Flame-retardant aromatic polycarbonate resin master batch and method for manufacturing same

Abstract

Provided is a flame-retardant aromatic polycarbonate resin master batch containing: (A) an aromatic polycarbonate resin; (B) an organohydrogenpolysiloxane represented by formula (1) and having a weight average molecular weight of 700 to 7,000; and (C) (i) an additive selected from phosphorus-based antioxidants and the like. The flame-retardant aromatic polycarbonate resin master batch contains 20 mass% or more, relative to a total mass of the component (A), of an aromatic polycarbonate resin having an MVR, as measured at 300°C under a load of 1.2 kg in accordance with ISO 1133-1, of 2 to 8 cm3 / 10 minutes.　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 (R1 to R7 is an alkyl group or the like, Ar is an aryl group, x is 1 or 2, a is 0 < a ≤ 0.03, b is 0 < b ≤ 0.30, c is 0 ≤ c ≤ 0.45, d is 0.20 ≤ d ≤ 0.70, e is 0 ≤ e ≤ 0.20, f is 0 ≤ f ≤ 0.70, and a + b + c + d + e + f is 1.)

Description

Flame-retardant aromatic polycarbonate resin masterbatch and method for manufacturing the same

[0001] The present invention relates to a flame-retardant aromatic polycarbonate resin masterbatch and a method for producing the same, and more specifically, to a masterbatch formulated to impart flame retardancy to an aromatic polycarbonate resin, a method for producing the same, a flame-retardant aromatic polycarbonate resin composition using the same, and a molded article thereof.

[0002] Aromatic polycarbonate resins are formed into various molded products using 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, exemplified by their high light transmittance and extremely low haze. In these applications, light sources such as fluorescent lamps and incandescent bulbs become hot, or when used in bathrooms or outdoors, they are exposed to high humidity. Therefore, it is necessary for the resin to maintain its transparency, hue, and mechanical properties even when exposed to heat and humidity, and in addition to the transparency of the resin, the heat and humidity resistance of the resin is considered important.

[0003] Furthermore, in recent years, flame retardancy in the event of a fire has also attracted attention for these applications, and there is a demand for resin compositions that provide cured products with high flame retardancy in addition to the above-mentioned properties. Conventionally, flame-retardant aromatic polycarbonate resin compositions by adding halogen-based compounds or phosphorus-based compounds have been proposed as a method for imparting flame retardancy to aromatic polycarbonate resins, and these are used in office automation equipment, home appliances, etc., where there is a strong demand for flame retardancy. On the other hand, flame-retardant aromatic polycarbonate resin compositions containing components that replace these flame retardants have been developed and are being used in the products mentioned above. The purpose of this change in flame retardants is to suppress the generation of corrosive gases during molding and to improve the recyclability of the product.

[0004] As a new flame retardant to replace the flame retardants mentioned above, silicone compounds can be cited as an example. Flame retardant resin compositions in which silicone compounds are blended with aromatic polycarbonate resins have been actively studied in recent years, and various proposals have been made.

[0005] For example, Patent Document 1 proposes a method of compounding a polycarbonate resin with an alkali (earth) metal salt of perfluoroalkanesulfonic acid and an organic siloxane having an alkoxy group, a vinyl group and a phenyl group, while Patent Document 2 proposes a method of compounding a polycarbonate resin with 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.

[0006] Furthermore, Patent Document 3 proposes a method of blending a specific petroleum-based heavy oil or pitch and a silicone compound into a polycarbonate resin component, and Patent Document 4 proposes a method of blending a non-silicone resin having an aromatic ring with formula R 0 2SiO 1.0 (R 0 represents a monovalent hydrocarbon group. The same applies below.) and R 0 SiO 1.5 Methods have been proposed for incorporating silicone resins having the constituent units shown and a weight-average molecular weight of 10,000 to 270,000.

[0007] However, the polycarbonate resin composition proposed above did not exhibit sufficient transparency or flame retardancy after curing. In particular, problems arose such as dripping in the case of thin walls, failing to achieve the V-0 rank of UL standard 94; insufficient dispersion of silicone components resulting in clouding of molded products; and reduced transparency after moist heat treatment due to the aggregation of silicone components.

[0008] On the other hand, Patent Document 5 specifically proposes a resin composition to which an organic alkali metal salt and poly(methylhydrogen siloxane) are added to an aromatic polycarbonate resin. However, this resin composition itself becomes cloudy, and dispersion defects such as peeling occur on the surface of the molded product, resulting in insufficient transparency.

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

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

[0011] The aforementioned patent documents often use polytetrafluoroethylene, which has fibril-forming ability, as a drip inhibitor. However, when polytetrafluoroethylene is blended with aromatic polycarbonate resin, the molded product becomes cloudy due to the incompatibility of polytetrafluoroethylene and aromatic polycarbonate resin. Furthermore, while metal organic sulfonic acid salts, specifically potassium perfluorobutanesulfonate, are commonly used as flame retardants, they also have the drawback of becoming cloudy due to their incompatibility with aromatic polycarbonate resin.

[0012] Meanwhile, in recent years, fluorine compounds have become subject to 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 regulations on organofluorine compounds (PFAS), such as perfluoro and polyfluoroalkyl compounds represented by polytetrafluoroethylene, are also progressing, mainly in Europe and the United States.

[0013] Furthermore, because silicone resins generally have low surface tension, they tend to have poor compatibility with thermoplastic resins such as aromatic polycarbonates, making uniform dispersion difficult. This tendency is particularly strong in liquid silicone resins with low molecular weights; even when a predetermined amount of silicone resin is kneaded, the silicone resin concentration in the resulting pellets decreases and the variation increases. Therefore, Patent Document 9 proposes a thermoplastic organic resin masterbatch that suppresses the drawbacks unique to silicone resins and can impart flame retardancy easily and uniformly through kneading. However, the only silicone resins used in this invention are solids at room temperature, limiting the use of silicone resins with relatively low molecular weights that are liquid at room temperature.

[0014] JP-A-6-306265 JP-A-6-336547 JP-A-9-169914 JP-A-10-139964 JP-A-60 -38419 Publication Patent No. 3779623 Publication Patent No. 3779624 Publication JP 2019-19191 Publication Patent No. 3608607 Publication

[0015] Therefore, in order to comply with the above-mentioned PFBS and PFAS regulations, there is a strong need for polycarbonate resin compositions that exhibit excellent flame retardancy without relying on perfluorobutanesulfonic acid metal salts or polytetrafluoroethylene. However, achieving flame retardancy (V-0 according to UL-94 standards) without using perfluorobutanesulfonic acid and its metal salts, which are effective flame retardants, and polytetrafluoroethylene, which is an effective drip inhibitor, is not easy.

[0016] Furthermore, solid silicone resins require a separate powdering process, and the powder can fuse together and form clumps during storage, and there is a risk of dust explosions, making them difficult to handle. In the case of liquid silicone resins, shear is difficult to achieve during mixing, and they are prone to volatilization from vents, making it difficult to uniformly disperse the liquid silicone resin in the specified amount.

[0017] The present invention was made to solve the above problems, and aims to provide a flame-retardant aromatic polycarbonate resin masterbatch and a method for producing the same, which can easily and uniformly disperse a specific silicone resin in an aromatic polycarbonate resin, and a flame-retardant aromatic polycarbonate resin composition that, using the flame-retardant aromatic polycarbonate resin masterbatch, can provide molded articles with excellent transparency and flame retardancy with excellent prevention of resin drip during combustion, without the use of fluorine compounds.

[0018] As a result of intensive studies to achieve the above object, the present inventors have found that a flame-retardant aromatic polycarbonate resin masterbatch containing an aromatic polycarbonate resin, a specific organohydrogenpolysiloxane, and a specific additive can easily and uniformly disperse a specific silicone resin in the aromatic polycarbonate resin, and provides a flame-retardant aromatic polycarbonate resin composition excellent in transparency after curing and drip prevention of the resin during combustion, thus completing the present invention.

