JP2006257126A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a flame-retardant aromatic polycarbonate resin composition that comprises an aromatic polycarbonate resin and a rubber-modified resin as base materials, contains a flame retardant and has improved fluidity while maintaining heat resistance and mechanical properties. <P>SOLUTION: The flame-retardant aromatic polycarbonate resin composition comprises 100 parts wt. of the total of 20-99 parts wt. of the aromatic polycarbonate resin (component A) and 1-80 parts wt. of the rubber-modified resin (component B), 0.001-30 parts wt. of a flame retardant (component C) and 0.05-30 parts wt. of a fluidity modifier (component D). The rubber-modified resin (component B) is a rubber-like polymer or a combination of a rubber-like polymer and a styrene-based hard polymer except the component D and the fluidity modifier (component D) is a copolymer of a unit formed from a (meth)acrylic acid ester monomer (Da) represented by specific formula and an aromatic alkenyl compound monomer (Db) as a main constituent unit. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant aromatic polycarbonate resin composition having improved fluidity, comprising an aromatic polycarbonate resin, a rubber-modified resin and a flame retardant. More specifically, the present invention includes a flame retardant aromatic with improved fluidity without deteriorating mechanical properties typified by heat resistance and surface impact strength by incorporating a specific flow modifier. The present invention relates to a polycarbonate resin composition.

  Aromatic polycarbonate resins are widely used industrially because they have excellent mechanical and thermal properties. However, since the aromatic polycarbonate resin has a high melt viscosity, it has a drawback of poor flowability and poor moldability. Many polymer alloys with other thermoplastic resins have been developed to improve the flowability of aromatic polycarbonate resins. Among them, polymer alloys with rubber-modified resins typified by ABS resins and HIPS resins are widely used in the OA equipment field, the electronic / electrical equipment field, the automobile field, and the like. In addition, there is a strong demand for flame resistance of resin materials used mainly in applications such as office automation equipment and home appliances. In order to meet these demands, polymer alloys of aromatic polycarbonate resins and rubber-modified resins are also flame retardant. Many studies have been made.

  Conventionally, in such polymer alloys, it has been common to use a halogen-based flame retardant having bromine and a flame retardant aid such as antimony trioxide, but a halogen-based compound having bromine due to the generation of harmful substances during combustion. The study of flame retardants that do not contain benzene has become active. For example, many methods for adding organophosphorus flame retardants, organometallic salt flame retardants, and silicone flame retardants to polymer alloys of aromatic polycarbonate resins and ABS resins have already been proposed, and related knowledge is widely known. .

  For example, a method of blending triphenyl phosphate as a flame retardant organic phosphorus compound (Patent Document 1) or a method of blending a phosphate oligomer (Patent Document 2) with a polymer alloy of an aromatic polycarbonate resin and an ABS resin has been proposed. Yes.

  Both the method of blending the former triphenyl phosphate and the method of blending the latter phosphate oligomer are widely used because they have the effect of greatly improving the flame retardancy and the fluidity of the resin composition.

  Recently, however, products are becoming thinner and lighter, and there is an increasing demand for further improvement in moldability for such resin compositions. When improving the moldability of such a resin composition, a method of improving flowability while maintaining flame retardancy by increasing the amount of ABS resin and organophosphorus compound added is common. However, this method is accompanied by a decrease in mechanical properties and heat resistance typified by surface impact strength, and a method other than this method may be required.

Further, a method of blending an inorganic or organic metal salt flame retardant with a polymer alloy of polycarbonate resin and ABS resin (Patent Document 3), or a unit represented by the formula R ₂ SiO _1.0 and RSiO _1.5 in a non-silicone resin having an aromatic ring There are already methods for adding organometallic salt flame retardants and silicone flame retardants, such as a method of blending a silicone resin having a unit represented by formula (II) and having a weight average molecular weight of 10,000 to 270,000 (Patent Document 4). Many proposals have been made. Even when such a flame retardant is used, it is often difficult to improve fluidity while maintaining flame retardancy and surface impact strength.

  As a flow modifier for a polycarbonate resin, it is obtained by graft polymerization of a monomer constituting a polymer compatible or compatible with the polycarbonate resin in the presence of a polymer incompatible with the polycarbonate resin, It is known to use a thermoplastic resin composition having a mass-average molecular weight of a soluble component dissolved in chloroform of 10,000 to 100,000 (see Patent Document 5). According to this document, as a more specific embodiment, a flow modifier obtained by graft copolymerization of butyl acrylate with styrene and acrylonitrile is disclosed, and it is described that it has good compatibility without delamination.

  Further, it is composed of (meth) acrylic acid ester having a specific structure represented by phenyl methacrylate, a polymer unit composed of methyl (meth) acrylate, and a polymer unit composed of unsaturated nitrile and aromatic vinyl. It is known to use a copolymer as a compatibilizer between a polycarbonate resin and an ABS resin (see Patent Document 6).

  However, both methods improve fluidity and maintain surface impact characteristics in a resin composition comprising an aromatic polycarbonate resin, a rubber-modified resin typified by an ABS resin, and a flame retardant. In addition, it did not disclose knowledge effective for a flame retardant resin composition excellent in heat resistance.

JP-A-2-32154 JP-A-2-115262 JP-A 61-127759 Japanese Patent Laid-Open No. 10-139964 WO2003 / 072620 pamphlet JP-A-8-134144

  In view of the above, the object of the present invention is to maintain aromatic mechanical properties such as flame retardancy, heat resistance, and surface impact strength inherently containing an aromatic polycarbonate resin and a rubber-modified resin as a base and further containing a flame retardant. However, it is providing the flame-retardant aromatic polycarbonate resin group which has improved and has fluidity | liquidity. As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that such a purpose can be achieved by using a specific flow modifier, and further intensively studied to complete the present invention. It was.

  According to the present invention, the above-mentioned problems are 100 parts by weight in total of 20 to 99 parts by weight of the aromatic polycarbonate resin (component A) and 1 to 80 parts by weight of the rubber-modified resin (component B), and flame retardant (component C) 0. A flame retardant aromatic polycarbonate resin composition comprising 0.001 to 30 parts by weight and a flow modifier (D component) 0.05 to 30 parts by weight, wherein the rubber-modified resin (B component) Or a combination of a rubbery polymer and a styrenic hard polymer other than component D, and the flow modifier (component D) is (i) the following general formula (1) and / or (Ii) a copolymer having a main unit of a unit formed from a (meth) acrylic acid ester monomer (Da) and an aromatic alkenyl compound monomer (Db) represented by (ii) Of chloroform soluble components Weight average molecular weight is achieved by a flame retardant aromatic polycarbonate resin composition which is 10,000 to 200,000.

（式中、Ｒ^１は水素原子またはメチル基、Ｒ^２は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表し、ｎは１〜４の整数を表す。）

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )

  Hereinafter, the flame-retardant aromatic polycarbonate resin composition of the present invention may be simply referred to as a polycarbonate resin composition.

  The resin composition preferably further comprises 0.01 to 2 parts by weight of a fluorine-containing anti-dripping agent (E component) with respect to 100 parts by weight of the total of the A component and the B component. By such E component, the flame-retardant aromatic polycarbonate resin composition which has still more favorable flame retardance is achieved.

  The ratio of the monomer (Da) and the monomer (Db) in the D component is such that the total of both is 80% by weight or more in 100% by weight of the D component, It is preferable that Da) is 1 to 80% by weight and the monomer (Db) is 20 to 99% by weight.

  The monomer (Da) in the component D is preferably phenyl methacrylate, and the monomer (Db) in the component D is preferably styrene.

  In the resin composition, when the ratio of the rubber component of the rubbery polymer in the B component is br parts by weight and the ratio of the D component is d parts by weight, based on the total of 100 parts by weight of the A component and the B component 0.1 ≦ (br / d) ≦ 5 is preferably satisfied. This relationship is more preferably 1.05 ≦ (when the rubber-modified resin contains 10 parts by weight or more of a styrene-based hard polymer other than the D component, based on a total of 100 parts by weight of the A component and the B component. br / d) ≦ 5, more preferably 1.1 ≦ (br / d) ≦ 3. On the other hand, when the content of the styrenic hard polymer is less than 10 parts by weight, 0.1 ≦ (br / d) ≦ 0.95, more preferably 0.15 ≦ (br / d). ≦ 0.7.

  The above resin composition is 0.5 ≦ br ≦ 5 when the ratio of the rubber component of the rubber-like polymer in the B component is br parts by weight based on the total of 100 parts by weight of the A component and the B component. It is preferable. In such a range, the balance of flame retardancy, fluidity, and surface impact strength is particularly excellent.

  The component C is preferably at least one flame retardant selected from an organic phosphorus flame retardant, an organic metal salt flame retardant, and a silicone flame retardant.

  In particular, the C component flame retardant is an organophosphorus flame retardant represented by the following formula (3), and the ratio is 1 to 30 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. It is preferable.

（但し上記式中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ一価フェノールから誘導される一価の有機基を表し、ｎは０〜５の整数を表す。）

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a monovalent organic group derived from a monohydric phenol. And n represents an integer of 0 to 5.)

  Furthermore, it is preferable that this invention contains 0.1-100 weight part of reinforcement fillers (F component) further with respect to a total of 100 weight part of A component and B component. The content is more preferably 0.5 to 50 parts by weight, still more preferably 1 to 30 parts by weight. As the reinforcing filler (F component), silicate-based fillers such as talc, wollastonite and mica are preferably used. Of these, silicate minerals are particularly preferable, and talc, wollastonite, and mica are particularly preferable. Talc, wollastonite, and mica achieve a resin composition with good rigidity while suppressing a decrease in impact strength.

