Flame retardant aromatic polycarbonate resin composition and molded article of the same

Abstract

To provide a flame retardant aromatic polycarbonate resin composition which is excellent in transparency, and drip prevention property in combustion, without using a fluorine compound.SOLUTION: A flame retardant aromatic polycarbonate resin composition contains (A) an aromatic polycarbonate resin, (B) organohydrogenpolysiloxane represented by formula (1), and (C) an organic metal salt containing no fluorine, and contains a predetermined amount of an aromatic polycarbonate resin having predetermined MVR. Formula (1): [(R1O)(R2)2SiO1 / 2]a[(R3)3SiO1 / 2]b[(H)(R4)SiO2 / 2]c[(Ar)x(R5)2-xSiO2 / 2]d[(R6)2SiO2 / 2]e[(R7)SiO3 / 2]f. In the formula (1), R1 to R7 are alkyl groups, Ar is an aryl group, x is 1 or 2, 0<a≤0.03, 0<b≤0.30, 0≤c≤0.45, 0.20≤d≤0.70, 0≤e≤0.20, 0≤f≤0.70, and a+b+c+d+e+f is 1.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a flame-retardant aromatic polycarbonate resin composition and a molded article thereof. [Background technology]

[0002] Aromatic polycarbonate resins are formed into various molded products by simple and highly productive processing methods such as injection molding, and are used in a wide range of industrial fields. In particular, aromatic polycarbonate resins are widely used in applications requiring high transparency, such as various lighting covers and protective covers for transparent displays, taking advantage of their excellent transparency, represented by their high light transmittance and extremely low haze. In these applications, because light sources such as fluorescent lamps and light bulbs reach high temperatures, or are exposed to high humidity when used in bathrooms or outdoors, it is necessary to maintain transparency, hue, and mechanical properties even when exposed to heat or moisture, and in addition to the transparency of the resin composition, the moisture and heat resistance of the resin composition is emphasized.

[0003] In these applications, flame retardancy in the event of a fire has also been attracting attention in recent years, and resin compositions having high flame retardancy in addition to the above characteristics are required. As a method for imparting flame retardancy to aromatic polycarbonate resins, flame-retardant aromatic polycarbonate resin compositions containing halogen-based compounds or phosphorus-based compounds have been proposed and are used in office automation equipment, home appliances, and other products for which flame retardancy is highly desired, while flame-retardant aromatic polycarbonate resin compositions containing components that replace these flame retardants have been developed and are beginning to be used in the above-mentioned products. The purpose of this change in flame retardant is to suppress the generation of corrosive gases during molding and to improve the recyclability of products, etc.

[0004] As a new flame retardant replacing the flame retardants listed above, for example, a silicone compound can be mentioned. In recent years, flame-retardant resin compositions in which a silicone compound is blended with an aromatic polycarbonate resin have been vigorously studied, and various proposals have been made.

[0005] For example, Patent Document 1 proposes a method of blending an alkali (earth) metal salt of perfluoroalkanesulfonic acid and an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group with a polycarbonate resin, and Patent Document 2 proposes a method of blending an alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid and an organopolysiloxane containing an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group with a polycarbonate resin.

[0006] In addition, Patent Document 3 proposes a method of blending specific petroleum-based heavy oils or pitches and a silicone compound into a polycarbonate resin component, and Patent Document 4 proposes a method of blending a silicone compound with a non-silicone resin having an aromatic ring, which is represented by the formula R 0 2 SiO 1.0 (R 0 represents a monovalent hydrocarbon group. The same applies below.) and R 0 SiO 1.5 and a method of blending a silicone resin having a weight average molecular weight of 10,000 or more and 270,000 or less, which has a structural unit represented by the following formula:

[0007] However, the polycarbonate resin composition proposed above was not sufficient in transparency and flame retardancy. In particular, there were problems such as dripping in thin-walled products, failure to achieve V-0 rank under UL Standard 94, insufficient dispersion of the silicone component causing clouding in molded products, and reduced transparency after moist heat treatment due to aggregation of the silicone component.

[0008] On the other hand, Patent Document 5 specifically proposes a resin composition in which an organic alkali metal salt and poly(methyl hydrogen siloxane) are added to an aromatic polycarbonate resin. However, this resin composition itself becomes cloudy, and furthermore, poor dispersion such as peeling occurs on the surface of the molded product, and the transparency is not sufficient.

[0009] Furthermore, Patent Documents 6 and 7 propose transparent, flame-retardant polycarbonate resin compositions obtained by blending an aromatic polycarbonate resin with a silicone component containing an Si-H group and an aromatic group in the molecule.

[0010] Patent Document 8 proposes a flame-retardant polycarbonate resin composition that contains an aromatic polycarbonate resin blended with a specific core-shell type graft copolymer having a butadiene rubber core, and further contains a fluorinated polyolefin and an organic sulfonate metal salt flame retardant, specifically potassium perfluorobutanesulfonate.

[0011] In the above-mentioned prior art, polytetrafluoroethylene having fibril forming ability is often used as an anti-drip agent. However, when polytetrafluoroethylene is blended with aromatic polycarbonate resin, the appearance of the molded product becomes cloudy because polytetrafluoroethylene and aromatic polycarbonate resin are incompatible with each other. Furthermore, organic sulfonic acid metal salts, specifically potassium perfluorobutanesulfonate, are often used as flame retardants, but these are also incompatible with aromatic polycarbonate resins, and have the drawback of causing the appearance to become cloudy.

[0012] Meanwhile, in recent years, fluorine compounds have become the subject of international regulations, primarily in Japan, Europe, and the United States, and there are moves to further strengthen these regulations. In Europe, perfluorobutanesulfonic acid and its metal salts (PFBS) are regulated by REACH, and restrictions on organic fluorine compounds (PFAS), such as perfluoro and polyfluoroalkyl compounds, such as polytetrafluoroethylene, are also being implemented primarily in Europe and the United States. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] Japanese Patent Application Publication No. 6-306265 [Patent Document 2] Japanese Patent Application Publication No. 6-336547 [Patent Document 3] Japanese Patent Application Publication No. 9-169914 [Patent Document 4] Japanese Patent Application Publication No. 10-139964 [Patent Document 5] Special Publication No. 60-38419 [Patent Document 6] Patent No. 3779623 [Patent Document 7] Patent No. 3779624 [Patent Document 8] JP 2019-19191 A Summary of the Invention [Problem to be solved by the invention]

[0014] Therefore, in order to comply with the above PFBS and PFAS regulations, a polycarbonate resin composition that exhibits excellent flame retardancy without relying on perfluorobutanesulfonic acid metal salts or polytetrafluoroethylene is highly desired. However, it is not easy to achieve flame retardancy (V-0 in the UL-94 standard) without using perfluorobutanesulfonic acid and its metal salts, which are effective flame retardants, and polytetrafluoroethylene, which is an effective drip prevention agent.

[0015] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition which is excellent in transparency and in preventing resin dripping during combustion without using a fluorine compound, and a molded article thereof. [Means for solving the problem]

[0016] Means for Solving the Problems The present inventors have conducted intensive research in order to achieve the above object and have found that a resin composition containing a specific aromatic polycarbonate resin, a specific organohydrogenpolysiloxane, and a fluorine-free organic acid metal salt has excellent transparency and anti-dripping properties of the resin during combustion, thereby completing the present invention.