[0019] That is, the present invention provides: 1. A flame-retardant aromatic polycarbonate resin masterbatch containing (A) 100 parts by mass of an aromatic polycarbonate resin, (B) 5 to 30 parts by mass of an organohydrogenpolysiloxane represented by the following formula (1) and having a weight average molecular weight of 700 to 7,000, and (C) at least one additive selected from the group consisting of (i) a phosphorus-based antioxidant, (ii) a phenolic antioxidant, (iii) a lubricant not containing fluorine, (iv) an organic alkali metal salt not containing fluorine, and (v) an organic alkaline earth metal salt not containing fluorine: 0.001 to 10 parts by mass, wherein the melt volume flow rate (MVR) measured at 300 °C and a load of 1.2 kg in accordance with ISO 1133-1 is 2 to 8 cm 3 / 10 min, and containing 20% by mass or more of the aromatic polycarbonate resin with respect to the total mass of the component (A). [[(R 1 O)(R 2 )2SiO 1 / 2 ] a [(R <​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​1 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2 and R 3 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group, and R 4 R is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and Ar is independently an aryl group having 6 to 12 carbon atoms. 5 and R 6 Each of these is an alkyl group having 1 to 6 carbon atoms, and R 7 Each of these is an alkyl group having 1 to 8 carbon atoms, which may be substituted with an alkenyl group having 2 to 8 carbon atoms, an aryl or epoxy group having 6 to 12 carbon atoms, 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, and f is a number satisfying 0 ≤ f ≤ 0.70, and a + b + c + d + e + f is 1. However, when c is 0, R 2 and R 3One or more of them are hydrogen atoms.) 2. A flame-retardant aromatic polycarbonate resin masterbatch according to 1, wherein in formula (1), Ar is a phenyl group, x is 2, and f is 0. 3. A flame-retardant aromatic polycarbonate resin masterbatch according to 1 or 2, wherein the weight-average molecular weight of component (B) is 700 to 3,000. 4. A flame-retardant aromatic polycarbonate resin masterbatch according to any one of 1 to 3, wherein component (C) contains an alkali metal salt of an aromatic sulfonic acid that does not contain fluorine or an alkaline earth metal salt of an aromatic sulfonic acid that does not contain fluorine. 5. A method for producing a flame-retardant aromatic polycarbonate resin masterbatch according to any one of 1 to 4, comprising: (I) preparing a twin-screw extruder comprising a first feeder installed at the uppermost part of the raw material flow path, a second feeder installed at the same position as the first feeder or downstream thereof, a third feeder installed downstream of the second feeder, a barrel having an outlet equipped with a vacuum vent and a die, and a screw housed in the barrel; (II) supplying component (A) from the first feeder, component (C) from the second feeder, and component (B) from the third feeder into the barrel; (III) heating components (A), (B), and (C) supplied into the barrel at a temperature of 200 to 290°C in the barrel, and transporting the mixture from upstream to downstream in the barrel while kneading it with the screw while adjusting the vacuum level to -0.01 to -0.05 MPa using a vacuum vent, 6. A method for producing a flame-retardant aromatic polycarbonate resin masterbatch, comprising the steps of: (IV) passing the kneaded material through the die to obtain strands; (V) cooling the strands; and (VI) cutting the cooled strands to obtain masterbatch pellets. 7. A flame-retardant aromatic polycarbonate resin composition comprising: (A') 100 parts by mass of aromatic polycarbonate resin; (B') 2 to 70 parts by mass of the flame-retardant aromatic polycarbonate resin masterbatch according to any one of 1 to 4; and (C') 0 to 2.0 parts by mass of at least one selected from organic alkali metal salts that do not contain fluorine and organic alkaline earth metal salts that do not contain fluorine. 8. A molded article molded from the flame-retardant aromatic polycarbonate resin composition according to 6.

[0020] By using the flame-retardant aromatic polycarbonate resin masterbatch of the present invention, the silicone resin can be easily and uniformly dispersed in the aromatic polycarbonate resin. As a result, an aromatic polycarbonate resin composition exhibiting excellent transparency and flame retardancy, and capable of complying with PFAS regulations, can be obtained without the use of fluorine compounds.

[0021] This is a schematic diagram showing an example of a vented twin-screw melt-mixing extruder for producing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention. This is another example of a vented twin-screw melt-mixing extruder for producing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention, and is a schematic diagram showing the configuration and set temperature of the melt-mixing extruder used in Examples 1-1, 1-4, Comparative Example 1-1, and Comparative Examples 1-3 to 1-6. This is yet another example of a vented twin-screw melt-mixing extruder for producing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention, and is a schematic diagram showing the configuration and set temperature of the melt-mixing extruder used in Examples 1-2, 1-3 and Comparative Example 1-2.

[0022] The present invention will be described in detail below. [1] Flame-retardant aromatic polycarbonate resin masterbatch The flame-retardant aromatic polycarbonate resin masterbatch of the present invention contains the following components (A) to (C): (A) Aromatic polycarbonate resin (B) Organohydrogenpolysiloxane represented by formula (1) (C) At least one additive selected from the group consisting of (i) phosphorus-based antioxidants, (ii) phenol-based antioxidants, (iii) lubricants that do not contain fluorine, (iv) organic alkali metal salts that do not contain fluorine, and (v) organic alkaline earth metal salts that do not contain fluorine

[0023] [Component (A)] Component (A) in the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is an aromatic polycarbonate resin. For example, it can be obtained by reacting a divalent phenol with a carbonate precursor by interfacial polycondensation or molten transesterification, or by polymerizing a carbonate prepolymer by solid-phase transesterification, or by polymerizing a cyclic carbonate compound by ring-opening polymerization.

[0024] Specific examples of divalent phenols used here 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) roxy-3,5-dimethyl)phenyl}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) (Loxyphenyl)-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-di Examples include sopropylbenzene, 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, which can be used individually or in combination of two or more.

[0025] 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. 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 preferred.

[0026] Examples of carbonate precursors include carbonyl halides, carbonate esters, and haloformates. Specific examples include phosgene, diphenyl carbonate, and dihaloformates of divalent phenols.

[0027] When producing polycarbonate resin by reacting the above-mentioned divalent phenol with a carbonate precursor by interfacial polycondensation or molten transesterification, catalysts, end-terminating agents, divalent phenol antioxidants, etc., may be used as needed.

[0028] Furthermore, the polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic bifunctional carboxylic acid, or it may be a mixture of two or more of the obtained polycarbonate resins.

[0029] Specific examples of polyfunctional aromatic compounds with three or more functions include phloroglucin, phloroglucid, 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, and 4-{4-[1,1-bis(4-hydroxyphenyl Examples include trisphenols such as ethyl]benzene-α,α-dimethylbenzylphenol; tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 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.

[0030] When the above-mentioned polyfunctional compound that produces the branched polycarbonate resin is included, its proportion is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.5 mol%, and even more preferably 0.01 to 0.3 mol%, of the total amount of aromatic polycarbonate. Furthermore, especially in the case of the melt transesterification method, a branched structure may be formed as a side reaction, but the amount of this branched structure is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.5 mol%, and even more preferably 0.01 to 0.3 mol%, of the total amount of aromatic polycarbonate. Note that this proportion is as follows: 1 It can be calculated by H-NMR measurement.

[0031] The reaction by interfacial polycondensation is typically a reaction between a divalent phenol and phosgene, carried out in the presence of an acid binder and an organic solvent. Specific examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Specific examples of organic solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. To accelerate the reaction, catalysts such as tertiary amines, quaternary ammonium compounds, and quaternary phosphonium compounds, such as triethylamine, tetra-n-butylammonium bromide, and tetra-n-butylphosphonium bromide, can also be used. The reaction conditions are not particularly limited; for example, the reaction temperature is usually 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 higher.

[0032] In the polymerization reaction described above, end-terminating agents are typically used. Monofunctional phenols can be used as such end-terminating agents. Monofunctional phenols are commonly used as end-terminating agents to adjust molecular weight, and specific examples of monofunctional phenols include phenols or lower alkyl-substituted phenols, for example, monofunctional phenols represented by the following general formula (2).

[0033] (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 from 1 to 5, preferably from 1 to 3.)

[0034] Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol, and isooctylphenol.

[0035] Other monofunctional phenols include phenols or benzoic acid chlorides having long-chain alkyl groups or aliphatic polyester groups as substituents, and long-chain alkylcarboxylic acid chlorides. Among these, phenols having long-chain alkyl groups represented by the following general formulas (3) and (4) as substituents are preferably used.

[0036] (In the formula, n represents an integer between 10 and 50.)

[0037] (In the formula, E is -R-O-, -R-C(=O)-O-, or -R-O-C(=O)-, R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5, and n represents an integer from 10 to 50.)

[0038] The substituted phenols represented by the above general formula (3) are preferably those in which n is 10 to 30, and more preferably those in which n is 10 to 26. Specific examples include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, triacontylphenol, and the like.

[0039] The substituted phenols represented by the above general formula (4) are preferably compounds in which E is -R-C(=O)-O- and R is a single bond, and n is preferably 10 to 30, particularly 10 to 26. Specific examples include decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate, and triacontyl hydroxybenzoate. These end-stoppers may be used alone or in combination of two or more.

