the A-3-1 component is preferably 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  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 a polycarbonate resin having a plurality of polymer peaks in the molecular weight distribution chart by the GPC method, represented by the method shown in the Gazette, in the same system, the polycarbonate resin is a condition of the A-3 component of the present invention And (3) a polycarbonate resin obtained by such a production method (production method (2)), and separately produced A-3-1 component and / or A-3-2 component And the like.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., the 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

  In addition, calculation of the viscosity average molecular weight in the flame-retardant 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.

  Examples of the polyarylate resin include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the divalent phenol component is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

  Other typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and the dihydric phenol component is composed of bisphenol A and hydroquinone. The ratio of bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. .

  The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 in view of physical properties and extrusion processability. The polyarylate resin can be selected from any polymerization method of interfacial polycondensation and transesterification.

<B component: graphite>
As the graphite used as the component B in the present invention, any of natural graphite made of graphite by the 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 100% by weight of the B component, and particularly preferably, the total amount of the B component is substantially 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 particle size of the graphite 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. This is because the float on the surface may cause graphite to fall off the surface of the molded product and cause electrical damage to the electronic component. In addition, the above preferable average particle diameter has an advantage that the appearance of the molded product is improved and good slidability is easily obtained.

  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.

  The average particle diameter of graphite in the present invention refers to the particle diameter of the B component itself before becoming a composition, and the particle diameter is determined by a laser diffraction method.

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

<C component: organic sulfonate alkali (earth) metal salt>
The alkali (earth) metal sulfonate in the present invention is a metal salt of fluorine-substituted alkyl sulfonic acid such as a metal salt of perfluoroalkyl sulfonic acid and alkali metal or alkaline earth metal, and aromatic sulfonic acid and alkali metal. Or a metal salt with an alkaline earth metal salt.

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

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

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

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

  The amount of component C is 0.001 to 1 part by weight, preferably 0.01 to 0.3 part by weight, more preferably 0.03 to 0.2 part by weight, based on 100 parts by weight of component A. is there. When the component C is less than 0.001 part by weight per 100 parts by weight of the component A, flame retardancy is not achieved, and when it exceeds 1 part by weight, the thermal stability is lowered and the flame retardancy is also lowered. The amount of component C is preferably in the range of 0.0001 to 0.03 parts by weight, more preferably in the range of 0.0005 to 0.015 parts by weight, based on 100 parts by weight of component B.

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

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

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

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

  As a ratio of PTFE in the mixed form, PTFE is preferably 10 to 80% by weight, more preferably 15 to 75% by weight in 100% by weight of the PTFE mixture. When the ratio of PTFE is within such a range, good dispersibility of PTFE can be achieved.

  The blending amount of component D is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1 part by weight, still more preferably 0.1 to 0.6 parts based on 100 parts by weight of component A. Parts by weight. In such a range, it is possible to achieve both a sufficient melt dripping preventing effect and good appearance and flow characteristics. In addition, the ratio of the said D component shows the quantity of a net fluorine-containing dripping inhibitor, and in the case of mixed form PTFE, it shows a net PTFE quantity.

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

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

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

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

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

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

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

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

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

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

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

  Among such release agents, saturated fatty acid esters, particularly partial esters and / or full esters of higher fatty acids and polyhydric alcohols are preferred. Full esters are particularly preferred. Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms, 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 K 0070.

  Content of a mold release agent is 0.005-3 weight part on the basis of 100 weight part A component, Preferably it is 0.01-1 weight part.

(Iv) Ultraviolet Absorber The flame retardant resin composition of the present invention may be required to have good light resistance, and in such a case, the incorporation of an ultraviolet absorber is effective.

  Specific examples of the ultraviolet absorber include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2-hydroxy-4-benzyloxy. Benzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydride benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5- Benzoyl-4-hydroxy-2 Methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

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

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

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

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

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

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

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

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

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

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

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

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

(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 other than component D), colorants (for example, pigments and dyes such as carbon black and titanium oxide), fluorescent dyes, and inorganic phosphors (for example, aluminate as a base crystal). Phosphors), antistatic agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (eg fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), photochromic agents, etc. Is mentioned.

(Manufacture of flame retardant resin composition)
Arbitrary methods are employ | adopted in order to manufacture the flame-retardant resin composition of this invention. For example, components A to D, and optionally other components are mixed thoroughly using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, and extrusion mixer, respectively. 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 common shapes, such as a cylinder, a prism, and a sphere, it is a cylinder more suitably. 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 flame retardant resin composition of the present invention can be usually obtained by injection molding the pellet. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding.

  Moreover, according to this invention, a flame-retardant resin composition can be extrusion-molded and it can also be made into shapes, such as various profile extrusion molded articles, a sheet | seat, and a film. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. Furthermore, it can be formed as a heat-shrinkable tube by applying a specific stretching operation. Further, the flame-retardant 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 flame retardant resin composition of the present invention contains an organic sulfonic acid alkali (earth) metal salt, so that it does not substantially contain a chlorine flame retardant, a bromine flame retardant, and a phosphorus flame retardant. The present invention provides a flame retardant resin composition having good flame retardancy and further excellent flame retardancy by combining with a fluorine-containing anti-dripping agent, and a molded product thereof (particularly preferably a housing molded product).

  The flame retardant 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 a housing of a 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 devices such as VTR cameras, optical film cameras, digital still cameras, camera lens units, security devices, and mobile phones. In particular, the flame-retardant resin composition of the present invention is suitably used for a housing, a cover, and a frame of a digital image information processing apparatus such as a camera barrel or a digital camera.