[0017] That is, the present invention provides 1. (A) aromatic polycarbonate resin: 100 parts by mass, (B) 0.1 to 10 parts by mass of an organohydrogenpolysiloxane having a weight average molecular weight of 700 to 10,000 and represented by the following formula (1): (C) At least one selected from fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts: 0.001 to 1.0 parts by mass A flame-retardant aromatic polycarbonate resin composition comprising: The melt volume flow rate (MVR) measured at 300°C under a load of 1.2 kg in accordance with ISO1133-1 is 2 to 8 cm 3 % by mass or more of an aromatic polycarbonate resin having a flame retardant viscosity of 10 / 10 minutes, based on the total mass of the component (A). [(R 1 O)(R 2 ) 2 SiO 1 / 2 ] a [(R 3 ) 3 SiO 1 / 2 ] b [(H)(R 4 )SiO 2 / 2 ] c [(Ar) x (R 5 ) 2-x SiO 2 / 2 ] d [(R 6 ) 2 SiO 2 / 2 ] e [(R 7 )SiO 3 / 2 ] f (1) (In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, Ar is, independently of each other, an aryl group having 6 to 12 carbon atoms, R 5 and R 6 are, independently of each other, an alkyl group having 1 to 6 carbon atoms, R 7 is, independently of each other, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may be substituted with an epoxy group, an amino group, an acryloyl group, a methacryloyl group or a thiol group. x represents 1 or 2, a is a number satisfying 0 < a ≦ 0.03, b is a number satisfying 0 < b ≦ 0.30, c is a number satisfying 0 ≦ c ≦ 0.45, d is a number satisfying 0.20 ≦ d ≦ 0.70, e is a number satisfying 0 ≦ e ≦ 0.20, f is a number satisfying 0 ≦ f ≦ 0.70, a + b + c + d + e + f = 1. However, when c is 0, one or more of R 2 and R 3 are hydrogen atoms.) 2. The flame-retardant aromatic polycarbonate resin composition according to 1, wherein in the formula (1), Ar is a phenyl group, x is 2, and f is 0, 3. The flame-retardant aromatic polycarbonate resin composition according to 1 or 2, wherein the component (C) is an alkali metal salt of an aromatic sulfonic acid containing no fluorine or an alkaline earth metal salt of an aromatic sulfonic acid containing no fluorine, 4. A molded article formed from the flame-retardant aromatic polycarbonate resin composition according to any one of 1 to 3 is provided.

Advantages of the Invention

[0018] The flame-retardant aromatic polycarbonate resin composition of the present invention exhibits excellent transparency and flame retardancy without using a fluorine compound and can comply with PFAS regulations.

Embodiments for Carrying Out the Invention

[0019] The present invention will be specifically described below. [1] Flame-retardant aromatic polycarbonate resin composition The flame-retardant aromatic polycarbonate resin composition of the present invention contains the following components (A) to (C): (A) an aromatic polycarbonate resin, (B) an organohydrogenpolysiloxane represented by formula (1), and (C) at least one selected from the group consisting of fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts;

[0020] [Component (A)] The component (A) in the flame-retardant aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin, and examples of the resin that can be used include those obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, as well as those obtained by polymerizing a carbonate prepolymer by a solid-phase transesterification method and those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

[0021] Specific examples of the dihydric phenol used herein include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis{(4-hydroxyphenyl)propane, 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)pentane, 1,1-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene, Examples of the 4,4'-dihydroxydiphenyl ether include isopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester. These can be used alone or in combination of two or more.

[0022] Among these, homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferred, and in particular, homopolymers of bisphenol A and copolymers of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, or α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferably used.

[0023] Examples of carbonate precursors include carbonyl halides, carbonate esters, and haloformates, and specific examples thereof include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0024] When the above dihydric phenol and carbonate precursor are reacted by the interfacial polycondensation method or the melt transesterification method to produce a polycarbonate resin, a catalyst, a terminal terminator, an antioxidant for the dihydric phenol, etc. may be used as necessary.

[0025] The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic difunctional carboxylic acid, or may be a mixture of two or more of the obtained polycarbonate resins.

[0026] Specific examples of trifunctional or higher polyfunctional aromatic compounds include phloroglucin, phloroglucide, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4-hydroxyphenyl) )ethyl]benzene}-α,α-dimethylbenzylphenol and other trisphenols; tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0027] When the polyfunctional compound that produces the above branched polycarbonate resin is contained, the proportion thereof is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.5 mol %, and further preferably 0.01 to 0.3 mol %, based on the total amount of the aromatic polycarbonate. In particular, in the case of the melt transesterification method, a branched structure may be formed as a side reaction, and the amount of the branched structure is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.5 mol %, and further preferably 0.01 to 0.3 mol %, based on the total amount of the aromatic polycarbonate. 1 It can be calculated by H-NMR measurement.

[0028] 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. Specific examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Specific examples of the organic solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene. To accelerate the reaction, a catalyst such as a tertiary amine, a quaternary ammonium compound, or a quaternary phosphonium compound, for example, triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, can be used. The reaction conditions are not particularly limited, and for example, the reaction temperature is usually preferably 0 to 40° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or higher.

[0029] In the above polymerization reaction, a terminal terminator is usually used. As such a terminal terminator, a monofunctional phenol can be used. The monofunctional phenol is generally used as a terminal terminator for molecular weight control, and specific monofunctional phenols are generally phenol or lower alkyl-substituted phenols, and examples thereof include monofunctional phenols represented by the following general formula (2).

[0030] [ka] (In the formula, D is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, or a phenyl-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3.)

[0031] Specific examples of the monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol, and isooctylphenol.

[0032] Other monofunctional phenols include phenols having a long-chain alkyl group or an aliphatic polyester group as a substituent, benzoic acid chlorides, long-chain alkyl carboxylic acid chlorides, etc. Among these, phenols having a long-chain alkyl group as a substituent, represented by the following general formulas (3) and (4), are preferably used.

[0033] [ka] (In the formula, n represents an integer of 10 to 50.)

[0034] [ka] (In the formula, E is -RO-, -RC(=O)-O- or -ROC(=O)-, R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and n is an integer of 10 to 50.)

[0035] As the substituted phenols represented by the above general formula (3), those in which n is 10 to 30 are preferable, and those in which n is 10 to 26 are more preferable, and specific examples thereof include, for example, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol, etc.

[0036] As the substituted phenols represented by the above general formula (4), compounds in which E is -RC(=O)-O- and R is a single bond are preferred, and those in which n is 10 to 30, particularly 10 to 26, are suitable. Specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, triacontyl hydroxybenzoate, and the like. These end terminators may be used alone or in combination of two or more.

[0037] The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is carried out, for example, by mixing a dihydric phenol and a carbonate ester while heating them in the presence of an inert gas, and distilling off the resulting alcohol or phenol. The reaction conditions are not particularly limited, and the reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually preferably 120 to 350° C. In the latter stage of the reaction, it is preferable to reduce the pressure of the system to about 1.33×103 to 13.3 Pa to facilitate distillation of the produced alcohol or phenol. The reaction time is usually preferably about 1 to 4 hours.