  Moreover, according to another aspect of the present invention, the above-mentioned problems include 20 to 99 parts by weight of an aromatic polycarbonate resin (component A), and a rubbery polymer or a styrenic hard polymer other than the rubbery polymer and the D component. A total of 100 parts by weight of 1 to 80 parts by weight of a rubber-modified resin (B component), and 0.001 to 30 parts by weight of a flame retardant (C component) and 0.05 to 30 parts of a flow modifier (D component) A method for producing a flame-retardant aromatic polycarbonate resin composition having improved flowability obtained by melt-kneading 30 parts by weight, wherein the flow modifier (E component) is the flow modifier (D component) Is mainly composed of units formed from the (meth) acrylic acid ester monomer (Da) and the aromatic alkenyl compound monomer (Db) represented by the above general formula (1) and / or (2). It is a copolymer as a structural unit , (Ii) a weight average molecular weight of chloroform-soluble component is achieved by the method for producing a flame retardant aromatic polycarbonate resin composition having improved fluidity 10,000 to 200,000.

Hereinafter, the details of the present invention will be described.
(Component A: aromatic polycarbonate resin)
The aromatic polycarbonate resin (component A) of the present invention is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation 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 (hereinafter sometimes abbreviated as “BPA”) is particularly preferred because of its excellent toughness, and is widely used.

  In the present invention, in addition to the general-purpose polycarbonate bisphenol A-based polycarbonate, a special polycarbonate produced using other dihydric phenols can be used 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 a polycarbonate resin by interfacial polymerization of the above dihydric phenol and carbonate precursor, a catalyst, a terminal terminator, an antioxidant for preventing the dihydric phenol from being oxidized, etc., as necessary. May be used. The polycarbonate resin of the present invention is a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) difunctional carboxylic acid. And a copolymer polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with the bifunctional carboxylic acid and the bifunctional alcohol together. Moreover, the mixture which mixed 2 or more types of the obtained polycarbonate resin may be sufficient.

  The branched polycarbonate resin increases the melt tension of the resin composition of the present invention, and can improve the molding processability in extrusion molding, foam molding and blow molding based on such properties. As a result, a molded product by these molding methods, which is superior in dimensional accuracy, is obtained.

  Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include 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, and 4- {4- [1,1- Trisphenol such as bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol is preferably exemplified. Other polyfunctional aromatic compounds include phloroglucin, phloroglucid, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene. And trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and acid chlorides thereof. Of these, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable, and 1,1,1-tris (4- Hydroxyphenyl) ethane is preferred.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate resin is 0 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. 0.03 to 1 mol%, preferably 0.07 to 0.7 mol%, particularly preferably 0.1 to 0.4 mol%.

Further, such a branched structural unit is not only derived from a polyfunctional aromatic compound but also derived without using a polyfunctional aromatic compound, such as a side reaction during a melt transesterification reaction. Also good. The ratio of such a branched structure can be calculated by ¹ H-NMR measurement.

  On the other hand, the aliphatic bifunctional carboxylic acid is preferably α, ω-dicarboxylic acid, and specific examples thereof include sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosane diacid. Examples thereof include linear saturated aliphatic dicarboxylic acids such as acids and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the bifunctional alcohol, an alicyclic diol is suitable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol. Further, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can also be used.

  The component A may be a mixture of two or more of polycarbonates having different dihydric phenol components, polycarbonates containing branched components, various polyester carbonates, polycarbonate-polyorganosiloxane copolymers, and the like. 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.

  The reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, and is carried out 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, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, 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 may be used. it can. Usually, the reaction temperature is preferably 0 to 40 ° C., the reaction time is preferably 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 stopper is usually used. Monofunctional phenols can be used as such end terminators. As a specific example of monofunctional phenols, monofunctional phenols are preferably used. As such monofunctional phenols, phenol, p-tert-butylphenol, p-cumylphenol and the like are preferable. In addition, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosyl. Phenol, docosylphenol, triacontylphenol, etc. can be mentioned. These end terminators may be used alone or in combination of two or more.

The reaction by the melt transesterification method is a transesterification reaction between a dihydric phenol and a carbonate ester. Usually, an alcohol produced by mixing a dihydric phenol and a carbonate ester while heating them in the presence of an inert gas, or 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 is in the range of approximately 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 for the reaction, for example, an alkali metal compound such as sodium hydroxide, potassium hydroxide, sodium salt or potassium salt of dihydric phenol; an alkali such as calcium hydroxide, barium hydroxide or magnesium hydroxide. Catalysts such as earth metal compounds; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, triethylamine; and the like can be used. In addition, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc. The catalyst used for the exchange reaction can be used. These catalysts may be used alone or in combination of two or more. The polymerization catalyst is usually used 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 the raw material dihydric phenol.

  In the melt transesterification method, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonylphenyl is used in the latter stage or after completion of the polycondensation reaction for the purpose of reducing phenolic end groups in the resulting polymer. Compounds such as phenyl carbonate can also be added. In the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator used is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. The aromatic polycarbonate after polymerization is used in a proportion of 0.01 to 500 ppm, preferably 0.01 to 300 ppm, more preferably 0.01 to 100 ppm. Suitable deactivators include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate, ammonium salts such as tetraethylammonium dodecylbenzyl sulfate, and the like.

  As the A component aromatic polycarbonate of the present invention, not only virgin raw materials but also polycarbonate resins regenerated from used products, so-called material-recycled aromatic polycarbonates, can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, an automotive headlamp lens, an optical recording medium, and the like are preferred as preferred embodiments because they satisfy the more preferable conditions of the viscosity average molecular weight. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

  The viscosity average molecular weight of the aromatic polycarbonate is preferably 10,000 to 50,000, more preferably 14,000 to 30,000, and still more preferably 18,000 to 25,000. In the range of 18,000 to 25,000, both excellent impact resistance and fluidity are excellent. Most preferably, it is 21,000-24,000. The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights.

  In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (50,000) increases the melt tension of the resin composition of the present invention, and molding processing in extrusion molding, foam molding and blow molding based on such characteristics. Can improve sex. Such an improvement effect is even better than the branched polycarbonate.

  As a more suitable aspect, the A component has a viscosity average molecular weight of 70,000 to 2,000,000 polycarbonate resin (A-3-1 component), and a viscosity average molecular weight of 10,000 to 30,000 polycarbonate resin (A A polycarbonate resin (A-3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as a “high molecular weight component-containing polycarbonate resin”). it can.

  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 300,000, 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 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 an aromatic polycarbonate resin showing a plurality of polymer peaks in a molecular weight distribution chart by GPC method, represented by the method shown in Japanese Patent Publication No. Gazette, in the same system, the aromatic polycarbonate resin of the present invention A- A method of producing so as to satisfy the conditions of one component, and (3) an aromatic polycarbonate resin obtained by such a production method (production method of (2)), a separately produced A-3-1 component and / or Examples thereof include a method of mixing the A-3-2 component.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., and the specific viscosity calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the drop time of methylene chloride, t is the drop time of the sample solution]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
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

(B component: rubber-modified resin)
The rubber-modified resin (component B) of the present invention is a rubbery polymer or a combination of a rubbery polymer and a styrenic hard polymer other than the D component. The rubbery polymer is a copolymer of a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower and a monomer component copolymerizable with the rubber component. A polymerized polymer. The styrene-based hard polymer is a polymer other than D component obtained by copolymerizing a polymer or copolymer of an aromatic alkenyl compound, or other vinyl monomers copolymerizable therewith. When the polymer is amorphous, the polymer has a glass transition temperature of 40 ° C. or higher. When the polymer is crystalline, the melting point is 40 ° C. or higher. Refers to coalescence. Such glass transition temperature and melting point can be determined by differential scanning calorimetry (DSC) measurement based on JIS K7121. The structural unit formed from the aromatic alkenyl compound is preferably contained in at least 30% by weight or more in 100% by weight of the styrenic hard polymer. The structural unit formed from the aromatic alkenyl compound is more preferably 40 to 90% by weight, particularly preferably 50 to 80% by weight.

  The rubber component is a polymer having rubber elasticity which becomes a base of a rubbery polymer. Examples of such rubber components include polybutadiene, polyisoprene, and diene copolymers (for example, random and block copolymers of styrene / butadiene, acrylonitrile / butadiene copolymers, and acrylic / butadiene rubbers (alkyl acrylates). Ester or methacrylic acid alkyl ester and butadiene copolymer), copolymers of ethylene and α-olefin (eg, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers). And block copolymers), copolymers of ethylene and unsaturated carboxylic acid esters (such as ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (For example, Ethylene / vinyl acetate copolymer), ethylene / propylene and non-conjugated diene terpolymer (eg, ethylene / propylene / hexadiene copolymer), acrylic rubber (eg, polybutyl acrylate, poly (2-ethylhexyl acrylate), And a copolymer of butyl acrylate and 2-ethylhexyl acrylate), and silicone rubber (for example, polyorganosiloxane rubber, IPN type rubber comprising a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component; And rubber having a structure in which the two rubber components are entangled with each other so that they cannot be separated, and an IPN type rubber composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component. Still other rubber components include urethane rubber, amide rubber, phosphazene rubber, and fluorine rubber.

  Preferred examples of the monomer copolymerized with the rubber component include aromatic alkenyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds. Other monomer components include epoxy group-containing methacrylates such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride Examples include α, β-unsaturated carboxylic acids such as acid, phthalic acid, and itaconic acid, and anhydrides thereof.

  Examples of the aromatic alkenyl compound include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, vinyl naphthalene, and methoxy styrene. Styrene is particularly preferred. These may be used alone or in combination of two or more.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. These may be used alone or in combination of two or more.

  Specific examples of the (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and amyl (meth) acrylate. , Hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate And so on. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included.

  More specifically, the rubbery polymer in the present invention includes SB (styrene-butadiene) polymer, ABS (acrylonitrile-butadiene-styrene) polymer, MBS (methyl methacrylate-butadiene-styrene) polymer, MABS (methyl). Methacrylate-acrylonitrile-butadiene-styrene polymer, MB (methyl methacrylate-butadiene) polymer, ASA (acrylonitrile-styrene-acrylic rubber) polymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) polymer, MA (methyl methacrylate) -Acrylic rubber) polymer, MAS (methyl methacrylate-acrylic rubber-styrene) polymer, methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber Styrene copolymer, methyl methacrylate - and the like (acrylic silicone IPN rubber) polymer. The rubbery polymer is not particularly limited in its structure, but a graft polymer and a block polymer are generally used, and a graft polymer is more preferable.