[0040] The reaction by molten transesterification is typically a transesterification reaction between a divalent phenol and a carbonate ester. For example, it is carried out by heating and mixing the divalent phenol and the carbonate ester 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 resulting alcohol or phenol, but is generally preferred between 120 and 350°C. In the later stages of the reaction, it is preferable to reduce the pressure of the system to about 1.33 × 10³ to 13.3 Pa to facilitate the distillation off of the resulting alcohol or phenol. The reaction time is generally preferred between 1 and 4 hours.

[0041] Examples of carbonate esters include esters of aryl groups having 6 to 10 carbon atoms, aralkyl groups having 7 to 10 carbon atoms, and alkyl groups having 1 to 4 carbon atoms, which may be substituted. Specific examples include diphenyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate, with diphenyl carbonate being the most preferred.

[0042] Furthermore, a polymerization catalyst can be used to accelerate the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salts and potassium salts of divalent 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, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds, which are catalysts commonly used in esterification and transesterification reactions. The catalysts may be used individually or in combination of two or more types. The amount of these polymerization catalysts used is preferably 1 × 10⁻⁶ per mole of divalent phenol used as a raw material. -8 ~1 x 10 -3 Equivalent, more preferably 1 × 10 -7 ~5 x 10 -4 Selected within the range of equivalents.

[0043] Furthermore, in order to reduce the phenolic terminal groups in the polymerization reaction, compounds such as bis(chlorophenyl) carbonate, bis(bromophenyl) carbonate, bis(nitrophenyl) carbonate, bis(phenylphenyl) carbonate, chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate, and ethoxycarbonylphenylphenyl carbonate can be added in the later stages or after the completion of the polycondensation reaction. Among these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is more preferred.

[0044] Furthermore, it is preferable to use an inactivator to neutralize the activity of the catalyst in the polymerization reaction. Specific examples of such inactivators include, for example, 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 also naphthalenesulfonic acid, sulfonated polystyrene, methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonic acid-2-phenyl-2-propyl, dodecylbenzenesulfonic acid-2-phenyl-2-butyl, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, and tetraethylphosphonium dodecylbenzenesulfonate. Examples of compounds that can be used include, but are not limited to, tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, 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, phosphonium salts or ammonium salts are preferred.

[0045] The amount of these deactivators is preferably 0.5 to 50 moles per mole of remaining catalyst, and preferably 0.01 to 500 ppm relative to the polymerized polycarbonate resin, more preferably 0.01 to 300 ppm, and even more preferably 0.01 to 100 ppm.

[0046] (A) The molecular weight of the aromatic polycarbonate resin is not particularly limited, but from the viewpoint of mechanical properties at high temperatures and moldability, 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 determined by measuring the intrinsic viscosity [η] of a methylene chloride solution at 20°C and using Schnell's formula ([η] = 1.23 × 10⁻¹⁰). -5 It can be calculated from ×Mv0.83). Also, component (A) may be used alone or in combination of two or more types.

[0047] (A) As components, commercially available products can be used, for example, Novalex M-7027U, M-7025U (branched polycarbonate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd.), Panlite K-1300Y (polymer polycarbonate resin manufactured by Teijin Limited), Toughlon IR-2500 (polymer polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd.), FN-2200 (standard polycarbonate resin manufactured by Idemitsu Kosan Co., Ltd.), Yupiron S-3000N (standard polycarbonate resin manufactured by Mitsubishi Engineering Plastics Co., Ltd.).

[0048] Generally, commercially available polymeric and branched aromatic polycarbonate resins are preferred because they tend to have a low melt volume flow rate (MVR), an indicator of fluidity and moldability, and have a high viscosity-average molecular weight. Component (A) in the flame-retardant aromatic polycarbonate resin composition of the present invention has an MVR of 2 to 8 cm² at 300°C and a 1.2 kg load according to ISO 1133-1. 3The aromatic polycarbonate resin, which is 20% by mass or more of the total mass of component (A), is present, preferably 30% by mass or more, and more preferably 50% by mass or more. If the amount of such aromatic polycarbonate resin is less than 20% by mass, drip resistance cannot be obtained. There is no particular upper limit, but 95% by mass or less is preferred, and 90% by mass or less is more preferred. Also, the MVR is 2 cm 3 / With less than 10 minutes, fluidity is insufficient and moldability tends to be poor, 8cm 3 Exceeding this limit will reduce shock resistance and other properties.

[0049] Furthermore, the aromatic polycarbonate resin of component (A) is preferably one that does not contain a halogen-substituted skeleton such as a halogen-substituted divalent phenol in its molecule.

[0050] Furthermore, the aromatic polycarbonate resin of component (A) may include aromatic polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin), or aromatic polycarbonate resin manufactured from aromatic polycarbonate resin that has been chemically decomposed and returned to its raw materials (so-called chemical-recycled polycarbonate resin).

[0051] [Component (B)] Component (B) in the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is an organohydrogenpolysiloxane having a constituent unit ratio represented by the following formula (1). [(R 1 O) (R 2 ) 2SiO 1 / 2 ] a [(R 3 ) 3SiO 1 / 2 ] b [(H)(R 4 ) SiO 2 / 2 ] c [(Ar)] x (R 5 ) 2-x SiO 2 / 2 ] d [(R 6 ) 2SiO 2 / 2 ] e [(R 7 ) SiO 3 / 2 ]f (1)

[0052] In the formula, R 1 R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 2 and R 3 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group, and R 4 is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and Ar is independently an aryl group having 6 to 12 carbon atoms, and R 5 and R 6 Each of these is an alkyl group having 1 to 6 carbon atoms, and R 7 Each of these is 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 that 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, and f is a number satisfying 0 ≤ f ≤ 0.70, and a + b + c + d + e + f is 1. However, when c is 0, R 2 and R 3 One or more of them are hydrogen atoms.

[0053] R 1 Specific examples of alkyl groups having 1 to 3 carbon atoms include methyl, ethyl, and propyl groups, and among them, R 1 Preferably, this is a hydrogen atom or a methyl group.

[0054] R 2 and R 3 As for the alkyl group having 1 to 6 carbon atoms, 1 to 3 carbon atoms are preferred, and specific examples include methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. As for the aryl group having 6 to 12 carbon atoms, 6 to 10 carbon atoms are preferred, and specific examples include phenyl, tolyl, xylyl, and naphthyl groups. Among these, R 2 and R 3Preferably, it is a hydrogen atom, a methyl group, or a phenyl group, more preferably a methyl group.

[0055] R 4 Specific examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms for R 2 and R 3 are the same as the groups exemplified for R 4 Preferably, it is a methyl group or a phenyl group, more preferably a methyl group.

[0056] The aryl group having 6 to 12 carbon atoms represented by Ar preferably has 6 to 10 carbon atoms, and specific examples thereof are the same as the aryl groups exemplified for R 2 and R 3 Among them, preferably, it is a phenyl group.

[0057] R 5 and R 6 The alkyl group having 1 to 6 carbon atoms for R 2 and R 3 Preferably has 1 to 3 carbon atoms, and specific examples thereof are the same as the groups exemplified for R

[0058] R 7 The alkenyl group having 2 to 8 carbon atoms for R preferably has 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, butenyl, hexenyl, octenyl groups, etc. Specific examples of the aryl group having 6 to 12 carbon atoms are the same as the aryl groups exemplified for R 2 and R 3 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, etc. Among them, R 7Preferably, it is 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 even more preferably a phenyl group.

[0059] a is a number satisfying 0 < a ≦ 0.03, preferably a number satisfying 0.005 ≦ a ≦ 0.25. b is a number satisfying 0 < b ≦ 0.30, preferably a number satisfying 0.01 ≦ b ≦ 0.25. c is a number satisfying 0 ≦ c ≦ 0.45, preferably a number satisfying 0.1 ≦ c ≦ 0.40. d is a number satisfying 0.20 ≦ d ≦ 0.70, preferably a number satisfying 0.22 ≦ d ≦ 0.40. e is a number satisfying 0 ≦ e ≦ 0.20, preferably a number satisfying 0.02 ≦ e ≦ 0.15. f is a number satisfying 0 ≦ f ≦ 0.70, preferably a number satisfying 0 ≦ f ≦ 0.60. x is 1 or 2, preferably 2. 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.

[0060] 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.