[0038] Examples of carbonate esters include esters of an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, and the like, which may be substituted. Specific examples thereof include diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like, and among these, diphenyl carbonate is preferable.

[0039] In addition, a polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds such as sodium hydroxide, potassium hydroxide, and sodium and potassium salts of dihydric phenols; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine; alkoxides of alkali metals and alkaline earth metals; organic acid salts of alkali metals and alkaline earth metals; zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds, which are generally used in esterification reactions and transesterification reactions. The catalysts may be used alone or in combination of two or more. The amount of the polymerization catalyst used is preferably 1×10 -8 ~1×10 -3 equivalent, more preferably 1×10 -7 ~5×10 -4 is selected within the equivalent range.

[0040] In addition, in order to reduce the number of phenolic terminal groups in the polymerization reaction, compounds such as bis(chlorophenyl)carbonate, bis(bromophenyl)carbonate, bis(nitrophenyl)carbonate, bis(phenylphenyl)carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate, nitrophenylphenylcarbonate, phenylphenylcarbonate, methoxycarbonylphenylphenylcarbonate and ethoxycarbonylphenylphenylcarbonate can be added in the later stage or after the completion of the polycondensation reaction. Of these, 2-chlorophenyl phenyl carbonate, 2-methoxycarbonylphenyl phenyl carbonate and 2-ethoxycarbonylphenyl phenyl carbonate are preferred, with 2-methoxycarbonylphenyl phenyl carbonate being more preferred.

[0041] Furthermore, in the polymerization reaction, it is preferable to use a deactivator that neutralizes the activity of the catalyst.Specific examples of this deactivator include sulfonic acid esters such as benzenesulfonic acid, p-toluenesulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; and further, naphthalenesulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonate, 2-phenyl-2-butyl dodecylbenzenesulfonate, tetrabutyl octyl sulfonate, tetrabutyl decyl sulfonate, tetrabutyl benzenesulfonate, tetraethyl dodecylbenzenesulfonate, Examples of compounds that can be mentioned include, but are not limited to, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, decylammonium butyl sulfate, decylammonium decyl sulfate, dodecylammonium methyl sulfate, dodecylammonium ethyl sulfate, dodecylmethylammonium methyl sulfate, dodecyldimethylammonium tetradecyl sulfate, tetradecyldimethylammonium methyl sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, and tetramethylammonium dodecylbenzyl sulfate. These compounds may be used alone or in combination of two or more. Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred.

[0042] The amount of these deactivators is preferably 0.5 to 50 mol per mol of the remaining catalyst, and is preferably 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and further preferably 0.01 to 100 ppm, based on the polycarbonate resin after polymerization.

[0043] The molecular weight of the aromatic polycarbonate resin of component (A) is not particularly limited, but from the viewpoint of mechanical properties and moldability at high temperatures, the viscosity average molecular weight is preferably 10,000 to 50,000, more preferably 14,000 to 45,000, and even more preferably 14,000 to 40,000. The viscosity average molecular weight is calculated by measuring the intrinsic viscosity [η] of a methylene chloride solution at 20°C and calculating it according to the Schnell formula ([η] = 1.23 × 10 -5 ×Mv 0.83 ) can be calculated. The component (A) may be used alone or in combination of two or more kinds.

[0044] As the component (A), commercially available products can be used, such as NOVAREX M-7027U, M-7025U (branched polycarbonate resins manufactured by Mitsubishi Engineering Plastics Corporation), Panlite K-1300Y (polymeric polycarbonate resin manufactured by Teijin Limited), Toughlon IR-2500 (polymeric polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd.), FN-2200 (standard polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd.), and Iupilon S-3000N (standard polycarbonate resin manufactured by Mitsubishi Engineering Plastics Corporation).

[0045] In general, the high molecular weight and branched type resins commercially available are aromatic polycarbonate resins with high viscosity average molecular weights, which tend to have a low melt volume flow rate (MVR), which is an index of fluidity and moldability, and are therefore preferred. The component (A) in the flame-retardant aromatic polycarbonate resin composition of the present invention has an MVR of 2 to 8 cm at 300° C. and a load of 1.2 kg according to ISO 1133-1. 3The aromatic polycarbonate resin having a viscosity of 100 / 10 minutes is contained in an amount of 20% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the component (A). If the aromatic polycarbonate resin is less than 20% by mass, drip resistance cannot be obtained. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less. In addition, the MVR is 2 cm 3 If it is less than 10 minutes, the fluidity is insufficient and moldability tends to be poor. 3 If the temperature exceeds 100°C / min, impact resistance, etc. will decrease.

[0046] The aromatic polycarbonate resin of component (A) preferably does not contain a halogen-substituted skeleton such as a halogen-substituted dihydric phenol in the molecule.

[0047] The aromatic polycarbonate resin of component (A) may contain an aromatic polycarbonate resin regenerated from used products (so-called material recycled polycarbonate resin), or an aromatic polycarbonate resin produced from an aromatic polycarbonate resin that has been chemically decomposed and returned to its raw materials (so-called chemically recycled polycarbonate resin).

[0048] [(B) Component] The component (B) in the flame-retardant aromatic polycarbonate resin composition of the present invention is an organohydrogenpolysiloxane having a structural unit ratio represented by the following formula (1). [(R 1 O)(R 2 ) 2 SiO 1 / 2 ] a [(R 3 ) 3 SiO 1 / 2 ] b [(H)(R 4 )SiO 2 / 2 ] c [(Ar) x (R 5 ) 2-x SiO 2 / 2 ] d [(R6 ) 2 SiO 2 / 2 e [(R 7 )SiO 3 / 2 f (1)

[0049] In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, R 4 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, Ar is each independently an aryl group having 6 to 12 carbon atoms, R 5 and R 6 are each independently an alkyl group having 1 to 6 carbon atoms, and R 7 is each independently an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may be substituted with epoxy, amino, acryloyl, methacryloyl or thiol. x represents 1 or 2, a is a number satisfying 0 < a ≤ 0.03, b is a number satisfying 0 < b ≤ 0.30, c is a number satisfying 0 ≤ c ≤ 0.45, d is a number satisfying 0.20 ≤ d ≤ 0.70, e is a number satisfying 0 ≤ e ≤ 0.20, f is a number satisfying 0 ≤ f ≤ 0.70, and a + b + c + d + e + f = 1. However, when c is 0, at least one of R 2 and R 3 is a hydrogen atom.

[0050] Specific examples of the alkyl group having 1 to 3 carbon atoms for R 1 include a methyl group, an ethyl group, a propyl group, etc. Among them, R 1 is preferably a hydrogen atom or a methyl group.

[0051] R 2 and R 3 ​​The alkyl group having 1 to 6 carbon atoms is preferably one having 1 to 3 carbon atoms, specific examples of which include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups, and the aryl group having 6 to 12 carbon atoms is preferably one having 6 to 10 carbon atoms, specific examples of which include phenyl, tolyl, xylyl, and naphthyl groups. Among them, R 2 and R 3 is preferably a hydrogen atom, a methyl group, or a phenyl group, and more preferably a methyl group.

[0052] R 4 Specific examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include the above-mentioned R 2 and R 3 Among them, R 4 is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0053] The aryl group having 6 to 12 carbon atoms represented by Ar is preferably an aryl group having 6 to 10 carbon atoms, and specific examples thereof include the above-mentioned R 2 and R 3 Among them, a phenyl group is preferable.