  Other rubbery polymers include thermoplastic elastomers such as styrene elastomers such as hydrogenated styrene-butadiene block copolymers, polyester elastomers, polyurethane elastomers, and polyamide elastomers, polyethylene, polyorganosiloxane, and olefins. Examples include copolymers with saturated carboxylic acid esters, which are widely known as impact modifiers in the impact resistance of aromatic polycarbonate resins and as impact modifiers in aromatic polycarbonate-based polymer alloys. It is.

  When a graft copolymer is produced in a rubbery polymer, the graft copolymer and a polymer or copolymer of a graft component not grafted to the rubber component (for example, an AS polymer in the case of an ABS polymer) Often a mixture is obtained. Such a mixture is often marketed as a graft copolymer and is easily available. Therefore, in the present invention, the rubber-modified resin may be used in the production of the resin composition of the present invention as a rubber polymer and a styrene hard polymer as independent raw materials. What united unity may be used as a raw material at the time of manufacture of this resin composition.

  The rubbery polymer of the present invention may be produced by any polymerization method of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. There is no problem. Moreover, the mixture with the copolymer of only the graft component byproduced in the case of manufacture may be sufficient. Furthermore, examples of the polymerization method include a general emulsion polymerization method, a soap-free polymerization method using an initiator such as potassium persulfate, a seed polymerization method, and a two-stage swelling polymerization method. In the suspension polymerization method, the aqueous phase and the monomer phase are individually maintained, both are accurately supplied to the continuous disperser, and the particle diameter is controlled by the rotation speed of the disperser, and the continuous production is performed. In the method, a method may be used in which the monomer phase is supplied by passing it through a fine orifice having a diameter of several to several tens of μm or a porous filter in an aqueous liquid having dispersibility to control the particle size. In the case of a core-shell type graft polymer, the reaction may be one stage or multistage for both the core and the shell.

  Such rubbery polymers are commercially available and can be easily obtained. A rubbery polymer in which an alkyl acrylate component typified by methyl methacrylate is copolymerized in the shell portion is likely to be selectively present in the aromatic polycarbonate resin matrix even in the presence of a styrenic hard polymer. This contributes to an improvement in impact properties of the entire resin composition. Examples of the rubbery polymer in which the alkyl acrylate component is copolymerized include, for example, a butadiene rubber, an acrylic rubber, or a butadiene-acrylic composite rubber as a rubber component. B-56 etc.), Mitsubishi Rayon Co., Ltd. Metabrene C series (eg C-223A etc.), W series (eg W-450A etc.), Kureha Chemical Industry Co., Ltd. Paraloid EXL series (eg EXL-2602 etc.) , HIA series (eg, HIA-15), BTA series (eg, BTA-III), KCA series, Rohm & Haas Paraloid EXL series, KM series (eg, KM-336P, KM-357P, etc.), Ube UCL Modification of Saikon Co., Ltd. -Resin series (UMG AXS resin series of UMG ABS Co., Ltd.) is listed, and those that are mainly composed of acrylic-silicone composite rubber as the rubber component are called Metabrene S-2001 or SRK-200 from Mitsubishi Rayon Co., Ltd. What is marketed with a brand name is mentioned.

  These rubbery polymers may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but are particularly preferably produced by emulsion polymerization.

  The ratio of the rubber component in the rubber polymer is preferably 40 to 90% by weight, more preferably 60 to 85% by weight, and particularly preferably 70 to 85% by weight in 100% by weight of the rubber polymer. Further, the rubber particle diameter in the rubbery polymer is preferably 0.05 to 2 μm in terms of weight average particle diameter, and the distribution of the rubber particle diameter is either a single distribution or one having a plurality of peaks. Can be used. The rubber particle diameter in the rubbery polymer in which the alkyl acrylate component is copolymerized is more preferably 0.1 to 1.0 μm, still more preferably 0.1 to 0.5 μm.

  On the other hand, representative examples of the rubber-modified resin of the present invention include ABS resin, AES resin, and ASA resin, which are also widely used. Here, the ABS resin is a copolymer resin mainly composed of acrylonitrile, polybutadiene (or styrene-butadiene) rubber, and styrene, and the AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene, an ASA resin. Is a copolymer resin mainly composed of acrylonitrile, styrene, and acrylic rubber. These resins usually consist of a mixture of each rubbery polymer and a styrene-based hard polymer of acrylonitrile-styrene copolymer (AS copolymer).

The free AS copolymer has a molecular weight of preferably 40,000 to 500,000, preferably 70,000 to 200,000, expressed by a weight average molecular weight (Mw) calculated by GPC measurement (gel permeation chromatography measurement). 000 is more preferable, and 80,000 to 160,000 is still more preferable. In addition, the weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line by standard polystyrene resin. Further, the proportion of the graft polymer component grafted to the rubber component of the rubber polymer in the ABS resin, AES resin, and ASA resin in 100% by weight of the AS copolymer (the graft component relative to the weight of the diene rubber component) % Of the weight), that is, the graft ratio (% by weight) is preferably 20 to 200%, more preferably 20 to 80%.

  Such ABS resin, AES resin, and ASA resin may be produced by any method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In particular, for the ABS resin, an ABS resin produced by a bulk polymerization method is preferable because of excellent thermal stability. Further, as such bulk polymerization method, typically, the continuous bulk polymerization method (so-called Toray method) described in Chemical Engineering, Vol. 48, No. 6, page 415 (1984), and Chemical Engineering, Vol. 53, No. 6, page 423 (1989). ) Is a continuous bulk polymerization method (so-called Mitsui Toatsu method). Any ABS resin is preferably used as the ABS resin of the present invention. In particular, the latter ABS resin by the continuous bulk polymerization method is particularly excellent in thermal stability and moist heat resistance, there is little reduction in impact strength during molding under a high thermal history, and it is also excellent in long-term characteristics of various characteristics. Is obtained. The copolymerization method may be copolymerized in a single stage or in multiple stages.

  The rubber particle diameter of the rubber polymer in the ABS resin, AES resin, and ASA resin is preferably 0.05 to 5 μm, more preferably 0.1 to 2.0 μm, and more preferably 0.2 to 1.5 μm in weight average particle diameter. Is more preferable. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  A rubber-modified resin in which a rubbery polymer such as an ABS resin and a styrene-based hard polymer are combined has excellent molding processability for a thin molded product, and also has good impact resistance. On the other hand, a rubber-modified resin substantially made of a rubbery polymer such as an MBS copolymer gives the resin composition good impact resistance against a thin molded article. Taking these into consideration, the rubber-modified resin can be appropriately adjusted.

(C component: flame retardant)
As the flame retardant (component C) of the present invention, various compounds conventionally known as flame retardants for aromatic polycarbonate resins can be applied. More preferably, (i) an organophosphorous flame retardant (for example, a monophosphate compound, Phosphate oligomer compounds, (ii) organometallic salt flame retardants (eg, alkali (earth) metal sulfonates, borate metal stannate flame retardants, metal stannate flame retardants, etc.), phosphonate oligomer compounds, phospho Nitrile oligomeric compounds and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogen flame retardants (eg brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (oligomers) Etc.), brominated polyacrylates, chlorinated polyethylene, etc.) And the like. 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 property, fluidity, rigidity, and thermal stability based on the properties of each compound.

Among these flame retardants, (i) organophosphorous flame retardants, (ii) organometallic salt flame retardants, and (iii) silicone flame retardants composed of silicone compounds are preferred.
(Ci) Organophosphorus Flame Retardant As the organophosphorus flame retardant of the present invention, an aryl phosphate compound is suitable. Such a phosphate compound is effective in improving flame retardancy, and since the phosphate compound has a plasticizing effect, it is advantageous in that the molding processability of the resin composition of the present invention can be improved although the heat resistance is lowered. is there. As the phosphate compound, various phosphate compounds known as conventional flame retardants can be used, and more preferably, one or more phosphate compounds represented by the following general formula (3) can be mentioned.

（但し上記式中のＸは、二価フェノールから誘導される二価の有機基を表し、Ｒ^１１、Ｒ^１２、Ｒ^１３、およびＲ^１４はそれぞれ一価フェノールから誘導される一価の有機基を表し、ｎは０〜５の整数を表す。）

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a monovalent organic group derived from a monohydric phenol. And n represents an integer of 0 to 5.)

  The phosphate compound of formula (3) may be a mixture of compounds having different n numbers, and in the case of such a mixture, the average n number is preferably 0.5 to 1.5, more preferably 0.8. To 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

  Preferable specific examples of the dihydric phenol for deriving X include hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxyphenyl) ketone and bis (4-hydroxyphenyl) sulfide are exemplified, among which resorcinol, bisphenol A, and dihydroxydiphenyl are preferable.

Preferable specific examples of the monohydric phenol for deriving R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ include phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol. Are phenol and 2,6-dimethylphenol.

Such a monohydric phenol may substitute a halogen atom. Specific examples of the phosphate compound having a group derived from the monohydric phenol include tris (2,4,6-tribromophenyl) phosphate and tris. Examples include (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like.
On the other hand, specific examples of phosphate compounds not substituted with halogen atoms include monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate, and resorcinol bisdi (2,6-xylyl) phosphate). Preferred are phosphate oligomers mainly composed of phosphate oligomers, phosphate oligomers mainly composed of 4,4-dihydroxydiphenylbis (diphenyl phosphate), and phosphate oligomers mainly composed of bisphenol A bis (diphenyl phosphate). Indicates that a small amount of other components having different degrees of polymerization may be contained, and more preferably, the component of n = 1 in the above formula (4) is 80% by weight or more, more preferably 85% by weight or more, still more preferably Containing 90% by weight or more Show.).