[0061] 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 component (B) include, but are not limited to, those represented by the following formula. [(R 11 O)(CH3)2SiO 1 / 2 a [(CH3)3SiO 1 / 2 b [H(CH3)SiO 2 / 2 c1 [(C6H5)2SiO 2 / 2 d [(CH3)2SiO 2 / 2 e1 [(R 11 O)(CH3)2SiO​​​​​1 / 2 ] a [H(CH3)2SiO 1 / 2 ] b [(C6H5)2SiO 2 / 2 ] d [(CH3)2SiO 2 / 2 ] e1 [C6H5SiO 3 / 2 ] f1 (In the formula, R 11 (where a is a hydrogen atom or a methyl group, and a, b, d, and f are the same as above. c1 is a number satisfying 0.1 ≤ c1 ≤ 0.40, e1 is a number satisfying 0.02 ≤ e1 ≤ 0.15, and f1 is a number satisfying 0.10 ≤ f1 ≤ 0.60.)

[0062] The weight-average molecular weight (Mw) of component (B) determined by gel permeation chromatography (GPC) is 700 to 7,000, preferably 700 to 3,000. If Mw is less than 700, it becomes more volatile during mixing, leading to gas generation from vents, and the amount of component (B) added decreases, resulting in a lack of flame retardant effect. On the other hand, if it is greater than 7,000, the compatibility and dispersibility with component (A) decreases, making mixing difficult, leading to venting and uneven mixing, which reduces the transparency and flame retardancy of the cured composition.

[0063] (B) Component contains chloride ions (Cl) derived from the acid catalyst used in manufacturing. - ) and sulfate ions (SO4 2- Although residual ions may remain, these residual ions may cause thermal decomposition of the composition and corrosion of metal parts of the apparatus at high temperatures such as during kneading or injection molding. Therefore, the content of chloride ions and sulfate ions relative to the mass of component (B) is preferably 3 ppm by mass or less.

[0064] Furthermore, if component (B) contains volatile components, the volatilization of these components during mixing or injection molding may cause defects such as molding failures. Therefore, it is preferable that the mass loss when heated at 150°C for 30 minutes at 1 atmosphere is 3% by mass or less relative to the mass of component (B).

[0065] Component (B) preferably has a hydrogen gas volume of 30 to 80 mL / g per unit mass generated by the alkaline decomposition method. More preferably, it is 40 to 70 mL / g. If it is 30 mL / g or more, the structure formation of component (B) is facilitated, and drip during combustion can be suppressed. If it is 80 mL / g or less, it can be suppressed that excess Si-H groups react with moisture in the air during heat treatment, generating hydrogen gas from the resin composition and causing foaming, which can lead to the molded product becoming cloudy. Here, the structure of component (B) refers to a network structure formed by the interaction of organohydrogenpolysiloxane itself, or by the reaction between aromatic polycarbonate resin and organohydrogenpolysiloxane.

[0066] As reported in the aforementioned Patent Documents 6 and 7, organohydrogenpolysiloxanes containing Si-H groups and aromatic groups in their molecules are known to act as flame retardants, but component (B) in the present invention further contains these groups along with [(R 1 O) (R 2 ) 2SiO 1 / 2 ] (R 1 and R 2 The same applies below. The presence of a constituent unit represented by (R) improves flame retardancy. This is because during combustion, component (B) migrates to the surface, and in addition to the formation of a structure by Si-H groups, (R 1 O) Cross-linking between groups or (R 1 It is presumed that dripping is suppressed by increasing the formation of structures through crosslinking between O groups and Si-H groups.

[0067] In the flame-retardant aromatic polycarbonate resin composition of the present invention, from the viewpoint of improving the dispersibility of component (B) and suppressing clouding of the composition or a decrease in transparency due to moist heat treatment, the amount of aryl groups in component (B) is preferably 10 to 80% by mass, and more preferably 15 to 70% by mass. Here, the amount of aryl groups can be calculated by the following formula: Amount of aryl groups = [Ar / Mw] × 100 (mass%) Ar: Total formula weight of aryl groups per molecule of component (B) Mw: Weight-average molecular weight of component (B)

[0068] (B) Component may be used alone or in combination of two or more types.

[0069] The amount of component (B) is 5 to 30 parts by mass per 100 parts by mass of aromatic polycarbonate resin of component (A), preferably 7 to 28 parts by mass, and more preferably 10 to 26 parts by mass. An amount less than 5 parts by mass is insufficient for a masterbatch, and an amount exceeding 30 parts by mass makes backflow and vent-up of component (B) more likely to occur during kneading, resulting in a low content of component (B) in the resulting masterbatch and failure to maintain uniform dispersion, leading to poor kneading.

[0070] (B) The organohydrogenpolysiloxane can be obtained, for example, by co-hydrolysis condensation of organochlorosilanes and removal of by-products such as hydrochloric acid and low-boiling point components. [(R 1 O) (R 2 ) 2SiO 1 / 2 As a method for introducing the ] unit, a silane having an Si-H group, such as dimethylchlorosilane (H(CH3)2SiCl), is used as a starting material, and the hydrochloric acid produced as a by-product during the reaction removes the hydrogen atom of the Si-H group R 1 It can be easily converted to an O group.

[0071] Furthermore, when linear siloxanes, cyclic siloxanes, or alkoxysilanes are used as starting materials, the organohydrogenpolysiloxane of component (B) can be obtained by carrying out equilibration and condensation reactions using acid catalysts such as sulfuric acid and methanesulfonic acid, and then removing the used acid catalysts and low-boiling components. In this case, hexamethyldisiloxane or the like is used as the terminal component, and the equilibration reaction is carried out with highly acidic trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc., to obtain the trimethylsilyl group [(CH3)3SiO 1 / 2 A portion of the methyl group in ] is cleaved, R 1 It is converted to an O group.

[0072] [Component (C)] Component (C) in the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is at least one additive selected from the group consisting of (i) phosphorus-based antioxidants, (ii) phenol-based antioxidants, (iii) lubricants that do not contain fluorine, (iv) organic alkali metal salts that do not contain fluorine, and (v) organic alkaline earth metal salts that do not contain fluorine.

[0073] (i) Any of the following compounds can be used as phosphorus-based antioxidants: phosphite-based, phosphonite-based, phosphate-based, etc.

[0074] Specific examples of phosphite compounds 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.

[0075] Specific examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite.

[0076] Specific examples of phosphate compounds include trimethyl phosphate.

[0077] (ii) Phenolic antioxidants can suppress discoloration during heat exposure and are also effective in improving flame retardancy. Specific examples of phenolic 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, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate.

[0078] When using (i) phosphorus-based antioxidants or (ii) phenol-based antioxidants, the amount added is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.5 parts by mass, and even more preferably 0.01 to 0.2 parts by mass, per 100 parts by mass of component (A).

[0079] (iii) Examples of lubricants that do not contain fluorine include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes, modified polyolefin waxes, polysiloxanes other than component (B) (e.g., linear or cyclic polydimethylsiloxane, linear or cyclic polymethylphenylsiloxane, functional group modified polysiloxane, etc.), paraffin wax, beeswax, saturated fatty acid esters (e.g., monoglycerides such as monoglyceride stearate, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, lower fatty acid esters such as stearate stearate, higher fatty acid esters such as behenate sebacate, and erythritol esters such as pentaerythritol tetrastearate), among which saturated fatty acid esters, linear or cyclic polydimethylsiloxane, and linear or cyclic polymethylphenylsiloxane are preferred.

[0080] When a lubricant is used, the amount added is preferably 0.001 to 1 part by mass per 100 parts by mass of component (A).

[0081] (iv) Fluorine-free organic alkali metal salts and (v) fluorine-free organic alkaline earth metal salts are components that improve flame retardancy. Preferably, the aromatic polycarbonate resin masterbatch 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.

[0082] Specific examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, while specific examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium, with lithium, sodium, and potassium being particularly preferred.

[0083] As organometallic salts that do not contain fluorine, 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 viewpoint of dispersibility with component (A), alkali metal salts of aromatic sulfonic acids that do not contain fluorine or alkaline earth metal salts of aromatic sulfonic acids that do not contain fluorine are more preferred.

[0084] Examples of aliphatic sulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, and octanesulfonic acid.

[0085] Specific examples of alkali (earth) metal salts of aliphatic sulfonic acids that do not contain fluorine include lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, lithium butanesulfonate, sodium butanesulfonate, potassium butanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, and barium methanesulfonate.

[0086] Examples of aromatic sulfonic acids include sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and their esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfon-sulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids with methylene-type bonds.

[0087] Specific examples of alkali (earth) metal sulfonates of monomeric or polymeric aromatic sulfides include disodium diphenyl sulfide-4,4'-disulfonate and dipotassium diphenyl sulfide-4,4'-disulfonate.

[0088] Specific examples of alkali (earth) metal sulfonates of aromatic carboxylic acids and their esters include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonic acid.

[0089] Specific examples of alkali (earth) metal sulfonic acid salts 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.

[0090] Specific examples of alkali (earth) metal salts of aromatic sulfonates include potassium sulfonate of benzenesulfonate.