[0054] R 5 and R 6 The alkyl group having 1 to 6 carbon atoms is preferably an alkyl group having 1 to 3 carbon atoms, and specific examples thereof include the above-mentioned R 2 and R 3 Among them, a methyl group is preferable.

[0055] R 7 The alkenyl group having 2 to 8 carbon atoms is preferably an alkenyl group having 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, butenyl, hexenyl, and octenyl groups. Specific examples of the aryl group having 6 to 12 carbon atoms include the above-mentioned R 2 and R 3 Examples of the aryl groups include the same aryl groups as those exemplified by aryl groups listed above. Specific examples of the alkyl group having 1 to 8 carbon atoms which may be substituted with an epoxy group, an amino group, an acryloyl group, a methacryloyl group or a thiol group include methyl, ethyl, propyl, butyl, hexyl, octyl, glycidoxypropyl, aminopropyl, (meth)acryloylpropyl, mercaptopropyl groups and the like. Among them, R 7 is preferably a methyl group, a glycidoxypropyl group, an aminopropyl group, a (meth)acryloylpropyl group, a mercaptopropyl group, or a phenyl group, more preferably a methyl group or a phenyl group, and still more preferably a phenyl group.

[0056] a is a number satisfying 0 < a ≤ 0.03, and preferably a number satisfying 0.005 ≤ a ≤ 0.025. b is a number satisfying 0 < b ≤ 0.30, and preferably a number satisfying 0.01 ≤ b ≤ 0.25. c is a number satisfying 0 ≤ c ≤ 0.45, and preferably a number satisfying 0.1 ≤ c ≤ 0.40. d is a number satisfying 0.20 ≤ d ≤ 0.70, and preferably a number satisfying 0.22 ≤ d ≤ 0.40. e is a number satisfying 0 ≤ e ≤ 0.20, and preferably a number satisfying 0.02 ≤ e ≤ 0.15. f is a number satisfying 0 ≤ f ≤ 0.70, and preferably a number satisfying 0 ≤ f ≤ 0.60. x is 1 or 2, and 2 is preferred. However, when c is 0, one or more of R 2 and R 3 are hydrogen atoms, and preferably one of R 3 is a hydrogen atom.

[0057] The sequence order of the siloxane units of component (B) is not particularly limited, and any form of random copolymerization, block copolymerization, or tapered copolymerization may be used.

[0058] As component (B), in formula (1), those in which Ar is a phenyl group and x is 2 are preferred, and those in which Ar is a phenyl group, x is 2, and f is 0 are more preferred. Specific examples of the component (B) include, but are not limited to, those represented by the following formulas: [(R 11 O)(CH 3 ) 2 SiO 1 / 2 ] a [(CH 3 ) 3 SiO 1 / 2 ] b [H(CH 3 )SiO 2 / 2 ] c1 [(C 6 H 5 ) 2 SiO 2 / 2 ] d [(CH 3 ) 2 SiO 2 / 2 ] e1 [(R 11 O)(CH 3 ) 2 SiO 1 / 2 ] a [H(CH 3 ) 2 SiO 1 / 2 ] b [(C 6 H 5 ) 2 SiO 2 / 2 ] d [(CH 3 ) 2 SiO 2 / 2 ] e1 [C 6 H 5 SiO 3 / 2 ] f1 (In the formula, R 11 is a hydrogen atom or a methyl group, a, b, d, and f are the same as above, c1 is a number that satisfies 0.1≦c1≦0.40, e1 is a number that satisfies 0.02≦e1≦0.15, and f1 is a number that satisfies 0.10≦f1≦0.60.

[0059] The weight average molecular weight (Mw) of component (B) measured by gel permeation chromatography (GPC) is 700 to 10,000, preferably 800 to 9,000. If Mw is less than 700, component (B) tends to volatilize during kneading, resulting in a reduced amount of component (B) to be blended and failing to provide a flame retardant effect. On the other hand, if Mw is more than 10,000, the compatibility and dispersibility with component (A) is reduced, resulting in a reduced transparency and flame retardancy of the composition.

[0060] Component (B) contains chloride ions (Cl) derived from the acid catalyst used in the production process. - ) and sulfate ion (SO 4 2- ) may remain in the composition, and these remaining ions may cause thermal decomposition of the composition and corrosion of metal parts of the apparatus at high temperatures during kneading, injection molding, etc., so the content of chloride ions and sulfate ions relative to the mass of component (B) is preferably 3 ppm by mass or less.

[0061] Furthermore, if component (B) contains volatile matter, there is a risk that evaporation of the volatile matter during kneading or injection molding may cause problems such as molding defects. Therefore, it is preferable that the mass loss when heated at 150°C for 30 minutes at 1 atmospheric pressure is 3 mass% or less relative to the mass of component (B).

[0062] The volume of hydrogen gas generated per unit mass by the alkali decomposition method of the component (B) is preferably 30 to 80 mL / g. More preferably, it is 40 to 70 mL / g. When it is 30 mL / g or more, the structure of the component (B) is easily formed, and dripping during combustion can be suppressed. When it is 80 mL / g or less, it is possible to suppress the molded product from becoming cloudy due to foaming caused by the reaction of excess Si-H groups with moisture in the air during heat treatment, which generates hydrogen gas from the resin composition. Here, the structure of the component (B) refers to a network structure generated by the mutual reaction of the organohydrogenpolysiloxane itself, or the reaction of the aromatic polycarbonate resin with the organohydrogenpolysiloxane.

[0063] As reported in the above-mentioned Patent Documents 6 and 7, organohydrogenpolysiloxanes containing Si-H groups and aromatic groups in the molecule are known to act as flame retardants. In the present invention, component (B) further contains, in addition to these groups, [(R 1 O)(R 2 ) 2 SiO 1 / 2 ](R 1 and R 2 is the same as above. The same applies below.) improves flame retardancy. This is because component (B) migrates to the surface during combustion, and in addition to the formation of a structure by the Si-H group, (R 1 O) groups and (R 1 It is presumed that dripping is suppressed by increasing the formation of structure through cross-linking between the Si-H groups and the O groups.

[0064] In the flame-retardant aromatic polycarbonate resin composition of the present invention, from the viewpoint of improving the dispersibility of the (B) component and suppressing the composition from becoming cloudy or losing transparency due to wet heat treatment, the amount of aryl groups in the (B) component is preferably 10 to 80% by mass, more preferably 15 to 70% by mass. Here, the amount of aryl groups can be calculated by the following formula. Aryl group amount = [A / M] x 100 (mass%) A: Sum of formula weights of aryl groups per molecule of component (B) M: Weight average molecular weight of component (B)

[0065] The component (B) may be used alone or in combination of two or more kinds.

[0066] The blending amount of the (B) component is 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, and more preferably 1 to 5 parts by mass, based on 100 parts by mass of the aromatic polycarbonate resin (A) component. If it is less than 0.1 part by mass, flame retardancy cannot be obtained, and if it exceeds 10 parts by mass, the transparency of the composition decreases or molding defects occur.