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

  In addition, the flame-retardant resin composition of the present invention includes various vehicle parts, batteries, power generation devices, circuit boards, integrated circuit molds, optical disk boards, disk cartridges, optical cards, IC memory cards, connectors, cable couplers, electronic 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.

The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated.
(I) Flame 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.
(Ii) Appearance Evaluation Molding with a weight of about 90 g including a three-stage plate with 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.
(Iii) 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.
(Iv) Antistatic performance (charged voltage half-life before drying treatment): Using the 2 mm thick part of the above three-stage plate, the plate is stored for one week in an environment of a temperature of 23 ° C. and a relative humidity of 50%. After the adjustment, the charged voltage half-life (seconds) of the test piece was determined with a static Honest meter (H-0110 manufactured by Shido Static Electric Co., Ltd.). The smaller the value of the charged voltage half-life, the better the antistatic performance. Those whose half-life could not be measured are indicated by x in the table.

The following were used as raw materials.
(A component)
PC: Linear aromatic polycarbonate resin powder synthesized by interfacial polycondensation method from bisphenol A and p-tert-butylphenol as a terminator and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX, viscosity average molecular weight) 19,700)
PC-BCF: Aromatic polycarbonate resin powder made of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (abbreviated as “BCF”) and bisphenol A (abbreviated as “BPA”) produced by the following method PEN: Polyethylene naphthalate resin (manufactured by Teijin Chemicals Ltd .: Teonex TN8770 (trade name)), the resin having a dicarboxylic acid component of 92 mol% of 2,6-naphthalenedicarboxylic acid component and a total of 100 mol of terephthalic acid component of 100 (Mole%, IV value is 0.7, glass transition temperature is 115 ° C.)
PAR: Polyarylate resin (manufactured by Unitika Ltd .: U polymer U-100 (trade name))
“Teonex TN8770” manufactured by Teijin Chemicals Ltd. (92 mol% of 2,6-dimethyl naphthalate, 8 mol% of dimethyl terephthalate, IV: 0.70)
[Method for producing PC-BCF]: A reactor equipped with a thermometer and a stirrer was charged with 19580 parts of ion-exchanged water and 3850 parts of a 48.5% by weight aqueous sodium hydroxide solution, to which 1175 parts of BCF, 2835 parts of BPA, and hydrosulfite 9 After dissolving the parts, 13210 parts of methylene chloride was added and 2000 parts of phosgene was blown in at 40 ° C. for about 40 minutes with vigorous stirring. After completion of the phosgene blowing, the temperature was raised to 28 ° C., 94 parts of p-tert-butylphenol and 640 parts of sodium hydroxide were added to emulsify, 6 parts of triethylamine was added, and stirring was continued for 1 hour to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the methylene chloride was evaporated in a kneader. 4080 parts of a colorless powder of copolymer having a BCF: BPA molar ratio of 20:80 was obtained. The viscosity average molecular weight of this copolymer polycarbonate (PC-BCF) powder was 20,300. The reaction system was carried out under nitrogen bubbling and nitrogen reflux to block contact with oxygen during the reaction.

(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: Perfluorobutanesulfonic acid potassium salt [Dainippon Ink Co., Ltd. product: MegaFuck F-114P (trade name)]
C-2: 2: 8 mixture of diphenylsulfone-3,3′-disulfonic acid dipotassium salt and diphenylsulfone-3-monosulfonic acid dipotassium salt [manufactured by UCB Japan: KSS (trade name)]
(D component)
PTFE: polytetrafluoroethylene having a fibril forming ability [manufactured by Daikin Industries, Ltd .: Polyflon MPA FA500 (trade name)]
(Other)
SL: fatty acid ester mainly composed of stearyl stearate and glycerin tristearate [manufactured by Riken Vitamin Co., Ltd .: Riquemar SL900 (trade name)]
TMP: Trimethyl phosphate [manufactured by Daihachi Chemical Industry Co., Ltd .: TMP (trade name)]

[Examples 1 to 10, Comparative Examples 1 to 8]
The composition shown in Table 1 and Table 2 is used to prepare a preliminary mixture by uniformly mixing an aromatic polycarbonate resin, graphite, an organic sulfonate alkali (earth) metal salt, and other components using a tumbler. It supplied from the 1st supply port located in the screw root of an 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 with a hot air circulation dryer at 120 ° C. for 5 hours. After drying, a test piece for evaluation of flammability at a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 40 seconds using an injection molding machine (Toshiba Machine Co., Ltd .: IS-150EN), 3-stage sample plate and bending A test piece for elastic modulus evaluation was molded. The evaluation results are shown in Tables 1 and 2.

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

Claims (5)

(A) 100 parts by weight of thermoplastic resin (component A), (B) 5 to 100 parts by weight of graphite (component B) having an average particle size of 5 μm to 300 μm, (C) alkali (earth) metal salt of organic sulfonate (C component) The flame-retardant resin composition which consists of 0.001-1 weight part and does not contain carbon fiber .   The flame-retardant resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of (D) a fluorine-containing anti-dripping agent (D component) with respect to 100 parts by weight of the thermoplastic resin of component A.   The flame-retardant resin composition according to any one of claims 1 and 2, wherein the thermoplastic resin of component A is 50% by weight or more of 100% by weight of polycarbonate resin.   The flame retardant resin composition according to any one of claims 1 to 3, wherein 80% by weight or more of the B component graphite is scaly graphite out of 100% by weight.   The molded article for electronic components formed from the flame-retardant resin composition of any one of the said Claims 1-4.