[0091] Specific examples of monomeric or polymeric alkali (earth) metal salts of aromatic sulfonic acids 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.

[0092] Specific examples of monomeric or polymeric alkali (earth) metal salts of aromatic sulfonesulfonic acid include sodium diphenylsulfon-3-sulfonate, potassium diphenylsulfon-3-sulfonate, dipotassium diphenylsulfon-3,3'-disulfonate, and dipotassium diphenylsulfon-3,4'-disulfonate.

[0093] Specific examples of alkali (earth) metal salts of aromatic ketones include dipotassium benzophenone-3,3'-disulfonate.

[0094] Specific examples of heterocyclic alkali (earth) metal salts of sulfonic acid include disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, and sodium benzothiophenesulfonate.

[0095] Specific examples of alkali (earth) metal salts of aromatic sulfoxides include potassium diphenyl sulfoxide-4-sulfonate.

[0096] Specific examples of condensates formed by methylene-type bonds of alkali (earth) metal salts of aromatic sulfonic acids include formalin condensates of sodium naphthalene sulfonate and formalin condensates of sodium anthracene sulfonate.

[0097] For components (iv) and (v), alkali (earth) metal salts of sulfate esters that do not contain fluorine can be used, and examples of alkali (earth) metal salts of sulfate esters include alkali (earth) metal salts of sulfate esters of monohydric or polyhydric alcohols. Specific examples of sulfate esters of monohydric or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, sulfate ester of polyoxyethylene alkylphenyl ether, mono, di, tri or tetra sulfate of pentaerythritol, sulfate ester of laurate monoglyceride, sulfate ester of palmitate monoglyceride, sulfate ester of stearate monoglyceride, and the like. Among these, alkali (earth) metal salts of lauryl sulfate are preferred.

[0098] Components (iv) and (v) may be used individually or in combination of two or more. Among components (iv) and (v), potassium diphenylsulfon-3-sulfonate and sodium polystyrenesulfonate are preferred.

[0099] When using component (iv) and component (v), the amount of each component is preferably 0.001 to 5 parts by mass per 100 parts by mass of component (A).

[0100] The amount of component (C) is 0.001 to 10 parts by mass per 100 parts by mass of component (A) in total, preferably 0.001 to 8 parts by mass, more preferably 0.005 to 7 parts by mass, and even more preferably 0.005 to 6 parts by mass. If the amount is less than 0.001 parts by mass, the content of component (C) in the masterbatch will be low, and uniform dispersion cannot be maintained, leading to poor mixing. If it exceeds 10 parts by mass, the transparency of the masterbatch will decrease, or molding defects will occur.

[0101] [Other Components] The flame-retardant aromatic polycarbonate resin masterbatch of the present invention may contain other components, such as thermoplastic resins other than component (A) and additives other than component (C), to the extent that they do not impair the purpose of the present invention.

[0102] Specific examples of thermoplastic resins other than component (A) include, for example, general-purpose plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyacrylicstyrene 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 crystalline polyarylate); and so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. Furthermore, thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used. These thermoplastic resins can be blended within a range that does not affect flame retardancy.

[0103] (C) Examples of additives other than component include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass beads, glass balloons, milled fiber, glass flakes, carbon fiber, carbon flakes, carbon beads, carbon milled fiber, metal flakes, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flakes, silica, ceramic particles, ceramic fiber, aramid particles, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers, etc.), and flame retardants (halogen-based, phosphoric acid). The following can be incorporated: ester-based, red phosphorus, metal hydrate-based, etc.), heat stabilizers, antioxidants other than components (i) and (ii), mold release agents, ultraviolet absorbers, light stabilizers, lubricants, colorants (pigments and dyes such as carbon black and titanium dioxide), light diffusing agents (acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles, etc.), fluorescent whitening agents, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine particle titanium dioxide, fine particle zinc oxide, etc.), impact modifiers represented by graft rubber, infrared absorbers, photochromic agents, etc. It is preferable to exclude fluorine-containing additives from the various additives used in the flame-retardant aromatic polycarbonate resin masterbatch of the present invention.

[0104] Examples of antioxidants other than the components (i) and (ii) above include sulfur-based antioxidants, which are particularly suitable when the molding method is rotational molding or compression molding. Specific examples of sulfur-based antioxidants include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, 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).

[0105] When using a sulfur-based antioxidant, the amount added 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).

[0106] Examples of UV absorbers include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and hydroxyphenyltriazine-based UV absorbers.

[0107] Specific examples of benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 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.

[0108] Specific examples of benzotriazole-based UV 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)phenyl)benzotriazole. Examples include methyl-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'',benzotriazole-2'',yl)phenol], and methyl-3'',[3'',tert-butyl'',5'',(2H'',benzotriazole-2'',yl)-4'',hydroxyphenyl]propionate-polyethylene glycol condensates.

[0109] Specific examples of hydroxyphenyltriazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol and 2-(4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol.

[0110] Hindered amine-based light stabilizers can be used, and specific examples 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 condensate of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol, and tridecyl alcohol, and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl -4-piperidinol and tridecyl alcohol condensate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, poly{[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, poly{[6-morpholino-s-triazine-2,4-diyl][(2,2, 6,6-tetramethylpiperidyl)imino]hexamethylene[(2,2,6,6-tetramethylpiperidyl)imino]}, condensate of 1,2,3,4-butanetetracarboxylic acid and 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-aminopropyl)ethylenediamine and 2,4-bis[N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino]-chloro- Examples include condensates with 1,3,5-triazine, condensates of 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, and polymethylpropyl 3-oxy-[4-(2,2,6,6-tetramethyl)piperidinyl]siloxane.

[0111] When using an ultraviolet absorber and a light stabilizer, the amount of each is preferably 0.001 to 5 parts by mass, and more preferably 0.01 to 1 part by mass, per 100 parts by mass of component (A).

[0112] Furthermore, the flame-retardant aromatic polycarbonate resin masterbatch of the present invention may contain a bluing agent to counteract the yellow discoloration caused by ultraviolet absorbers, etc. Any bluing agent used for polycarbonate resins can be used without any particular problems, but anthraquinone dyes are preferred because they are readily available.

[0113] [2] Method for manufacturing flame-retardant aromatic polycarbonate resin masterbatch The method for manufacturing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is not particularly limited, and any method can be used. For example, components (A) to (C) and other components as needed may be thoroughly mixed using premixing means such as a hand mixer, V-type blender, Henschel mixer, mechanochemical device, or extruder mixer, then granulation may be performed using an extruder granulator or briquetting machine, and then melt-kneading in a melt-kneader such as a bent twin-screw kneader, and pelletizing with equipment such as a pelletizer.

[0114] Preferably, components (A) to (C) and, if necessary, other components can be supplied independently to a melting kneader, such as a vented twin-screw kneader, or a method can be used in which parts of two or more of components (A) to (C) are pre-mixed and then supplied to the melting kneader independently of the remaining components. If any of the components to be blended are liquid, a so-called liquid injection device or liquid additive device can be used to supply them to the melting kneader. The heating temperature during kneading is not particularly limited, but for example, 60 to 330°C is preferred, and 200 to 290°C is more preferred.

[0115] Particularly preferred is a method for producing a flame-retardant aromatic polycarbonate resin masterbatch, comprising the following steps (I) to (VI). (I) A step of preparing a twin-screw extruder such as a twin-screw meshing type melt-kneading extruder, which comprises a first feeder installed at the uppermost part of the raw material flow path, a second feeder installed at the same position as the first feeder or downstream thereof, a third feeder installed downstream of the second feeder, a barrel having an outlet equipped with a vacuum vent and a die, and a screw housed in the barrel. (II) A step of supplying component (A) from the first feeder, component (C) from the second feeder, and component (B) from the third feeder into the barrel. (III) A step of heating components (A), (B), and (C) supplied into the barrel at a temperature of 200 to 290°C in the barrel, kneading them with the screw while adjusting the vacuum level to -0.01 to -0.05 MPa using a vacuum vent, and transporting them from upstream to downstream of the raw material flow path in the barrel to obtain a kneaded product. (IV) A step of obtaining a strand from the kneaded product by passing it through the die. (V) A step of cooling the strand (VI) A step of cutting the cooled strand to obtain a masterbatch pellet

[0116] As a specific example, schematic diagrams of a vented twin-screw melt-mixing extruder (hereinafter also referred to as "apparatus") for producing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention are shown in Figures 1 to 3. In Figure 1, the apparatus 100 includes a twin-screw extruder (hereinafter also referred to as "extruder") 110, a cooling water tank 111 for cooling the strands extruded from the extruder 110, and a pelletizer 112 for cutting the strands into pellets. The extruder 110 includes a first feeder 120, a second feeder 121, a third feeder 122 for supplying raw materials to the inside, an open vent 130 for discharging air, a vacuum vent 131 for vacuum suction, a barrel 150 equipped with a cylinder 140 composed of C1 to C15 and a die 141, a heater 151 configured to heat the barrel 150, a screw mechanism 152 rotatably housed inside the barrel 150 (cylinder 140), and a motor 153 for driving the screw mechanism 152.