[0067] The organohydrogenpolysiloxane of component (B) can be obtained, for example, by cohydrolytic condensation of organochlorosilanes and removing the by-product hydrochloric acid and low-boiling components. [(R 1 O)(R 2 ) 2 SiO 1 / 2 The method for introducing the ] unit is dimethylchlorosilane (H(CH 3 ) 2 By using silanes having Si-H groups such as SiCl as raw materials, the hydrogen atoms of the Si-H groups are converted to R by the hydrochloric acid by-product in the reaction. 1 It can be easily converted to an O group.

[0068] Furthermore, when linear siloxanes, cyclic siloxanes, or alkoxysilanes are used as the starting materials, the organohydrogenpolysiloxane of component (B) can also be obtained by proceeding with the equilibration reaction and condensation reaction using an acid catalyst such as sulfuric acid or methanesulfonic acid, and then removing the acid catalyst and low-boiling point components used. In this case, hexamethyldisiloxane or the like is used as the terminal component, and an equilibration reaction is carried out with highly acidic acids such as trifluoromethanesulfonic acid and p-toluenesulfonic acid to form a trimethylsilyl group [(CH 3 ) 3 SiO 1 / 2 ] is partially cleaved to form R 1 It is converted to an O group.

[0069] [(C) component] The component (C) in the flame-retardant aromatic polycarbonate resin composition of the present invention is at least one selected from fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts, and is a component that improves flame retardancy. It is preferable that the aromatic polycarbonate resin composition of the present invention does not contain fluorinated organic alkali metal salts and organic alkaline earth metal salts such as potassium perfluorobutanesulfonate, which are typical conventional flame retardants.

[0070] Specific examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Specific examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, with lithium, sodium, and potassium being particularly preferred.

[0071] As the fluorine-free organic metal salt, any of the fluorine-free alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids are preferred, and from the standpoint of dispersibility in component (A), the fluorine-free alkali metal salts of aromatic sulfonic acids and the fluorine-free alkaline earth metal salts of aromatic sulfonic acids are more preferred.

[0072] Examples of the aliphatic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, and octanesulfonic acid.

[0073] Specific examples of alkali (earth) metal salts of fluorine-free aliphatic sulfonic acids include lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, lithium butanesulfonate, sodium butanesulfonate, potassium butanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, and barium methanesulfonate.

[0074] Examples of the aromatic sulfonic acid include sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters thereof, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfonesulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids with a methylene bond.

[0075] Specific examples of the alkali (earth) metal sulfonate salts of monomeric or polymeric aromatic sulfides include disodium diphenylsulfide-4,4'-disulfonate and dipotassium diphenylsulfide-4,4'-disulfonate.

[0076] Specific examples of the alkali (earth) metal sulfonate salts of aromatic carboxylic acids and their esters include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

[0077] Specific examples of alkali (earth) metal sulfonates of monomeric or polymeric aromatic ethers include calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, and lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate.

[0078] Specific examples of the alkali (earth) metal sulfonate salts of aromatic sulfonates include potassium sulfonate of benzenesulfonate.

[0079] Specific examples of monomeric or polymeric aromatic sulfonate alkali (earth) metal salts include sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, potassium p-toluenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, and sodium polystyrenesulfonate.

[0080] Specific examples of monomeric or polymeric aromatic sulfonesulfonic acid alkali (earth) metal salts include sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, and dipotassium diphenylsulfone-3,4'-disulfonate.

[0081] Specific examples of the alkali (earth) metal sulfonate salts of aromatic ketones include dipotassium benzophenone-3,3'-disulfonate.

[0082] Specific examples of the alkali (earth) metal salt of heterocyclic sulfonate include disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, and sodium benzothiophene sulfonate.

[0083] Specific examples of the alkali (earth) metal sulfonate salts of aromatic sulfoxides include potassium diphenyl sulfoxide-4-sulfonate.

[0084] Specific examples of the condensation product of an aromatic sulfonate alkali (earth) metal salt with a methylene bond include a formalin condensation product of sodium naphthalenesulfonate, and a formalin condensation product of sodium anthracenesulfonate.

[0085] As the component (C), an alkali (earth) metal salt of a sulfate ester not containing fluorine can be used, and examples of the alkali (earth) metal salt of a sulfate ester include alkali (earth) metal salts of sulfate esters of monohydric or polyhydric alcohols. Specific examples of the sulfate esters of monohydric or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfate esters of polyoxyethylene alkylphenyl ether, mono-, di-, tri- or tetrasulfate esters of pentaerythritol, sulfate esters of lauric acid monoglyceride, sulfate esters of palmitic acid monoglyceride, sulfate esters of stearic acid monoglyceride, etc. Among these, the alkali (earth) metal salts of lauryl sulfate are preferred.

[0086] The component (C) may be used alone, or in combination of two or more types. Of these, potassium diphenylsulfone-3-sulfonate and sodium polystyrenesulfonate are preferred as component (C).

[0087] The blend amount of component (C) is 0.001 to 1.0 part by mass, preferably 0.001 to 0.5 part by mass, more preferably 0.005 to 0.45 part by mass, and even more preferably 0.005 to 0.4 part by mass, per 100 parts by mass of component (A). If the content is less than 0.001 part by mass, flame retardancy cannot be obtained, whereas if the content exceeds 1.0 part by mass, the transparency of the composition decreases and molding defects occur.

[0088] [Other ingredients] The flame-retardant aromatic polycarbonate resin composition of the present invention may contain other components such as thermoplastic resins other than component (A) and additives, provided that the object of the present invention is not impaired.

[0089] Specific examples of thermoplastic resins other than component (A) include general-purpose plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, and polyalkyl methacrylate resin; engineering plastics such as aliphatic polycarbonate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, polyamide resin, cyclic polyolefin resin, and polyarylate resin (amorphous polyarylate, liquid crystal polyarylate); and so-called super engineering plastics such as polyether ether ketone, polyetherimide, polysulfone, polyether sulfone, and polyphenylene sulfide. In addition, thermoplastic elastomers such as styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, polyester-based thermoplastic elastomer, and polyurethane-based thermoplastic elastomer can also be used. These thermoplastic resins can be blended within a range that does not affect flame retardancy.

[0090] Specific examples of additives include reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons, milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc.), flame retardants (halogen-based, Phosphate ester-based, red phosphorus, metal hydrate-based, etc.), heat stabilizers, antioxidants, release agents, ultraviolet absorbers, light stabilizers, lubricants, sliding agents, colorants (pigments, dyes, such as carbon black and titanium oxide), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium oxide, fine particle zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers, photochromic agents, etc. may be blended. Of the various additives used in the flame-retardant aromatic polycarbonate resin composition of the present invention, those containing fluorine are preferably excluded.

[0091] The heat stabilizer may be a phosphorus-based stabilizer, etc. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, phosphate-based compounds may be used.

[0092] Specific examples of the phosphite compound include distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and 4,4'-isopropylidenediphenol tetratridecyl phosphite.

[0093] Specific examples of the phosphonite compound include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-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, and the like.

[0094] A specific example of the phosphate stabilizer is trimethyl phosphate.

[0095] Examples of the antioxidant include phenol-based antioxidants and sulfur-based antioxidants.

[0096] The phenol-based antioxidant can suppress discoloration when exposed to heat and is also effective in improving flame retardancy. Specific examples of phenol-based antioxidants include vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and further include n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate.