(C-ii) 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 compounding 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 100 parts by weight of the total of component A and component B. More preferably, it is 0.008-0.13 weight part. The effect (for example, flame retardancy, antistatic property, etc.) expected by blending the fluorine-containing organic metal salt is exhibited as the preferable range is reached.

  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 such an aromatic sulfonate alkali (earth) metal salt is blended, its content is preferably 0.001 to 1 part by weight, more preferably based on 100 parts by weight of the total of component A and component B, more preferably 0.005 to 0.5 part by weight, more preferably 0.01 to 0.1 part by weight.

(C-iii) 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 organic residues 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.

  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 (4) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（４）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（４）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (4), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (4), n is 2) In these cases, different types of X can be taken.)

  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.

  As the silicone compound having a Si—H group, a silicone compound containing at least one of structural units represented by the following general formulas (5) and (6) is preferably exemplified.

（式（５）および式（６）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（７）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（５）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (5) and formula (6), 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 (7). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and in formula (5), when m1 is 2 or more, the repeating unit is a plurality of different repeating units. Can take units.)

（式（７）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。ｍ２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ｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (7), Z ^{4 to} Z ⁸ each independently represent 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 an integer of 0 or 1. Further, in the formula (7), when m2 is 2 or more, the repeating unit can take a plurality of repeating units.

  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 (8) and the general formula (9).

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

(In Formula (8), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

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

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

  The blending amount of the silicone-based flame retardant is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, and still more preferably 1 based on a total of 100 parts by weight of the component A and the component B. ~ 5 parts by weight.

(D component: flow modifier)
The flow modifier (D component) of the present invention comprises (i) a (meth) acrylate monomer (Da) represented by the following general formula (1) and / or (2) and an aromatic alkenyl compound. A copolymer having a unit formed from the monomer (Db) as a main constituent unit, and (ii) the chloroform-soluble component has a weight average molecular weight of 10,000 to 200,000. is there.

（式中、Ｒ^１は水素原子またはメチル基、Ｒ^２は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

（式中、Ｒ^３は水素原子またはメチル基、Ｒ^４は炭素環基自体であるか、または炭素環を結合した炭素鎖からなる炭化水素基を表し、ｎは１〜４の整数を表す。）

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )

  In the flow modifier of the present invention, it is preferable that all monomer components are contained in a copolymer of the monomer (Da) and the monomer (Db). However, in the production of a copolymer, it is inevitable that a polymer composed of not only one monomer but also a monomer (Da) or monomer (Db) is formed in the present invention. A homopolymer may be included. This is because such a homopolymer has good compatibility with the copolymer and acts as a unit on the polycarbonate resin.

  In the flow modifier (D component) of the present invention, the ratio of the monomer (Da) and the monomer (Db) is 100% by weight of the D component in consideration of the balance between fluidity and mechanical properties. % Is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more. Further, in the total of 100% by weight of both, the monomer (Da) is preferably 1 to 80% by weight. And the monomer (Db) is 20 to 99% by weight, more preferably the monomer (Da) is 3 to 50% by weight and the monomer (Db) is 50 to 97% by weight, still more preferably The monomer (Da) is 5 to 30% by weight and the monomer (Db) is 70 to 95% by weight, most preferably the monomer (Da) is 5 to 20% by weight and the monomer (Db). Is 80 to 95% by weight.

  When the amount of the monomer (Da) is less than the lower limit of the above range, it is difficult to achieve improvement in delamination or compatibility with the flow reforming effect. When the amount of the monomer (Da) exceeds the upper limit of the above range, it is difficult to obtain a fluid reforming effect and the mechanical properties may be deteriorated.

  Moreover, it is preferable that all the copolymer of a monomer (Da) and a monomer (Db) is a non-crosslinked copolymer. For example, when 10 ml of chloroform and 1 g of a flow modifier (component D) are stirred and mixed for 30 minutes, it is preferable that a crosslinked structure insoluble in chloroform is not observed. However, as long as the properties of excellent fluidity modification are not impaired, all of the copolymers need not be non-crosslinked, and some crosslinked structures insoluble in organic solvents such as chloroform and acetone exist. There is no particular problem.

  In the copolymer of component D, the weight average molecular weight of the chloroform-soluble component excluding a part of the solvent-insoluble crosslinked structure is 10,000 to 200,000. Such molecular weight keeps a good balance between formability and physical properties such as heat resistance and impact resistance.

  Such molecular weight is calculated by GPC (gel permeation chromatography) measurement under the following conditions. That is, GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, and two columns of ResiPore (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories were connected in series as a column, and chloroform as a mobile phase. Polymer Laboratories' Easy Cal PS-2 as a standard substance, and a photodiode array detector at a wavelength of 254 nm as a detector, chloroform as a developing solvent, and a solution of 10 mg of sample dissolved in 5 ml of chloroform, 100 μl is injected into the GPC measurement apparatus, and the measurement is performed under conditions of a column temperature of 40 ° C. and a flow rate of 1 ml / min.

  From the obtained results, the molecular weight is calculated from the peak in a range excluding the peak corresponding to the monomer and dimer which are difficult to be called a copolymer. Under the above conditions, since these peaks to be excluded are detected at a retention time of 20 minutes or later, the molecular weight is calculated from the peaks up to 20 minutes.

  In the weight average molecular weight of the flow modifier of the present invention, a more preferable lower limit is 20,000, further preferably 30,000, and most preferably 40,000. Moreover, the upper limit with more preferable this weight average molecular weight is 150,000, More preferably, it is 140,000, Most preferably, it is 130,000. The soluble component in chloroform is mainly composed of a non-crosslinked copolymer composed of the monomer (Da) and the monomer (Db). A polymer of a monomer (Da) or a monomer (Db) may be included.

  When the weight-average molecular weight of the soluble component is less than 10,000, relatively low molecular weight substances are increased, which may reduce various functions such as heat resistance and rigidity. In addition, there is a risk that problems such as smoke generation, mist, mechanical contamination, and appearance defects such as fish eyes during molding may increase.

  On the other hand, when the weight average molecular weight is larger than 200,000, the melt viscosity of the flow modifier itself increases, and a sufficient fluidity modifying effect may not be obtained.

  Moreover, in the flow modifier of the present invention, it is preferable to use one having a melt viscosity of 300 Pa · s or less.

  The melt viscosity is a melt viscosity measured using a capillary rheometer under the conditions of nozzle D = 1 mm, L / D = 16, barrel temperature = 170 ° C., and shear rate = 3000 seD−1.

  The copolymer of component D may be any of a random copolymer, a block copolymer, and a graft copolymer, or a mixture thereof. The random copolymer is more preferable in the present invention in that the refractive index of the copolymer is uniform even at a micro level and that it can be produced relatively easily. In the block copolymer, when the polymer unit of the monomer (Da) is A and the polymer unit of the monomer (Db) is B, AB type, ABA type, B Any block copolymer such as -A-B type and A-B-A-B type may be used. Furthermore, when the random copolymer unit of the monomer (Da) and the monomer (Db) is AB, a block copolymer in which either A or B is substituted with AB may be used. . Further, in the graft copolymer, a copolymer in which the polymer unit B is grafted to the polymer unit A, a copolymer in which the polymer unit A is grafted to the polymer unit B, and either A or B is AB. Any of the graft copolymers having a structure substituted by

  The method for producing the copolymer of component D is not particularly limited, and it is represented by radical polymerization such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization, various living anion polymerizations, and use of TEMPO. Living radical polymerization methods such as nitroxide-mediated radical polymerization, radical polymerization using reversible addition-fragmentation chain transfer agent (RAFT), and atom transfer radical polymerization (ATRP) can be used.

  Hereinafter, as a preferred method for producing the flow modifier of the present invention, a method for synthesizing a copolymer by an emulsion radical polymerization method will be described.

(Synthesis of copolymer by emulsion radical polymerization)
Examples of the method for synthesizing a copolymer by the emulsion radical polymerization method include water, an emulsifier, a (meth) acrylate monomer (Da) represented by the general formula (1) and / or (2), and aromatic. A copolymer is added to the alkenyl compound monomer (Db) and optionally a mixture of other monomers, a polymerization initiator, a chain transfer agent, etc., if necessary, and polymerization is carried out at a high temperature to obtain a copolymer. Is synthesized.

  Examples of the emulsifier include nonionic emulsifiers, anionic emulsifiers, cationic emulsifiers, and zwitterionic emulsifiers.

  Specific examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, dialkylphenoxy poly (ethyleneoxy) ethanol, polyvinyl alcohol, polyacrylic acid, and alkyl cellulose.

  Specific examples of the anionic emulsifier include fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, sulfates of aliphatic amines and aliphatic amides, fatty alcohol phosphates, dibasic fatty acid esters. Examples thereof include sulfone salts, fatty acid amide sulfonates, alkylaryl sulfonates, and naphthalene sulfonates of formalin condensates.

Specific examples of the cationic emulsifier include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts.
Specific examples of the zwitterionic emulsifier include alkylbetaines.

  The (meth) acrylic acid ester monomer (Da) represented by the general formula (1) and / or (2) is a carbocyclic ring in the molecule, that is, a carbocyclic ring itself, or a carbon bonded to a carbocyclic ring. It contains a hydrocarbon group consisting of a chain. The carbocycle may be an alicyclic ring such as a cyclohexane ring or an aromatic ring such as a benzene ring and a naphthalene ring. These carbocycles may be substituted with an alkyl group. In the present invention, the notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included.