[0117] The first feeder 120, located at the uppermost part of the raw material flow path in the barrel 150, supplies aromatic polycarbonate resin, which is component (A), to the extruder 110. The second feeder 121, located at the same position as the first feeder or downstream thereof, supplies additive, which is component (C), to the extruder 110. The third feeder, located further downstream than the second feeder, supplies organohydrogenpolysiloxane, which is component (B). In this case, the aromatic polycarbonate resin, component (A), may be pre-dried using a hot air circulation dryer or the like before being supplied. Alternatively, a mixture of multiple components may be supplied, for example, by mixing component (C) with component (A) before supplying. When other additives are used, they can be supplied from any feeder as appropriate, either mixed with or without mixing them with components (A), (B), or (C).

[0118] The screw mechanism 152 inside the barrel 150 mixes and kneads components (A) to (C) and other additives as needed, transporting them from upstream to downstream within the barrel. The resulting mixture is passed through a die 141 to form strands, cooled by a cooling water tank 111, and cut into pellets by a pelletizer 112. At this time, the heater 151 heats the cylinders (C1 to C15) 140 to a temperature of 80 to 330°C, preferably 100 to 300°C, and more preferably 200 to 290°C. The screw mechanism 152 is composed of various elements not shown. For example, it can be arbitrarily configured by combining a full-flight screw for feeding out the supplied raw materials and a kneading disc for kneading. In Figure 1, the screws inside cylinders C4, C8, C11, C12, and C13 are equipped with kneading discs (not shown) for kneading, while the screws inside the other cylinders are equipped with full-flight screws (not shown) for feeding out the material. The extruders shown in Figures 2 and 3 have the same configuration as the extruder in Figure 1, and these similar components are denoted by the same reference numerals as in Figure 1; their descriptions are omitted.

[0119] [3] Flame-retardant aromatic polycarbonate resin composition The flame-retardant aromatic polycarbonate resin composition of the present invention comprises the following components (A') and (B'): (A') Aromatic polycarbonate resin (B') Flame-retardant aromatic polycarbonate resin masterbatch of the present invention

[0120] [Component (A')] Component (A') in the flame-retardant aromatic polycarbonate resin composition of the present invention is the same as that exemplified as component (A) above, and its preferred range is also the same.

[0121] [Component (B')] Component (A') in the flame-retardant aromatic polycarbonate resin composition of the present invention is the flame-retardant aromatic polycarbonate resin masterbatch of the present invention described above.

[0122] The amount of component (B') is 2 to 70 parts by mass, preferably 2 to 65 parts by mass, and more preferably 2 to 60 parts by mass, per 100 parts by mass of component (A'). If the amount is less than 2 parts by mass, flame retardancy will not be exhibited, and if it exceeds 70 parts by mass, the transparency and mechanical properties of the composition will decrease, or molding defects will occur.

[0123] [(C') component] The flame-retardant aromatic polycarbonate resin composition of the present invention may contain at least one selected from organic alkali metal salts and organic alkaline earth metal salts that do not contain fluorine (C').

[0124] The fluorine-free organic alkali metal salt and fluorine-free organic alkaline earth metal salt of component (C') are the same as those exemplified as components (iv) and (v) above, and the preferred range is also the same.

[0125] The amount of component (C') is 0 to 2.0 parts by mass, and when component (C') is used, the amount is preferably 0.001 to 1.0 parts by mass, more preferably 0.001 to 0.5 parts by mass, and even more preferably 0.005 to 0.4 parts by mass, per 100 parts by mass of component (A').

[0126] 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, to the extent that it does not impair the objectives of the present invention. Examples of thermoplastic resins other than component (A') include those exemplified as thermoplastic resins other than component (A), and examples of other components such as additives include antioxidants exemplified as (i) phosphorus-based antioxidants and (ii) phenol-based antioxidants, lubricants exemplified as (iii) lubricants that do not contain fluorine, and other components such as additives other than component (C).

[0127] The method for producing the flame-retardant aromatic polycarbonate resin composition of the present invention is not particularly limited, and any method can be employed. For example, components (A'), (B'), and optionally (C') and other components may be thoroughly mixed using premixing means such as a hand mixer, V-type blender, Henschel mixer, mechanochemical device, or extruder mixer, followed by granulation using an extruder or briquetting machine, and then melt-kneading in a melt-kneader such as a vented twin-screw kneader, and pelletizing using equipment such as a pelletizer.

[0128] Other methods include supplying components (A'), (B'), and optionally (C') and other components independently to a melting kneader such as a vented twin-screw kneader, and supplying two or more of these components to the melting kneader separately after pre-mixing them. If any of the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used to supply them to the melting kneader. The heating temperature during kneading is not particularly limited, but for example, 200 to 350°C is preferred.

[0129] [4] Molding Method and Molded Products Various molded products can be manufactured by injection molding the flame-retardant aromatic polycarbonate resin composition of the present invention. In injection molding, it is possible to manufacture not only the conventional cold runner molding method but also the product using a hot runner that enables runnerless molding. Furthermore, as injection molding methods, gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, etc., can be used.

[0130] Furthermore, the flame-retardant aromatic polycarbonate resin composition of the present invention can be molded into various shapes such as extruded products, sheets, and films by extrusion molding. Inflation molding and casting methods can also be used for molding sheets and films.

[0131] Furthermore, the transparent flame-retardant aromatic polycarbonate resin composition of the present invention can be molded as a heat-shrinkable tube by stretching, and can also be molded into a molded product by rotational molding. The heating temperature during molding is not particularly limited, but the mold temperature is preferably 60°C or higher, and injection molding at 80 to 120°C is particularly preferred. In this case, the resin temperature during injection molding is preferably, for example, 250 to 360°C, and more preferably 280 to 330°C.

[0132] The present invention will be described in more detail below with reference to synthesis examples, comparative synthesis examples, examples, and comparative examples, but the present invention is not limited to these examples. The physical properties of the organohydrogenpolysiloxanes in the following synthesis examples and comparative synthesis examples were measured by the methods described below.

[0133] (1) Weight-average molecular weight (Mw) Measured by gel permeation chromatography (GPC) with standard polystyrene as the reference. <GPC measurement conditions> Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Column: TSKgel G4000HXL + G3000HXL + G2000HXL + G2000HXL manufactured by Tosoh Corporation (each with an inner diameter of 6 mm and a length of 150 mm) Developing solution: Tetrahydrofuran column bath Temperature: 40°C Flow rate: 1 mL / min Detector: Refractive index (RI) Standard: Monodisperse polystyrene (2) Volatile content Calculated as the mass loss (mass%) when heated at 1 atmosphere at 150°C for 30 minutes. (3) Chloride ions (Cl - ) and sulfate ions (SO4 2- ) The obtained amount of 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. Chloride ions and sulfate ions in the aqueous layer were measured by ion chromatography. (4) Amount of hydrogen gas generated When 2 g of organohydrogenpolysiloxane was diluted with 5 mL of 1-butanol at 25°C and 10 mL of 20% by mass sodium hydroxide aqueous solution 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 quantified with gas burette (mL)] / [Amount of sample (g)] (5) Average composition unit ratio 29 The peak areas originating from each unit in the Si-NMR spectrum were calculated by setting the total peak area of ​​the siloxane unit to 1.

[0134] [1] Synthesis of organohydrogenpolysiloxane [Synthesis Example 1] In a 1 L flask equipped with a stirrer, cooler, and thermometer, 75.6 g of hexamethyldisiloxane, 62.9 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 38.5 g of octamethylcyclotetrasiloxane, and 394.0 g of diphenyldimethoxysilane were stirred while adding 25.0 g of p-toluenesulfonic acid. After cooling to an internal temperature of 10°C, 31.5 g of water was added and the mixture was stirred for 5 hours to carry out the equilibrium reaction. Thereafter, 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 as a colorless, transparent liquid. Organohydrogenpolysiloxane B-1 has a Mw of 910, volatile content of 1.4% by mass, chloride ion and sulfate ion content of 1 ppm by mass or less each, hydrogen gas generation rate of 51.0 mL / g, and the average constituent unit ratio is [(R 11 O)(CH3)2SiO 1 / 2 ] 0.010 [(CH3)3SiO 1 / 2 ] 0.231 [H(CH3)SiO 2 / 2 ] 0.332 [(C6H5)2SiO 2 / 2 ] 0.305 [(CH3)2SiO 2 / 2 ] 0.122 (R 11 (Methyl group or hydrogen atom).