[0097] The sulfur-based antioxidant is particularly suitable when the molding method is rotational molding or compression molding. Specific examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodipropionic acid ester, pentaerythritol tetra(β-laurylthiopropionate) ester, bis[2-methyl-4-(3-laurylthiopropionyloxy)-5-tert-butylphenyl]sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole, and 1,1'-thiobis(2-naphthol).

[0098] When these phosphorus-based stabilizers, phenol-based antioxidants, and sulfur-based antioxidants are used, the amount thereof is preferably 0.0001 to 1 part by mass, more preferably 0.0005 to 0.5 parts by mass, and even more preferably 0.001 to 0.2 parts by mass, per 100 parts by mass of component (A).

[0099] Examples of the release agent include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, modified polyolefin waxes, polysiloxanes other than component (B) (e.g., linear or cyclic polydimethylsiloxanes, linear or cyclic polymethylphenylsiloxanes, functional group-modified polysiloxanes, etc.), paraffin wax, beeswax, saturated fatty acid esters (e.g., monoglycerides such as stearic acid monoglyceride, polyglycerol fatty acid esters such as decaglycerol decaglycerate and decaglycerol tetrastearate, lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacate behenate, and erythritol esters such as pentaerythritol tetrastearate), and among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxanes, and linear or cyclic polymethylphenylsiloxanes are preferred.

[0100] When a release agent is used, the amount added is preferably 0.01 to 0.3 parts by mass per 100 parts by mass of the component (A).

[0101] Examples of the ultraviolet absorbing agent include a benzophenone-based ultraviolet absorbing agent, a benzotriazole-based ultraviolet absorbing agent, and a hydroxyphenyltriazine-based ultraviolet absorbing agent.

[0102] Specific examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, and bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane.

[0103] Specific examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole, and 2-(2'-hydroxy-3',5'-bis(α,α'-dimethylbenzyl)phenylbenzotriazole. 2-[2'-hydroxy-3'-(3",4",5",6"-tetraphthalimidomethyl)-5'-methylphenyl]benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2,2'methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], and methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenylpropionate-polyethylene glycol condensate.

[0104] Specific examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, 2-(4,6-bis-(2,4-dimethylphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol, and the like.

[0105] As the light stabilizer, a hindered amine light stabilizer can be used. Specific examples thereof include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2n-butylmalonate, a condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and tridecyl alcohol, and 1, Condensation product of 2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]he hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, poly{[6-morpholino-s-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol, N,N'-bis(3-amino propyl)ethylenediamine and 2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-chloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)diethanol condensate, and polymethylpropyl 3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]siloxane.

[0106] When an ultraviolet absorber and a light stabilizer are used, the amount thereof is preferably 0.01 to 5 parts by mass, and more preferably 0.02 to 1 part by mass, per 100 parts by mass of the component (A).

[0107] In addition, the flame-retardant aromatic polycarbonate resin composition of the present invention can be blended with a bluing agent in order to counteract the yellow coloring resulting from an ultraviolet absorber, etc. As the bluing agent, any agent that is used for polycarbonate resins can be used without any particular problems, but anthraquinone dyes are preferred because they are easily available.

[0108] The method for producing the flame-retardant aromatic polycarbonate resin composition of the present invention is not particularly limited, and any method can be adopted. For example, the components (A) to (C) and other components as necessary are thoroughly mixed using a premixing means such as a hand mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc., and then granulated using an extrusion granulator or a briquetting machine, etc., and then melt-kneaded using a melt kneader typified by a vent-type twin-screw extruder, and pelletized using a device such as a pelletizer.

[0109] Other examples include a method of feeding the components (A) to (C) and, if necessary, other components independently to a melt kneader, such as a vented twin-screw extruder; a method of premixing two or more of the components (A) to (C) and feeding them to the melt kneader independently of the remaining components; a method of diluting the component (B) with an organic solvent and feeding it to the melt kneader; and a method of premixing a mixture of the component (B) diluted with an organic solvent with other components and feeding it to the melt kneader. If any of the components to be blended is liquid, a so-called liquid injection device or liquid addition device can be used to feed the components to the melt kneader. The heating temperature during kneading is not particularly limited, but is preferably, for example, 200 to 350°C.

[0110] [2] Molding method and molded products By injection molding the flame-retardant aromatic polycarbonate resin composition of the present invention, various molded articles can be produced. In injection molding, not only the ordinary cold runner type molding method but also production by a hot runner enabling runnerless is possible. Further, as the injection molding method, gas assist injection molding, injection compression molding, ultra-high speed injection molding, etc. can be used.

[0111] Also, by extrusion molding the flame-retardant aromatic polycarbonate resin composition of the present invention, it can also be used in the form of various shaped extruded articles, sheets, films, etc. Further, for forming sheets and films, an inflation method, a casting method, etc. can also be used.

[0112] Furthermore, the transparent flame-retardant aromatic polycarbonate resin composition of the present invention can also be formed into a heat-shrinkable tube by a stretching operation, and can also be formed into a molded article by rotational molding. The heating temperature during molding is not particularly limited, but it is preferably injection molded at a mold temperature of 60°C or higher, particularly 80 to 120°C. At this time, the resin temperature in injection molding is preferably, for example, 250 to 360°C, more preferably 280 to 330°C.

Examples

[0113] Hereinafter, the present invention will be described in more detail by showing synthesis examples, comparative synthesis examples, examples and comparative examples, but the present invention is not limited to these examples. The physical properties of the organohydrogenpolysiloxane in the following synthesis examples and comparative synthesis examples were measured by the following methods.

[0114] (1) Weight average molecular weight (Mw) It was measured by gel permeation chromatography (GPC) based on standard polystyrene. <GPC measurement conditions> Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Column: TSKgel G4000HXL + G3000HXL + G20 manufactured by Tosoh Corporation 00HXL+G2000HXL (inner diameter 6mm, length 150mm) Developing solution: Tetrahydrofuran Column tank temperature: 40℃ Flow rate: 1mL / min Detector: Refractive Index (RI) Standard: Monodisperse polystyrene (2) Volatile content The mass loss (mass %) was calculated when heated at 150°C for 30 minutes at 1 atmosphere. (3) Chloride ion (Cl - ) and sulfate ion (SO 4 2- )amount 20 g of the obtained organohydrogenpolysiloxane was dissolved in 20 mL of toluene, 20 g of pure water was added, and the mixture was shaken for 2 hours to extract the ions into the aqueous layer. The chloride ions and sulfate ions in the aqueous layer were measured by ion chromatography. (4) Amount of hydrogen gas generated At 25°C, 2 g of organohydrogenpolysiloxane was diluted with 5 mL of 1-butanol, and 10 mL of a 20% by mass aqueous solution of sodium hydroxide was added and stirred. The amount of hydrogen gas generated was quantified using a gas burette, and the amount of hydrogen gas generated was calculated using the following formula. Amount of hydrogen gas generated (mL / g) = [Amount of hydrogen gas measured using a gas burette (mL)] / [Amount of sample (g)] (5) Average composition unit ratio 29 The peak area attributable to each unit in the Si-NMR spectrum was calculated assuming that the total peak area of ​​the siloxane units is 1.