  Specific examples of the (meth) acrylic acid ester represented by the general formulas (1) and (2) include cyclohexyl (meth) acrylate, 3,4,5-trimethylcyclohexyl (meth) acrylate, and 4-tert-butylcyclohexyl. (Meth) acrylate, cyclohexylmethyl (meth) acrylate, 3-cyclohexylpropyl (meth) acrylate, 2-cyclohexylpropyl (meth) acrylate, phenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, 4-tert-butyl Phenyl (meth) acrylate, benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 1-phenylethyl (meth) acrylate, 2-phenylethyl (meth) acrylate, 3-phenylpropyl (meth) ) Acrylate, 2-phenylpropyl (meth) acrylate, 2-naphthyl (meth) acrylate, cyclohexoxymethyl (meth) acrylate, 2-cyclohexoxyethyl (meth) acrylate, 3-cyclohexoxypropyl (meth) acrylate, 3, 4,5-trimethylcyclohexoxymethyl (meth) acrylate, 2- (3,4,5-trimethylcyclohexoxy) ethyl (meth) acrylate, 3- (3,4,5-trimethylcyclohexoxy) propyl (meth) acrylate 4-tert-butylcyclohexoxymethyl (meth) acrylate, 2- (4-tert-butylcyclohexoxy) ethyl (meth) acrylate, 3- (4-tert-butylcyclohexoxy) propyl (meth) acrylate, Xymethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-phenoxypropyl (meth) acrylate, 2-phenoxypropyl (meth) acrylate, 4-tert-butylphenoxymethyl (meth) acrylate, 2- (4- tert-Butylphenoxy) ethyl (meth) acrylate, 3- (4-tert-butylphenoxy) propyl (meth) acrylate, 3,4-dimethylphenyl (meth) acrylate, 3,4,5-trimethylphenyl (meth) acrylate 4-methylphenoxymethyl (meth) acrylate, 2- (4-methylphenoxy) ethyl (meth) acrylate, 3- (4-methylphenoxy) propyl (meth) acrylate, 2- (4-methylphenoxy) propyl (meth) Acryle 2-naphthoxymethyl (meth) acrylate, 2- (2-naphthoxy) ethyl (meth) acrylate, and 3- (2-naphthoxy) propyl (meth) acrylate, 2- (2-naphthoxy) propyl (meth) ) Acrylate and the like, and these may be used alone or in combination of two or more.

  Among these, in the present invention, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, benzyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 4-tert-butyl Cyclohexyl (meth) acrylate, 4-tert-butylphenyl (meth) acrylate, cyclohexoxymethyl (meth) acrylate, 2-cyclohexoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, and 2-phenoxyethyl (meth) Acrylates are preferred, cyclohexyl methacrylate and phenyl methacrylate are more preferred, and phenyl methacrylate is particularly preferred.

  The copolymer of component D of the present invention is mainly a (meth) acrylic acid ester monomer (Da) and an aromatic alkenyl compound monomer (Db) represented by the general formula (1) and / or (2). However, other copolymerizable monomers may be used in combination as necessary. Examples of such monomers include alkyl (meth) acrylates having an alkyl group having 2 to 20 carbon atoms such as methyl (meth) acrylate and ethyl (meth) acrylate, and vinyl cyanide compounds. These can be used alone or in combination of two or more. Still other copolymerizable monomers include amino groups, hydroxy groups, mercapto groups, carboxylic acids such as maleic anhydride, (meth) acrylic acid, glycidyl (meth) acrylate, and hydroxyethyl (meth) acrylate. It may be a monomer containing various functional groups such as an acid group, a carboxylic acid anhydride, a dicarboxylic acid, a halogen group, and a carbonyl halide.

  A monomer having two or more unsaturated groups can be used as a copolymerizable monomer. By using such a monomer, a macromonomer having one or more unsaturated double bonds at the side chain or terminal of the polymer is synthesized, and the other monomer is polymerized in the presence thereof to graft copolymer. A polymer can be produced.

  Specific examples of the monomer having two or more unsaturated groups include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, Examples thereof include 1,3-butylene glycol di (meth) acrylate and 1,4-butylene glycol di (meth) acrylate. In consideration of the fluidity of the polycarbonate resin composition, monomers having two or more unsaturated groups having different reactivities such as allyl (meth) acrylate, triallyl cyanurate, and triallyl isocyanurate are preferable. Triallyl cyanurate and triallyl isocyanurate have three allyl groups, but the reactivity of the allyl group that reacts first is different from the reactivity of the allyl group that reacts second and third. Allyl (meth) acrylate is particularly preferable.

  Examples of the polymerization initiator include peroxides such as tert-butyl hydroperoxide and cumene hydroperoxide, azo initiators such as azobisisobutyronitrile, and redox in which an oxidizing agent and a reducing agent are combined. A system initiator is mentioned.

  Specific examples of redox initiators include sulfoxylate initiators in which ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, and hydroperoxide are combined.

  Examples of the chain transfer agent include n-octyl mercaptan and tert-dodecyl mercaptan.

  The chain transfer agent is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 1.5 parts by weight per 100 parts by weight of the total of the monomers forming the D component copolymer.

  Examples of the aromatic alkenyl compound monomer (Db) include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl xylene, ethyl styrene, dimethyl styrene, p-tert-butyl styrene, and vinyl naphthalene. In particular, styrene and α-methylstyrene, particularly styrene, is preferably 90% by weight or more in 100% by weight of the monomer (Db). In a most preferred embodiment, the total amount of the monomer (Db) is styrene.

  If the molecular weight distribution of the copolymer of component D is too wide, the flowability of the resin composition will be lowered, or relatively low molecular weight substances will be increased, so that heat resistance and thermal stability will be reduced, smoke generation during molding, mist There is a high possibility that problems such as mechanical stains and poor appearance such as fish eyes will occur. Therefore, the molecular weight distribution expressed by weight average molecular weight / number average molecular weight (Mw / Mn) is preferably 1-30. The upper limit is more preferably 10, and still more preferably 3. In addition, the calculation method of this molecular weight is based on the above-mentioned GPC measurement. The lower limit is practically preferably 1.3, more preferably 1.8. Further, within the range in which the molecular weight of the copolymer is measured, the peak of the molecular weight distribution by GPC measurement may be single or plural. A copolymer having a single peak is preferable because it can be easily produced.

  Moreover, it is preferable that the refractive index (nd) of the copolymer of D component is 1.52-1.60, More preferably, it is the range of 1.565-1.59. In particular, the difference in refractive index from the refractive index (nd) of the polycarbonate resin of component A is preferably adjusted to within 0.015, particularly within 0.01.

  An embodiment in which the D component is a graft copolymer will be described. A preferred embodiment when the D component of the present invention is a graft copolymer is a graft copolymer obtained by graft polymerization of the monomer (Db) in the presence of the polymer formed from the monomer (Da). A graft copolymer obtained by graft polymerization of a monomer (Da) in the presence of a polymer or a polymer formed from the monomer (Db). In any embodiment, such a graft copolymer may be produced using a macromonomer formed from the monomer (Da) or a macromonomer formed from the monomer (Db) as described above. preferable.

  In such a macromonomer, in consideration of the balance of fluidity, impact resistance, and delamination resistance, it has two or more unsaturated groups with respect to 100 parts by weight of the monomer (Da) or the monomer (Db). More preferably, the monomer content is 0.7 to 5 parts by weight, and still more preferably 0.8 to 3 parts by weight. When the amount of the monomer having two or more unsaturated groups is less than 0.5 parts by weight, the macromonomer may not form a necessary and sufficient graft bond with the monomer (Db). When the content of one or more monomers is too large, the proportion of the crosslinked structure insoluble in the organic solvent increases, and the excellent fluidity improving effect is impaired.

  The production of such a macromonomer can be performed according to the production of the copolymer. In the polymerization system of the obtained macromonomer, a mixture containing a monomer to be grafted and, if necessary, other monomers copolymerizable with the monomer, a polymerization initiator, a chain transfer agent, and the like is supplied. The polymerization is carried out at a high temperature.

  As the polymerization initiator, chain transfer agent and the like, the same ones as described in the production of the copolymer can be applied.

  The above is basically a case where a macromonomer is a trunk and a polymer unit formed from a monomer to be grafted is a branch, but only a macromonomer having an unsaturated double bond at the terminal is used. The macromonomer is a branch, and a polymer unit formed from the monomer is a trunk.

(E component: fluorine-containing anti-dripping agent)
The fluorine-containing anti-drip agent (E component) used in the present invention is a polytetrafluoroethylene having a fibril-forming ability, which is used to prevent melt dripping during combustion and further improve flame retardancy. Polytetrafluoroethylene having a forming ability is preferably used. Hereinafter, polytetrafluoroethylene may be simply referred to as PTFE. PTFE having a fibril forming ability has a very high molecular weight, and tends to be bonded 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 from Daikin Chemical Industries, and F-201L. . Commercially available aqueous dispersions of PTFE include: Fullon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers Co., Ltd. Fullon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro A typical example is Teflon (registered trademark) 30J manufactured by Chemical 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 then a vinyl monomer is further polymerized in the mixed dispersion, and then a mixture is obtained (described in JP-A-11-29679, etc.). Those obtained by (Method) can be used. Commercially available products of PTFE in these mixed forms include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

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

  The content of the fluorine-containing anti-dripping agent (component E) is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1 part by weight, based on a total of 100 parts by weight of the component A and the component B. Preferably it is 0.1-0.6 weight part.

(F component: reinforcing filler)
In the present invention, various reinforcing fillers can be included as the F component. Such reinforcing fillers include, for example, talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fiber, glass beads, glass balloon, glass milled fiber, glass flake, carbon fiber, carbon flake. , Carbon beads, carbon milled fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, ceramic balloon, aramid particle, aramid fiber, polyarylate fiber, Examples of the whisker include graphite, potassium titanate whisker, aluminum borate whisker, and basic magnesium sulfate. Of these, silicate fillers such as talc, wollastonite, mica, glass fiber, and glass milled fiber are preferably used. Of these, talc, wollastonite and mica are particularly preferred. These reinforcing fillers may be used alone or in combination of two or more.