[0135] [Synthesis Example 2] In a 1 L flask equipped with a stirrer, cooler, and thermometer, 120.5 g of water, 3.6 g of toluene, and 2.2 g of hexane were stirred at an internal temperature of 80°C. A mixture of 94.4 g of phenyltrichlorosilane, 55.6 g of diphenyldichlorosilane, and 5.5 g of dimethyldichlorosilane was added dropwise over 2 hours using a dropping funnel. Then, 23.2 g of toluene was added, followed by the dropwise addition of 20.1 g of dimethylchlorosilane. Finally, 32.0 g of 70°C warm water was added and the mixture was stirred at 70°C for 1 hour. After the reaction was complete, 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 a Mw of 6,650, volatile content of 0.4% by mass, chloride ion and sulfate ion content of 1 ppm by mass or less each, hydrogen gas generation rate of 34.2 mL / g, and the average constituent unit ratio is [(R 11 O)(CH3)2SiO 1 / 2 ] 0.025 [H(CH3)2SiO 1 / 2 ] 0.190 [(C6H5)2SiO 2 / 2 ] 0.249 [(CH3)2SiO 2 / 2 ] 0.051 [C6H5SiO 3 / 2 ] 0.485 (R 11 (Methyl group or hydrogen atom).

[0136] [Comparative Synthesis Example 1] The same procedure as in Synthesis Example 1 was performed except that p-toluenesulfonic acid was replaced with 15 g of sulfuric acid to obtain organohydrogenpolysiloxane BR-1 as a colorless, transparent liquid. Organohydrogenpolysiloxane BR-1 had a Mw of 890, volatile content of 1.9% by mass, chloride ion and sulfate ion content of 1 ppm by mass or less each, hydrogen gas generation rate of 49.0 mL / g, and the average constituent unit ratio was [(CH3)3SiO 1 / 2 ] 0.255 [H(CH3)SiO 2 / 2 ] 0.329 [(C6H5)2SiO 2 / 2 ] 0.279[(CH3)2SiO 2 / 2 ] 0.137 That was the case.

[0137] [Comparative Synthesis Example 2] The same procedure as in Synthesis Example 2 was followed, except that dimethylchlorosilane was replaced with 21.5 g of trimethylchlorosilane, to obtain organopolysiloxane BR-2 as a white powder. Organopolysiloxane BR-2 had a Mw of 6,800, volatile content of 0.5% by mass, chloride ion and sulfate ion content of 1 ppm or less each, hydrogen gas generation rate of 0 mL / g, and the average constituent unit ratio was [(CH3)3SiO 1 / 2 ] 0.230 [(C6H5)2SiO 2 / 2 ] 0.262 [(CH3)2SiO 2 / 2 ] 0.062 [C6H5SiO 3 / 2 ] 0.446 That was the case.

[0138] [Comparative Synthesis Example 3] The same procedure as in Synthesis Example 2 was followed, except that the amount of water was changed to 188.9 g and the amount of dimethylchlorosilane to 11.6 g, to obtain organohydrogenpolysiloxane BR-3 as a white powder. Organohydrogenpolysiloxane BR-3 had a Mw of 11,500, volatile content of 0.2% by mass, chloride ion and sulfate ion content of 1 ppm or less each, hydrogen gas generation rate of 30.8 mL / g, and the average constituent unit ratio was [(R 11 O)(CH3)2SiO 1 / 2 ] 0.013 [H(CH3)2SiO 1 / 2 ] 0.102 [(C6H5)2SiO 2 / 2 ] 0.314 [(CH3)2SiO 2 / 2 ] 0.109 [C6H5SiO 3 / 2 ] 0.462 (R 11 (Methyl group or hydrogen atom).

[0139] [2] Manufacturing of polycarbonate resin masterbatch A polycarbonate resin masterbatch was manufactured using a co-rotating twin-screw molten compounding extruder [TEX30α-52.5BW-5V manufactured by Japan Steel Works Ltd., number of cylinders: 15, cylinder diameter: 32 mm, L / D (total cylinder length / cylinder diameter): 52.5], by kneading each of the following components in the composition ratio (parts by mass) shown in Table 1 according to the following procedure.

[0140] (A) Components A-1: ​​Branched polycarbonate resin (Novarex M-7027U pellets manufactured by Mitsubishi Engineering Plastics Corporation, MVR 2.9 cm) 3 (10 minutes) A-2: High-molecular-weight polycarbonate resin (Teijin Limited Panlite K-1300Y pellets, MVR 2.8cm) 3 (10 minutes) A-3: Standard polycarbonate resin (Mitsubishi Engineering Plastics Co., Ltd. Yupiron S-3000N pellets, MVR 14cm) 3 (10 minutes) A-4: Bisphenol A type polycarbonate resin pellets derived from recycled water bottles (MVR 14cm) 3 (10 minutes) A-5: Standard polycarbonate resin (Idemitsu Kosan Co., Ltd. Toughlon FN-2200 flakes, MVR 12cm) 3 / 10 minutes)

[0141] (B) Components 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: Organohydrogenpolysiloxane obtained in Comparative Synthesis Example 2 BR-3: Organohydrogenpolysiloxane obtained in Comparative Synthesis Example 3

[0142] (C) Components C-1: Phosphate antioxidant (ADEKA Stab PEP-36, manufactured by ADEKA Corporation) C-2: Phenolic antioxidant (ADEKA Stab AO-50, manufactured by ADEKA Corporation) C-3: Special fatty acid ester lubricant (Rikestar EW-440, manufactured by Riken Vitamin Co., Ltd.) C-4: Potassium diphenylsulfonate (KSS-FR, manufactured by Arichem)

[0143] [Example 1-1] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 210 shown in Figure 2. First, components A-1 and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, component A-1 was supplied into the barrel 250 (cylinder 240) from the first feeder 220 at a rate of 18 kg / h. In addition, a mixture of components A-5 and C-1 to C-4, mixed in a mixer, was supplied from the second feeder 221 at a rate of 2.3 kg / h. Furthermore, component B-1 was supplied from the third feeder 222 at a rate of 2.3 kg / h. At this time, the barrel 250 (cylinder 240) was heated with a heater 251 so that the temperature inside the barrel 250 (cylinder 240) reached the set temperature shown in Figure 2, and the pressure of the vacuum vent 231 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 250 (cylinder 240) with a screw 252 and transported from the upstream end where the first feeder 220 was installed to the downstream end where the die 241 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut with a pelletizer 212 to obtain pellet MB-1. Discharge rate: 22.6 kg / h, screw rotation speed: 250 rpm, resin temperature: 283°C, torque: 40.4 to 48.8%, resin pressure: 0.8 to 1.2 MPa.

[0144] [Example 1-2] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 310 shown in Figure 3. First, components A-2, A-3, and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-2 and A-3 were supplied into the barrel 350 (cylinder 340) from the first feeder 320 at a rate of 18 kg / h. In addition, a mixture of component A-5 and components C-1 to C-4, mixed in a mixer, was supplied from the second feeder 321 at a rate of 2.6 kg / h. Furthermore, component B-1 was supplied from the third feeder 322 at a rate of 2.3 kg / h. At this time, the barrel 350 (cylinder 340) was heated with a heater 351 so that the temperature inside the barrel 350 (cylinder 340) reached the set temperature shown in Figure 3, and the pressure of the vacuum vent 331 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 350 (cylinder 340) with a screw 352 and transported from the upstream end where the first feeder 320 was installed to the downstream end where the die 341 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut with a pelletizer 312 to obtain pellet MB-2. Discharge rate: 22.9 kg / h, screw rotation speed: 250 rpm, resin temperature: 281°C, torque: 35.8 to 42.4%, resin pressure: 0.5 to 1.5 MPa.

[0145] [Example 1-3] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 310 shown in Figure 3. First, components A-1, A-3, and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-1 and A-3 were supplied into the barrel 350 (cylinder 340) from the first feeder 320 at a rate of 18 kg / h. In addition, a mixture of component A-5 and components C-1 to C-3, mixed in a mixer, was supplied from the second feeder 321 at a rate of 2.1 kg / h. Furthermore, component B-2 was supplied from the third feeder 322 at a rate of 4.9 kg / h. At this time, the barrel 350 (cylinder 340) was heated with a heater 351 so that the temperature inside the barrel 350 (cylinder 340) reached the set temperature shown in Figure 3, and the pressure of the vacuum vent 331 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 350 (cylinder 340) with a screw 352 and transported from the upstream end where the first feeder 320 was installed to the downstream end where the die 341 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut with a pelletizer 312 to obtain pellet MB-3. Discharge rate: 23.0 kg / h, screw rotation speed: 250 rpm, resin temperature: 284°C, torque: 36.4 to 43.7%, resin pressure: 0.7 to 1.6 MPa.