[0115] [1] Synthesis of organohydrogenpolysiloxane [Synthesis Example 1] In a 1L flask equipped with a stirrer, a cooling device, and a thermometer, 75.6g of hexamethyldisiloxane, 62.9g of 1,3,5,7-tetramethylcyclotetrasiloxane, 38.5g of octamethylcyclotetrasiloxane, and 394.0g of diphenyldimethoxysilane were stirred while adding 25.0g of p-toluenesulfonic acid. After cooling to an internal temperature of 10°C, 31.5g of water was added and the mixture was stirred for 5 hours to carry out an equilibration reaction. After that, the toluene layer was repeatedly washed with water until it became neutral, and the resulting toluene solution was concentrated under reduced pressure to obtain organohydrogenpolysiloxane B-1, a colorless, transparent liquid. Organohydrogenpolysiloxane B-1 had Mw of 910, volatile matter of 1.4 mass%, chloride ion and sulfate ion amounts of 1 mass ppm or less each, and hydrogen gas generation rate of 51.0 mL / g. The average constitutional unit ratio was [(R 11 O)(CH 3 ) 2 SiO 1 / 2 ] 0.010 [(CH 3 ) 3 SiO 1 / 2 ] 0.231 [H(CH 3 )SiO 2 / 2 ] 0.332 [(C 6 H 5 ) 2 SiO 2 / 2 ] 0.305 [(CH 3 ) 2 SiO 2 / 2 ] 0.122 (R 11 : methyl group or hydrogen atom).

[0116] [Synthesis Example 2] In a 1 L flask equipped with a stirrer, a cooling device, and a thermometer, 154.6 g of water, 3.6 g of toluene, and 2.2 g of hexane were stirred at an internal temperature of 80° C. while a mixture of 94.4 g of phenyltrichlorosilane, 55.6 g of diphenyldichlorosilane, and 5.5 g of dimethyldichlorosilane was added dropwise using a dropping funnel over 2 hours, and then 23.2 g of toluene was added, 20.1 g of dimethylchlorosilane was added dropwise, and 38.0 g of hot water at 70° C. was added and stirred for 1 hour at 70° C. After the reaction was completed, 111.0 g of toluene was added, and the toluene layer was washed with water until it became neutral. The resulting toluene solution was concentrated under reduced pressure, and the resulting white solid was powdered using a mill mixer to obtain organohydrogenpolysiloxane B-2. Organohydrogenpolysiloxane B-2 has Mw of 8,000, volatile matter of 0.3 mass%, chloride ion and sulfate ion amounts of 1 mass ppm or less each, and hydrogen gas generation rate of 32.7 mL / g. The average constitutional unit ratio is [(R 11 O)(CH 3 ) 2 SiO 1 / 2 ] 0.023 [H(CH 3 ) 2 SiO 1 / 2 ] 0.184 [(C 6 H 5 ) 2 SiO 2 / 2 ] 0.246 [(CH 3 ) 2 SiO 2 / 2 ] 0.047 [C 6 H 5 SiO 3 / 2 ] 0.500 (R 11 : methyl group or hydrogen atom).

[0117] [Comparative Synthesis Example 1] The same procedure as in Synthesis Example 1 was carried out, except that 15 g of sulfuric acid was used instead of p-toluenesulfonic acid, to obtain organohydrogenpolysiloxane BR-1 in the form of a colorless, transparent liquid. Organohydrogenpolysiloxane BR-1 has Mw of 890, volatile matter of 1.9 mass%, chloride ion and sulfate ion amounts of 1 mass ppm or less, and hydrogen gas generation rate of 49.0 mL / g. The average constitutional unit ratio is [(CH 3 ) 3 SiO 1 / 2 ] 0.255 [H(CH 3 )SiO 2 / 2 ] 0.329 [(C 6 H 5 ) 2 SiO 2 / 2 ] 0.279 [(CH 3 ) 2 SiO 2 / 2 ] 0.137 It was.

[0118] [Comparative Synthesis Example 2] The same procedure as in Synthesis Example 2 was carried out, except that 21.5 g of trimethylchlorosilane was used instead of dimethylchlorosilane, to obtain organopolysiloxane BR-2 as a white powder. Organopolysiloxane BR-2 has Mw of 6,800, volatile matter of 0.5 mass%, chloride ion and sulfate ion amounts of 1 ppm or less, and hydrogen gas generation rate of 0 mL / g. The average constitutional unit ratio is [(CH 3 ) 3 SiO 1 / 2 ] 0.230 [(C 6 H 5 ) 2 SiO 2 / 2 ] 0.262 [(CH 3 ) 2 SiO 2 / 2 ] 0.062 [C 6 H 5 SiO 3 / 2 ] 0.446 It was.

[0119] [Comparative Synthesis Example 3] The same procedure as in Synthesis Example 2 was carried out except that the amount of water was changed to 188.9 g and the amount of dimethylchlorosilane was changed to 11.6 g, thereby obtaining a white powder of organohydrogenpolysiloxane BR-3. Organohydrogenpolysiloxane BR-3 has Mw of 11,500, volatile matter of 0.2 mass%, chloride ion and sulfate ion amounts of 1 ppm or less, and hydrogen gas generation rate of 30.8 mL / g. The average constitutional unit ratio is [(R 11 O)(CH 3 ) 2 SiO 1 / 2 ] 0.013 [H(CH 3 ) 2 SiO 1 / 2 ] 0.102 [(C 6 H 5 ) 2 SiO 2 / 2 ] 0.314 [(CH 3 ) 2 SiO 2 / 2 ] 0.109 [C 6 H 5 SiO 3 / 2 ] 0.462 (R 11 : methyl group or hydrogen atom).

[0120] [2] Production of polycarbonate resin composition [Examples 1 to 7 and Comparative Examples 1 to 6] The following components were mixed to prepare a resin composition. Specifically, first, each of the (A) components was pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, the A-1 to A-6 components were weighed out in the composition ratios (parts by mass) shown in Tables 2 and 3 and supplied to the first hopper. Also, a mixture of the A-7 component, the (B) component, the (C) component, and the (D) component mixed in a mixer was supplied to the second hopper. The components in each hopper were fed from a gravimetric weighing single-screw feeder (KS60 manufactured by K-Tron Co., Ltd.), and a resin composition was prepared using a co-rotating twin-screw extruder (OMega30H manufactured by STEER Co., Ltd.). A strand was extruded under the condition of a barrel set temperature of 280°C, cooled in a water bath, and then strand cut with a pelletizer to pelletize. The extrusion conditions were as follows. Discharge rate: 20 kg / h, screw speed: 150 rpm, resin temperature: 308°C, torque: 150-180 N·m, resin pressure: 2.1-2.5 MPa

[0121] The obtained pellets were dried in a hot air circulation dryer at 120°C for 6 hours, and molded into a molded product with a thickness of 2 mm using an electric injection molding machine (J100ADS-110 manufactured by The Japan Steel Works, Ltd.) at a cylinder temperature of 280 to 300°C and a mold temperature of 83°C. The injection conditions were as follows: Filling speed: 30mm / s, injection pressure: 155~165MPa, injection time: 0.7 seconds, holding pressure: 140MPa, holding pressure speed: 30mm / s, injection holding pressure time: 3 seconds, holding pressure time: 2.3 seconds, clamping force: 1000kN