  In the present invention, wollastonite having a number average fiber diameter of 0.5 to 5 μm is preferable. The number average fiber diameter is obtained by measuring a total of 1000 fiber diameters randomly extracted from an image observed with an electron micrograph and calculating the number average value. Moreover, the aspect ratio L / D (L: number average fiber length, D: number average fiber diameter) is preferably 5 or more, and more preferably 6 or more. The number average fiber length is calculated by observing wollastonite with an optical microscope or an electron microscope at a magnification at which the entire image of wollastonite can be observed almost completely, and inputting the image into an image analyzer. be able to. Examples of the image analysis apparatus include PIAS-III system made by Pierce. As wollastonite used in the present invention, the loss on ignition at 1000 ° C. is preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1% by weight or less.

  Furthermore, examples of talc suitable in the present invention include those having an average particle diameter of 5 μm or less. More preferred are those having an average particle size of 3 μm or less, particularly preferably 2 μm or less. An example of the lower limit is 0.05 μm. Here, the average particle diameter of talc refers to D50 (median diameter of particle diameter distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  Talc is preferably used in a granulated form. As a granulation method, there are a case where a binder is used and a case where it is not substantially used. What does not use a binder is more suitable. As a granulation method when a binder is not used, a degassing compression method (for example, a method of performing roller compression with a briquetting machine while degassing in a vacuum state), a rolling granulation method or an agglomeration granulation method Etc.

  Suitable mica in the present invention may be in the form of a powder having an average particle size of 1 to 80 μm. More preferably, an average particle diameter of 2-50 micrometers can be mentioned. The average particle diameter is a value measured by a laser diffraction / scattering method. When the average particle size is 1 to 80 μm, the flame retardancy is better and the fine dispersion condition in the resin is satisfied. As the thickness of mica, one having a thickness measured by observation with an electron microscope of 0.01 to 1 μm can be used. The thickness is preferably 0.03 to 3 μm. Further, such mica may be surface-treated with a silane coupling agent or the like, and further granulated with a binder such as epoxy, urethane or acrylic, and may be granulated.

  When the reinforcing filler is blended, the flame-retardant thermoplastic resin composition of the present invention can contain a surface coating lubricant for suppressing the bending of the reinforcing filler and improving the thermal stability of the resin composition. The folding inhibitor inhibits adhesion between the matrix resin and the reinforcing filler, reduces stress acting on the reinforcing filler during melt kneading, and suppresses filler folding. The effects of the surface coating lubricant include (I) improved rigidity (increases the filler aspect ratio), (II) improved toughness (easily exerting the toughness of the matrix resin, especially an aromatic polycarbonate resin with particularly good toughness) And (III) improved thermal stability, and (IV) improved conductivity (in the case of a conductive filler). Such a surface coating lubricant includes (i) a lubricant containing a functional group having reactivity with a silicate mineral, and (ii) a lubricant whose surface has been previously coated on the silicate mineral. Accordingly, among the above-mentioned surface treatment agents for silicate minerals, those having a lubricant effect act as a surface coating lubricant. A suitable surface coating lubricant is an acidic group-containing lubricant or an alkylalkoxysilane or alkylhydrogensilane having an alkyl group having 60 or less carbon atoms.

  The number of carbon atoms in the alkyl group of such a silane compound is preferably 4 or more. Furthermore, such carbon number is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less. The alkyl group in such a silane compound is preferably 1 or 2, particularly preferably 1. Further, preferred examples of the alkoxy group include a methoxy group and an ethoxy group.

  On the other hand, examples of the acidic group in the acidic group-containing lubricant include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. Suitable acidic groups are at least one of carboxyl groups, carboxylic anhydride groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups and phosphinic acid groups. In particular, a lubricant having at least one acidic group selected from a carboxyl group, a carboxylic acid anhydride group and a phosphonic acid group is preferable, and a lubricant having a carboxyl group and / or a carboxylic acid anhydride group is particularly preferable. In the acidic group-containing lubricant, the concentration of the acidic group is in the range of 0.05 to 10 meq / g, more preferably in the range of 0.1 to 6 meq / g, and still more preferably in the range of 0.5 to 4 meq / g.

  Here, the lubricant is a compound widely known for reducing friction with an apparatus or a mold in plastic molding and obtaining a good mold release, and specifically includes olefin wax, higher fatty acid (for example, Examples thereof include aliphatic carboxylic acids having 16 to 60 carbon atoms, polyalkylene glycols having a polymerization degree of about 10 to 200, silicone oils, and fluorocarbon oils. Examples of olefin waxes include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and α-olefin polymer as paraffin wax. Examples of polyethylene wax include polyethylene having a molecular weight of about 1,000 to 15,000. Examples include polypropylene. This molecular weight is a weight average molecular weight calculated based on a calibration curve obtained from standard polystyrene in GPC (gel permeation chromatography).

  Examples of a method for bonding carboxyl groups to such a lubricant (excluding higher fatty acids) include, for example, (a) a method of copolymerizing a monomer having a carboxyl group and an α-olefin monomer, and (b) the above The method etc. which couple | bond or copolymerize the compound or monomer which has carboxyl groups with respect to a lubricant can be mentioned.

  In the method (a), a living polymerization method can be employed in addition to radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization. Furthermore, a method of once forming a macromonomer and then polymerizing is also possible. The form of the copolymer can be used as a copolymer of various forms such as an alternating copolymer, a block copolymer, and a tapered copolymer in addition to the random copolymer. In the method (b), a radical generator such as peroxide or 2,3-dimethyl-2,3-diphenylbutane (commonly called “dicumyl”) is added to a lubricant, particularly an olefinic wax, if necessary, and a high temperature. A method of reacting or copolymerizing under the above can be adopted. In this method, a reactive site is thermally generated in the lubricant, and a compound or monomer that reacts with the active site is reacted. Other methods for generating active sites required for the reaction include irradiation with radiation and electron beam, and application of external force by mechanochemical technique. Furthermore, a method in which a monomer that generates an active site required for the reaction is copolymerized in advance in the lubricant. Examples of the active site for the reaction include an unsaturated bond and a peroxide bond, and a method for obtaining the active site includes a nitroxide-mediated radical polymerization method represented by TEMPO.

  Examples of the compound or monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, and citraconic anhydride, and maleic anhydride is particularly preferable.

  As the acidic group-containing lubricant, the carboxyl group is preferably 0.05 to 10 meq / g, more preferably 0.1 to 6 meq / g, still more preferably 0.5 to 4 meq / g per gram of the carboxyl group-containing lubricant. Carboxy group-containing olefin waxes contained in a concentration are preferred. Furthermore, the molecular weight of the olefin wax is preferably 1,000 to 10,000. Furthermore, a copolymer of an α-olefin and maleic anhydride that satisfies the conditions of such concentration and molecular weight is preferable. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  Such a surface coating lubricant is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and further 0.05 to 1 part by weight based on 100 parts by weight of the total of component A and component B. preferable.

(About the content of each component)
In the flame-retardant aromatic polycarbonate resin composition of the present invention, the ratio of the A component and the B component is 20 to 99 parts by weight for the A component and 1 to 80 parts by weight for the B component, based on the total of 100 parts by weight of both. It is. The component A is preferably 50 to 99 parts by weight, more preferably 60 to 99 parts by weight, still more preferably 70 to 98 parts by weight, based on the total of 100 parts by weight of both. Therefore, the component B is preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, and still more preferably 2 to 30 parts by weight.

  The blending amount of the flame retardant (C component) is 0.001 to 30 parts by weight based on a total of 100 parts by weight of the A component and the B component, although the appropriate content varies depending on the type of the flame retardant. If the amount is less than 0.001 part by weight, the flame retardancy of any flame retardant is insufficient, and if it exceeds 30 parts by weight, the heat resistance and mechanical strength are remarkably lowered, which is not suitable. The appropriate amount range for each flame retardant species is as described above.

  In the above, the amount of component D is 0.05 to 30 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 7 parts by weight, and still more preferably 2 to 5 parts by weight. If the content of component B is less than 0.05 parts by weight, the improvement in fluidity is insufficient, and if it exceeds 30 parts by weight, flame retardancy, heat resistance, and mechanical properties are deteriorated.

  Furthermore, as described above, the flame retardant resin composition of the present invention has a ratio of the rubber component of the rubber polymer in the B component of br parts by weight and the ratio of the D component of d parts by weight (br / It is preferable that d) satisfies a specific range. Further, such br is preferably 0.5 ≦ br ≦ 5.

(Other additives)
In the polycarbonate resin composition of the present invention, various stabilizers and coloring materials can be used to stabilize the molecular weight and hue at the time of molding. Examples of such stabilizers include phosphorus stabilizers, hindered phenol stabilizers, ultraviolet absorbers, and light stabilizers.

(I) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

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

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

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

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

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (10) are preferable.

（式（１０）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (10), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (10), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-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-thiodie Renbis- [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 Cyanurate, 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-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The compounding amount of the phosphorus stabilizer and the hindered phenol antioxidant is 0.005 to 1 part by weight, preferably 0.01 to 0.3 part by weight, based on the total of 100 parts by weight of component A and component B, respectively. Part.

(Iii) Mold Release Agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like.

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

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 0 parts on the basis of 100 parts by weight of the total of component A and component B. .5 parts by weight. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good release properties and roll release properties without impairing good hue.

(Iv) Ultraviolet absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Since the resin composition of the present invention may be inferior in weather resistance due to the influence of a rubber component or a flame retardant, the incorporation of an ultraviolet absorber is effective to prevent such deterioration.

  Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydro Shi-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.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

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

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

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-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) acrylate. The

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

  The content of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 1 part by weight, based on a total of 100 parts by weight of component A and component B. More preferably, it is 0.05-0.5 weight part.

(V) Dye / pigment The polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

  Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.

  The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the total of component A and component B.

(Vi) Other Heat Stabilizers The polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight based on 100 parts by weight of the total of the A component and the B component.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on the total of 100 parts by weight of the component A and the component B.

(Vii) White pigment for high light reflection The polycarbonate resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on the total of 100 parts by weight of the component A and the component B. Two or more kinds of white pigments for high light reflection can be used in combination.

(Viii) Antistatic agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonic acid phosphonium salts such as (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzene sulfonic acid phosphonium salts, and alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, based on a total of 100 parts by weight of component A and component B. More preferably, it is the range of 1.5-3 weight part.

  Antistatic agents include, for example: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on the total of 100 parts by weight of the component A and the component B, preferably 0.001 to 0.3 parts by weight, More preferably, it is 0.005-0.2 weight part. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkylsulfonic acid ammonium salt and arylsulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on a total of 100 parts by weight of component A and component B. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on a total of 100 parts by weight of component A and component B.

(Ix) Other additives The polycarbonate resin composition of the present invention includes thermoplastic resins other than the A component, B component and D component, other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalyst systems An antifouling agent, a heat ray absorbent, a photochromic agent, and the like can be blended.

  As thermoplastic resins other than A component, B component and D component, aromatic polyester resin (polyethylene terephthalate resin (PET resin), polybutylene terephthalate resin (PBT resin), cyclohexanedimethanol copolymerized polyethylene terephthalate resin (so-called PET-G) Resin), polyethylene naphthalate resin, and polybutylene naphthalate resin), polymethyl methacrylate resin (PMMA resin), cyclic polyolefin resin, polylactic acid resin, polycaprolactone resin, thermoplastic fluororesin (eg, polyvinylidene fluoride resin) And polyolefin resins (such as polyethylene resin, ethylene- (α-olefin) copolymer resin, polypropylene resin, and propylene- (α-olefin) copolymer resin). Is done. The other thermoplastic resin and rubbery polymer are preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on the total of 100 parts by weight of component A and component B.

(Manufacture of polycarbonate resin composition)
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, the components A to D and optionally other additives are sufficiently mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical apparatus, an extrusion mixer, and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

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

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

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such screens include wire meshes, screen changers, sintered metal plates (disk filters, etc.) 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. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical disks are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, 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.

  In addition, a master pellet is prepared by previously melting and kneading the A component and the D component in a melt kneader so as to contain the high concentration D component of the present invention, and the master pellet is added to the remaining A component and other additions. The method of mixing with an agent and pelletizing with a melt kneader is mentioned.

  The polycarbonate resin composition of the present invention can be produced in various products by usually injection-molding the pellets produced as described above to obtain molded products. 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.

  The polycarbonate resin composition of the present invention can also be used in the form of various shaped extrusions, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

  Thus, a molded article of a flame retardant aromatic polycarbonate resin composition with improved fluidity is provided without deteriorating mechanical properties typified by heat resistance and surface impact strength. That is, according to the present invention, 0.001 to 30 parts by weight of C component and 0.05 to 30 parts by weight of 100 parts by weight of component A 20 to 99 parts by weight and B component 1 to 80 parts by weight. There is provided a molded article obtained by melt-molding a flame retardant aromatic polycarbonate resin composition comprising a D component, more preferably 0.05 to 2 parts by weight of an E component.

  Specific examples of the molded product in which the resin composition of the present invention is used are suitable for application to internal parts and housings of OA equipment and home appliances. These products include, for example, personal computers, notebook computers, CRT displays, printers, mobile terminals, mobile phones, copiers, fax machines, recording media (CD, CD-ROM, DVD, PD, FDD, etc.) drives, parabolic antennas, electric motors. Tools, VTR, TV, iron, hair dryer, rice cooker, microwave oven, audio equipment, audio equipment such as audio, laser disc, compact disc, lighting equipment, refrigerator, air conditioner, typewriter, word processor, etc. Resin products formed from the flame-retardant thermoplastic resin composition of the present invention can be used for various parts such as these cases. Examples of other resin products include vehicle parts such as lamp sockets, lamp reflectors, lamp housings, instrument panels, center console panels, deflector parts, car navigation parts, and car stereo parts.

  Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  In addition, since the resin composition of the present invention is excellent in metal adhesion, application of vapor deposition treatment and plating treatment is also preferable. The molded product thus provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts, and the like. Such parts are particularly preferably sheet-like and film-like.

  The flame-retardant aromatic polycarbonate resin composition of the present invention has improved fluidity without deteriorating mechanical properties typified by heat resistance and surface impact strength. It is widely useful in various fields such as electrical / electronic equipment, automobiles, etc. Therefore, the industrial effect exhibited by the present invention is extremely great.

  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.

(I) Evaluation of Flame Retardant Aromatic Polycarbonate Resin Composition (i) Flame Retardancy According to UL standard 94V, a combustion test was conducted at a thickness of 1.5 mm, 1.6 mm or 2.0 mm.
(Ii) Fluidity An Archimedes spiral flow length having a channel thickness of 2 mm and a channel width of 8 mm was measured by an injection molding machine “SG150U manufactured by Sumitomo Heavy Industries, Ltd.”. The molding conditions are Examples 1 to 11, and Comparative Examples 1 to 9 are a cylinder temperature of 260 ° C., a mold temperature of 70 ° C., and an injection pressure of 98 MPa. In Examples 12 to 15 and Comparative Examples 10 to 13, a cylinder is used. The test was performed under the conditions of a temperature of 280 ° C., a mold temperature of 70 ° C., and an injection pressure of 98 MPa.
(Iii) Charpy impact strength According to ISO 179, Charpy impact strength with a notch was measured.
(Iv) Deflection temperature under load Deflection temperature under load was measured according to ISO 75-1 and 75-2. The measurement load was 1.80 MPa.
(V) Rigidity The flexural modulus was measured according to ISO178 (test specimen dimensions: length 80 mm × width 10 mm × thickness 4 mm).
(Vi) Surface impact strength A square plate having a size of 150 mm × 150 mm × 2 mmt was prepared, and the energy required for destruction (fracture energy) and the state of destruction were measured using a high-speed surface impact tester. Regarding the state of destruction,
○: Ductile fracture ×: Brittle fracture. Ductile fracture is a favorable result. The test machine uses a high-speed surface impact tester Hydroshot HTM-1 (manufactured by Shimadzu Corp.), and the test conditions are a strike core impact speed of 7 m / sec, a semi-circular tip, and a strike core with a radius of 6.35 mm And the diameter of the cradle hole was 25.4 mm.

[Examples 1-15, Comparative Examples 1-13]
The mixture which consists of a component except the C component (only in the case of the phosphate ester of FR-1) and F component (reinforced filler) with the composition shown in Table 1-Table 4 was supplied from the 1st supply port of the extruder. Such a mixture was obtained by mixing the following premix (i) with other components using a V-type blender. That is, (i) A mixture of an E component (fluorine-containing anti-dripping agent) and an A component aromatic polycarbonate, and the entire bag is shaken in a polyethylene bag so that the E component is 2.5% by weight. Mixture uniformly mixed with. However, when ABS-1 or ABS-2 was contained in B component, these components were supplied from the 2nd supply port using the side feeder. Moreover, all F components were supplied from the 2nd supply port using the side feeder. Further, the FR component C-1 is heated to 80 ° C., and a liquid supply device (HYM-JS-08 manufactured by Fuji Techno Industry Co., Ltd.) is used to supply the third supply port (second supply port and vent) in the middle of the cylinder. From the position between the exhaust port and the exhaust port, each was supplied to the extruder at a predetermined ratio. The liquid injection device was set to supply a constant amount, and the supply amounts of other raw materials were precisely measured with a measuring instrument [CWF manufactured by Kubota Corporation]. Extrusion is performed by using a vent type twin screw extruder (Nippon Steel Works TEX30α-38.5BW-3V) with a diameter of 30 mmφ, melt kneading at a screw speed of 150 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 3 kPa. Pellets were obtained. In addition, about the extrusion temperature, in the case of Examples 1-11 and Comparative Examples 1-9, it is set to 260 degreeC from a 1st supply port to a die part, In the case of Examples 12-15 and Comparative Examples 10-13, it is 1st. It implemented at 280 degreeC from 1 supply port to a die part.

  A part of the obtained pellets is 6 hours at 80 to 90 ° C in Examples 1 to 11 and Comparative Examples 1 to 9, and 100 to 110 ° C in Examples 12 to 15 and Comparative Examples 10 to 13. After drying with a hot air circulation dryer for 6 hours, an evaluation test piece was molded using an injection molding machine.

Each component represented by symbols in Tables 1 to 4 is as follows.
(A component)
PC-1 :: aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 22,500 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WP manufactured by Teijin Chemicals Ltd.]
PC-2: Aromatic polycarbonate resin [polycarbonate resin powder having a viscosity average molecular weight of 19,700 made from bisphenol A and phosgene by a conventional method, Panlite L-1225WX manufactured by Teijin Chemicals Ltd.]