[0122] Component (A) A-1: Branched polycarbonate resin (Novarex M-7027U pellets, MVR 2.9 cm, manufactured by Mitsubishi Engineering Plastics Corporation) 3 / 10 minutes) A-2: Branched polycarbonate resin (Novarex M-7025U pellets, MVR 8cm, manufactured by Mitsubishi Engineering Plastics Corporation) 3 / 10 minutes) A-3: Polymeric polycarbonate resin (Teijin Ltd. Panlite K-1300Y pellets, MVR 2.8 cm 3 / 10 minutes) A-4: Polymeric polycarbonate resin (Idemitsu Kosan Co., Ltd. Toughlon IR-2500 pellets, MVR 8 cm 3 / 10 minutes) A-5: Standard polycarbonate resin (Mitsubishi Engineering Plastics Corporation, Iupilon S-3000N pellets, MVR 14 cm 3 / 10 minutes) A-6: Bisphenol A polycarbonate resin pellets (MVR14cm) derived from recycled water bottles 3 / 10 minutes) A-7: Standard polycarbonate resin (Idemitsu Kosan Co., Ltd. Toughlon FN-2200 flakes, MVR 12 cm 3 / 10 minutes)

[0123] (B) Component B-1: Organohydrogenpolysiloxane obtained in Synthesis Example 1 B-2: Organohydrogenpolysiloxane obtained in Synthesis Example 2 BR-1: Organohydrogenpolysiloxane obtained in Comparative Synthesis Example 1 BR-2: Organopolysiloxane obtained in Comparative Synthesis Example 2 BR-3: Organohydrogenpolysiloxane obtained in Comparative Synthesis Example 3

[0124] (C) Component C-1: Potassium diphenylsulfonate (KSS-FR, Arichem) C-2: Sodium polystyrene sulfonate (VERSA-TL502 manufactured by Nouryon)

[0125] (D) Ingredients (other ingredients) D-1: Phosphate-based antioxidant (ADEKA STAB PEP-36, manufactured by ADEKA Corporation) D-2: Phenol-based antioxidant (ADEKA STAB AO-50 manufactured by ADEKA Corporation) D-3: Special fatty acid ester release agent (Rikestar EW-440, manufactured by Riken Vitamin Co., Ltd.)

[0126] [3] Evaluation of molded product characteristics The following properties were evaluated for the obtained molded product having a thickness of 2 mm. The results are shown in Tables 2 and 3. (6) Transparency (haze) The transparency of the molded product was measured by haze value in accordance with JIS K7105. (7) UL Standard 94 Vertical Flame Test A vertical flame test according to UL Standard 94 was conducted using a rectangular molded product with a length of 127 mm, width of 13 mm and thickness of 2 mm, which was manufactured according to the US UL standard. The flame of a burner was applied to the bottom end of the test piece held vertically for 10 seconds, and the flame retardancy was evaluated based on the flaming time and dripping property (cotton ignition due to dripping) according to the criteria shown in Table 1. Here, the flaming time is the length of time that the test specimen continues to burn with a flame after the ignition source is removed. Cotton ignition due to dripping is determined by whether or not the cotton marking located about 300 mm below the bottom end of the test specimen is ignited by dripping from the test specimen. Five test specimens were used for one molding material, and the flaming time was evaluated as the total time for the five specimens. Cotton ignition due to dripping was evaluated as "no ignition" if no ignition was observed in any of the five specimens.

[0127] [Table 1]

[0128] [Table 2]

[0129] [Table 3]

[0130] As shown in Table 2, the flame-retardant aromatic polycarbonate resin compositions of Examples 1 to 7 are excellent in flame retardancy. On the other hand, as shown in Table 3, in Comparative Example 1 in which component (B) was not blended, and in Comparative Example 2 in which component (C) was not blended, cotton ignition due to dripping occurred. In addition, the component (B) is a structural unit [(R 1 O)(R 2 ) 2 SiO 1 / 2 In Comparative Examples 3 and 4, in which the composition was changed to BR-1 and BR-2, which did not contain the above, ignition of cotton due to dripping occurred. In addition, the MVR is 8cm 3 In Comparative Example 5, in which only an aromatic polycarbonate resin was used, ignition of cotton due to dripping was observed even when the drying time exceeded 10 minutes. In Comparative Example 6, in which component (B) was changed to an organohydrogenpolysiloxane having a weight average molecular weight of more than 10,000, no cotton ignition due to dripping occurred, but the flaming combustion time was long, resulting in poor flame retardancy.

[0131] As is apparent from the above, the flame-retardant aromatic polycarbonate resin composition of the present invention contains at least one flame retardant selected from organopolysiloxane, organic alkali metal salt, and organic alkaline earth metal salt, and thus has good drip prevention performance and excellent transparency. The flame-retardant aromatic polycarbonate resin composition of the present invention has the advantage of being substantially free of fluorinated organic compounds. In addition, the resin composition of the present invention has high thermal stability even when melted at high temperatures during injection molding, etc. Therefore, it is extremely useful not only for lighting covers and protective covers for transmission type displays, but also for various industrial applications such as office automation equipment and electrical and electronic equipment, and the industrial effects it provides are extremely large.

Claims

1. (A) aromatic polycarbonate resin: 100 parts by mass, (B) 0.1 to 10 parts by mass of an organohydrogenpolysiloxane having a weight average molecular weight of 700 to 10,000 and represented by the following formula (1): (C) At least one selected from the group consisting of fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts: 0.001 to 1.0 parts by mass A flame-retardant aromatic polycarbonate resin composition comprising: The melt volume flow rate (MVR) measured according to ISO1133-1 at 300°C and a load of 1.2 kg is 2 to 8 cm 3 % or more by mass of an aromatic polycarbonate resin having a flame retardant viscosity of 10 / 10 minutes, based on the total mass of component (A). [(R 1 O)(R 2 ) 2 SiO 1 / 2 ] a [(R 3 ) 3 SiO 1 / 2 ] b [ (H) (R). 4 )SiO 2 / 2 ] c [ (Ar) x (R 5 ) 2-x SiO 2 / 2 ] d [(R 6 ) 2 SiO 2 / 2 ] e [(R 7 )SiO 3 / 2 ] f (1) (In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, R 4 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, Each Ar is independently an aryl group having 6 to 12 carbon atoms; R 5 and R 6 are each independently an alkyl group having 1 to 6 carbon atoms, R 7 each independently represents an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may be substituted with an epoxy group, an amino group, an acryloyl group, a methacryloyl group, or a thiol group. x represents 1 or 2; a is a number satisfying 0<a≦0.03, b is a number satisfying 0<b≦0.30, c is a number satisfying 0≦c≦0.45, d is a number satisfying 0.20≦d≦0.70, e is a number satisfying 0≦e≦0.20, f is a number satisfying 0≦f≦0.70, a+b+c+d+e+f is 1. However, when c is 0, R 2 and R 3 At least one of is a hydrogen atom.)

2. 2. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein, in the formula (1), Ar is a phenyl group, x is 2, and f is 0.

3. 2. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein said component (C) is an alkali metal salt of a fluorine-free aromatic sulfonic acid or an alkaline earth metal salt of a fluorine-free aromatic sulfonic acid.

4. A molded article made from the flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3.

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