(B component)
ABS-1: ABS resin [700-314 (trade name) manufactured by Toray Industries, Inc., about 12% by weight of butadiene rubber component, average rubber particle size is 350 nm]
ABS-2: ABS resin [Santac AT-08 (trade name) manufactured by Japan A & L Co., Ltd .; butadiene rubber component about 20% by weight, average rubber particle size is 1,200 nm]
ABS-3: ABS resin (manufactured by Japan A & L Co., Ltd., S3710 (trade name); amount of rubber component made of polybutadiene is about 50% by weight, average rubber particle size is 400 nm)
MBS-1: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd .: Methbrene C-223A (trade name); Graft copolymer having 70% by weight of polybutadiene core and styrene and methyl methacrylate as the core, average rubber (Particle size is 270 nm)
MBS-2: Core-shell graft copolymer (manufactured by Kureha Chemical Industry Co., Ltd .: Paraloid EXL-2602 (trade name); the core is polybutadiene 80 wt%, the shell is methyl methacrylate 16 wt% and ethyl acrylate 4 wt% A certain graft copolymer)
MBS-3: Core-shell graft copolymer (Mitsubishi Rayon Co., Ltd .: Methbrene S-2001 (trade name); Core is a structure in which a dimethylsiloxane polymer and an (n-butyl acrylate) polymer are intertwined with each other (A graft copolymer having 80% by weight of a composite rubber and 20% by weight of a methyl methacrylate shell)
(Part of B component)
AS: acrylonitrile-styrene copolymer (Nippon A & L Co., Ltd .; Litec-A BS-218 (trade name), weight average molecular weight in terms of standard polystyrene by GPC measurement: 78,000, acrylonitrile component content: 26% by weight, Styrene component content: 74% by weight)

(C component)
FR-1: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741 (trade name))
FR-2: potassium perfluorobutanesulfonate (manufactured by Dainippon Ink & Chemicals, Inc., MegaFuck F-114P (trade name))
FR-3: organosiloxane flame retardant containing Si-H group, methyl group and phenyl group (X-40-2600J (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.)
FR-4: Phosphate ester mainly composed of resornol bis [di (2,6-dimethylphenyl) phosphate] (manufactured by Daihachi Chemical Industry Co., Ltd .: PX-200 (trade name))

(D component)
D-1: A flow modifier having a weight average molecular weight of 54,500 (manufactured by Mitsubishi Rayon Co., Ltd .: Metabrene KP4493). The flow modifier is an emulsified radical in which the monomer (Da) is phenyl methacrylate, the monomer (Db) is styrene, and the weight ratio of Da to Db (Da: Db) is 13:87. It was a random copolymer produced by a polymerization method. When 1 g of the copolymer was mixed with 10 ml of chloroform and stirred for 30 minutes, the copolymer was insoluble and contained substantially no crosslinked structure. Its molecular weight distribution (Mw / Mn) was 2.4.
D-2: A flow modifier having a weight average molecular weight of 115,000 (Mitsubishi Rayon Co., Ltd .: Metabrene KP4494). The flow modifier had the same configuration as D-1 except that the molecular weight was 115,000 and the molecular weight distribution was 2.6.
D-3 (for comparison): Flow modifier D-4 prepared by the following production method: In the production method of (D-3), phenyl methacrylate is used instead of butyl acrylate, and the weight ratio of phenyl methacrylate to styrene is A flow modifier having a weight average molecular weight of 42,000, prepared in the same manner as D-3 except that the ratio was 20:80

(GPC measurement of D-1 to D-4)
GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, and two columns of ResiPore (length 300 mm, inner diameter 7.5 mm) manufactured by Polymer Laboratories were connected in series as a column, chloroform as a mobile phase, Using a polymer laboratory Easy Cal PS-2 as a standard substance, a photodiode array detector at a wavelength of 254 nm as a detector, using chloroform as a developing solvent, a solution in which 10 mg of a sample was dissolved per 5 ml of chloroform was dissolved in GPC. 100 μl was injected into the measuring apparatus, GPC measurement was performed under conditions of a column temperature of 40 ° C. and a flow rate of 1 ml / min, the molecular weight of the flow modifier was measured, and the weight average molecular weight was calculated. The measuring apparatus is pump: L-6000 manufactured by Hitachi, Ltd., autosampler: L-7200 manufactured by Hitachi, Ltd., column oven: L-7300 manufactured by Hitachi, Ltd., photodiode array detector: (stock) ) L-2450 manufactured by Hitachi, Ltd.
(Manufacturing method of D-3)
A separable flask equipped with a condenser and a stirrer was charged with 1.0 part by weight of dipotassium alkenyl succinate (Ramtel ASK manufactured by Kao) and 290 parts by weight of distilled water as a solid content, and in a water bath at 80 ° C. in a nitrogen atmosphere. Until heated. Next, 0.0004 parts by weight of ferrous sulfate, 0.0012 parts by weight of ethylenediaminetetraacetate disodium salt and 0.5 parts by weight of Rongalite are dissolved in 5 parts by weight of distilled water, and then 10 parts by weight of butyl acrylate, allyl methacrylate are added. A mixture of 0.1 part by weight, 0.05 part by weight of tert-butyl hydroperoxide and 0.1 part by weight of n-octyl mercaptan was added dropwise over 18 minutes. The mixture was then stirred for 60 minutes to complete the first stage polymerization.
To this, 0.0004 parts by weight of ferrous sulfate, 0.0012 parts by weight of ethylenediaminetetraacetic acid disodium salt and 0.5 parts by weight of Rongalite were dissolved in 5 parts by weight of distilled water, and then 90 parts by weight of styrene, A mixture of 0.45 parts by weight of tert-butyl hydroperoxide and 1.8 parts by weight of n-octyl mercaptan was added dropwise over 162 minutes. The mixture was then stirred for 60 minutes to complete the second stage polymerization to obtain an emulsion. The solid content of the obtained emulsion was measured and found to be 24.2%. Moreover, when this emulsion was poured into dilute sulfuric acid aqueous solution and the resulting precipitate was dried, the weight average molecular weight (Mw) of the soluble component in chloroform was 28,000.

(E component)
PTFE: polytetrafluoroethylene (manufactured by Daikin Industries, Ltd., Polyflon MP FA500 (trade name))

(F component)
WSN: Wollastonite (manufactured by Shimizu Kogyo; H-1250F (trade name))
Talc: Talc (Made by Hayashi Kasei Co., Ltd .; HST0.8 (trade name))
(Other ingredients)
DC30M: Olefin wax by copolymerization of α-olefin and maleic anhydride (Mitsubishi Chemical Co., Ltd .; Diacarna 30M (trade name))
SL
: Fatty acid ester release agent (Riken Vitamin Co., Ltd .; Riquemar SL900 (trade name))
WAX: Montanate ester (manufactured by Clariant Japan KK; Licolub WE-1 (trade name))
TMP: Phosphate heat stabilizer (manufactured by Daihachi Chemical Industry Co., Ltd .; TMP (trade name))
IRGX: Phenol-based heat stabilizer (Ciba Specialty Chemicals KK; IRGANOX 1076 (trade name))
D048: Isobutyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd .: AY43-048)

  From the above table, it can be seen that by adding a specific amount of the specific fluid reforming material of the present invention, the fluidity can be greatly improved without lowering the impact strength, heat resistance and flame retardancy.

It is a GPC chart of D-1 used in the example. The horizontal axis is the retention time (minutes), and the vertical axis is the detection intensity.

Explanation of symbols

1 Peak of polymer component of flow modifier 2 Peak of dimer component of flow modifier 3 Peak of styrene monomer in flow modifier (content of styrene monomer calculated from the detected intensity of the peak is About 0.4% by weight)

Claims (10)

A total of 100 parts by weight of aromatic polycarbonate resin (component A) 20 to 99 parts by weight and rubber-modified resin (component B) 1 to 80 parts by weight, and flame retardant (component C) 0.001 to 30 parts by weight and flow modification Flame retardant aromatic polycarbonate resin composition comprising 0.05 to 30 parts by weight of agent (component D), wherein the rubber-modified resin (component B) is a rubber polymer or a rubber polymer The flow modifier (D component) is a combination of (i) (meth) acrylic represented by the following general formula (1) and / or (2): It is a copolymer having as a main constituent unit a unit formed from an acid ester monomer (Da) and an aromatic alkenyl compound monomer (Db). (Ii) The chloroform-soluble component has a weight average molecular weight of 10 , 000 Flame retardant aromatic polycarbonate resin composition which is 200,000.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )   2. The resin composition according to claim 1, wherein the resin composition further comprises 0.01 to 2 parts by weight of a fluorine-containing anti-dripping agent (E component) based on 100 parts by weight of the total of the A component and the B component. Flame retardant aromatic polycarbonate resin composition.   The ratio of the monomer (Da) and the monomer (Db) in the D component is such that the total of both is 80% by weight or more in 100% by weight of the D component, The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 and 2, wherein Da) is 1 to 80 wt% and the monomer (Db) is 20 to 99 wt%.   The flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the monomer (Da) in the component D is phenyl methacrylate.   The flame retardant aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the monomer (Db) in the component D is styrene.   In the resin composition, when the ratio of the rubber component of the rubbery polymer in the B component is br parts by weight and the ratio of the D component is d parts by weight, based on the total of 100 parts by weight of the A component and the B component The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein 0.1 ≦ (br / d) ≦ 5 is satisfied.   The above resin composition is 0.5 ≦ br ≦ 5 when the ratio of the rubber component of the rubber-like polymer in the B component is br parts by weight based on the total of 100 parts by weight of the A component and the B component. The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 6.   The flame retardant according to any one of claims 1 to 7, wherein the component C is one or more flame retardants selected from an organic phosphorus flame retardant, an organic metal salt flame retardant, and a silicone flame retardant. Aromatic polycarbonate resin composition. The component C flame retardant is an organophosphorus flame retardant represented by the following formula (3), and the proportion thereof is 1 to 30 parts by weight with respect to 100 parts by weight of the total of the A component and the B component. The flame-retardant aromatic polycarbonate resin composition according to 8.

(However, X in the above formula represents a divalent organic group derived from a dihydric phenol, and R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a monovalent organic group derived from a monohydric phenol. And n represents an integer of 0 to 5.) 20 to 99 parts by weight of aromatic polycarbonate resin (component A), and rubber-modified resin (component B) 1 to 80 weights which are a rubber polymer or a combination of a rubbery polymer and a styrenic hard polymer other than component D Flame retardant with improved fluidity obtained by melt-kneading 0.001 to 30 parts by weight of a total of 100 parts by weight, 0.001 to 30 parts by weight of a flame retardant (C component) and 0.05 to 30 parts by weight of a flow modifier (D component) The flow modifier (D component) is (i) a (meth) acrylic acid ester represented by the following general formula (1) and / or (2): A copolymer comprising a unit formed from a monomer (Da) and an aromatic alkenyl compound monomer (Db) as a main structural unit, and (ii) the chloroform-soluble component has a weight average molecular weight of 10,000. ~ Method for producing a flame retardant aromatic polycarbonate resin composition which has improved and is flowable 00,000.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring.)

(In the formula, R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a carbocyclic group itself or a hydrocarbon group composed of a carbon chain bonded to a carbocyclic ring, and n represents an integer of 1 to 4. )

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