[0146] [Example 1-4] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 210 shown in Figure 2. First, components A-2, A-4, and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-2 and A-4 were supplied into the barrel 250 (cylinder 240) from the first feeder 220 at a rate of 18 kg / h. In addition, a mixture of component A-5 and components C-1 to C-3, mixed in a mixer, was supplied from the second feeder 221 at a rate of 2.1 kg / h. Furthermore, component B-1 was supplied from the third feeder 222 at a rate of 4.0 kg / h. At this time, the barrel 250 (cylinder 240) was heated with a heater 251 so that the temperature inside the barrel 250 (cylinder 240) reached the set temperature shown in Figure 2, and the pressure of the vacuum vent 231 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 250 (cylinder 240) with a screw 252 and transported from the upstream end where the first feeder 220 was installed to the downstream end where the die 241 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut with a pelletizer 212 to obtain pellet MB-4. Discharge rate: 22.8 kg / h, screw rotation speed: 250 rpm, resin temperature: 282°C, torque: 33.8 to 40.1%, resin pressure: 0.3 to 1.2 MPa.

[0147] [Comparative Example 1-1] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 210 shown in Figure 2. First, components A-1 and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, component A-1 was supplied into the barrel 250 (cylinder 240) from the first feeder 220 at a rate of 18 kg / h. Component A-5 was supplied from the second feeder 221 at a rate of 2.0 kg / h. Furthermore, component B-1 was supplied from the third feeder 222 at a rate of 2.3 kg / h. At this time, the barrel 250 (cylinder 240) was heated with a heater 251 so that the temperature inside the barrel 250 (cylinder 240) reached the set temperature shown in Figure 2, and the pressure of the vacuum vent 231 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 250 (cylinder 240) with a screw 252 and transported from the upstream end where the first feeder 220 was installed to the downstream end where the die 241 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut with a pelletizer 212 to obtain pellet MBR-1. Discharge rate: 20.3 kg / h, screw rotation speed: 250 rpm, resin temperature: 282°C, torque: 40.2 to 50.7 N・m, resin pressure: 0.6 to 1.0 MPa.

[0148] [Comparative Example 1-2] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 310 shown in Figure 3. First, components A-2, A-3, and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-2 and A-3 were supplied into the barrel 350 (cylinder 340) from the first feeder 320 at a rate of 18 kg / h. Components A-5 and C-1 to C-4 were supplied from the second feeder 321 at a rate of 2.3 kg / h. Furthermore, component B-1 was supplied from the third feeder 322 at a rate of 7.0 kg / h. At this time, the barrel 350 (cylinder 340) was heated with a heater 351 so that the temperature inside the barrel 350 (cylinder 340) reached the set temperature shown in Figure 3, and the pressure of the vacuum vent 331 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 350 (cylinder 340) with a screw 352 and transported from the upstream end where the first feeder 320 was installed to the downstream end where the die 341 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut with a pelletizer 312 to obtain pellet MBR-2. Discharge rate: 20.0 kg / h, screw rotation speed: 250 rpm, resin temperature: 282°C, torque: 37.4 to 40.1 N・m, resin pressure: 0.1 to 0.3 MPa.

[0149] [Comparative Example 1-3] A polycarbonate resin masterbatch was manufactured using the apparatus configuration and cylinder setting temperature of the extruder 210 shown in Figure 2. First, components A-1, A-3, and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-1 and A-3 were supplied into the barrel 250 (cylinder 240) from the first feeder 220 at a rate of 18 kg / h. Components A-5 and C-1 to C-4 were supplied from the second feeder 221 at a rate of 2.3 kg / h. Furthermore, component B-1 was supplied from the third feeder 222 at a rate of 2.3 kg / h. At this time, the barrel 250 (cylinder 240) was heated with a heater 251 so that the temperature inside the barrel 250 (cylinder 240) reached the set temperature shown in Figure 2, and the pressure of the vacuum vent 231 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 250 (cylinder 240) with a screw 252 and transported from the upstream end where the first feeder 220 was installed to the downstream end where the die 241 was installed to obtain a kneaded material. The obtained kneaded material was extruded from the die 241 into strands under the following conditions, cooled in a water tank (water bath) 211, and then 212 strands were cut with a pelletizer to obtain pellet MBR-3. Discharge rate: 22.6 kg / h, screw rotation speed: 250 rpm, resin temperature: 280°C, torque: 40.2 to 50.7 N・m, resin pressure: 0.5 to 1.0 MPa.

[0150] [Comparative Examples 1-4 to 1-6] Polycarbonate resin masterbatches were manufactured using the apparatus configuration and cylinder setting temperature of the extruder 210 shown in Figure 2. First, components A-1 and A-5 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, component A-1 was supplied into the barrel 250 (cylinder 240) from the first feeder 220 at a rate of 18 kg / h. Components A-5 and C-1 to C-4 were supplied from the second feeder 221 at a rate of 2.3 kg / h. Furthermore, BR-1 (Comparative Example 1-4), BR-2 (Comparative Example 1-5), or BR-3 (Comparative Example 1-6) were supplied from the third feeder 222 at a rate of 2.3 kg / h each. At this time, the barrel 250 (cylinder 240) was heated with a heater 251 so that the temperature inside the barrel 250 (cylinder 240) reached the set temperature shown in Figure 2, and the pressure of the vacuum vent 231 was adjusted from -0.01 to -0.05 MPa. The above components were kneaded in the barrel 250 (cylinder 240) with a screw 252 and transported from the upstream end where the first feeder 220 was installed to the downstream end where the die 241 was installed to obtain a kneaded material. The obtained kneaded material was passed through the die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut with a pelletizer 212 to obtain pellets MBR-4 to 6. Discharge rate: 22.6 kg / h, screw rotation speed: 250 rpm, resin temperature: 283 to 285°C, torque: 40.2 to 46.5%, resin pressure: 0.7 to 1.2 MPa.

[0151]

[0152] The following properties were evaluated for the obtained polycarbonate resin masterbatch. The results are shown in Table 2.

[0153] (6) Melt extrusion state The state of the strand when it was extruded was visually checked and evaluated according to the following indicators. Good: (No feeder clogging, vent-up, or strand pulsation) Poor: (Feeder clogging, vent-up, or strand pulsation present) (7) Melt volume rate (MVR) Measured at 300°C and 1.2 kg using the following apparatus. Apparatus: Melt indexer L220 manufactured by Tateyama Kagaku Kogyo Co., Ltd. (8) Siloxane introduction rate 1 g of masterbatch was weighed out, 10 g of concentrated sulfuric acid was added, and it was heated at 160°C for 16 hours. After cooling to room temperature, it was transferred to a platinum dish and treated by the sulfuric acid ashing method to dry it out. The total mass was measured, and the mass of SiO2 (measured SiO2 content) was determined by subtracting the mass of the platinum dish. The siloxane introduction rate (%) was calculated by taking the theoretical SiO2 content per gram of masterbatch, which was converted from the blending amount, as 100% and determining the percentage of the measured SiO2 content.

[0154]

[0155] As shown in Table 2, in Examples 1-1 to 1-4 and Comparative Examples 1-3 to 1-6, where the melt extrusion state was good, the siloxane introduction rate in the masterbatch was generally high at over 90%, while in Comparative Examples 1-1 and 1-2, where defects occurred in the melt extrusion state, the siloxane introduction rate was low.

[0156] [3] Production of Polycarbonate Resin Composition [Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-4] Resin compositions were prepared using the obtained masterbatches. Specifically, first, polycarbonate components A-1 and A-2 were pre-dried at 120°C for 10 hours using a hot air circulation dryer. Next, components A-1 and A-2 and masterbatches MB-1 to MB-4 and MBR-3 to MBR-6 were weighed out in the composition ratios (parts by mass) shown in Table 4, and the mixture was blended for 5 minutes and supplied to the first hopper. At that time, the blend was adjusted so that the polysiloxane content was 2% by mass in the total mixture of component A and each masterbatch. The other components were mixed in a mixer and supplied to the second hopper. The components in each hopper were fed from a gravimetric weighing single-screw feeder (KS60, manufactured by K-Tron), and the resin composition was prepared using a co-rotating twin-screw extruder (OMega30H, manufactured by STEER). The strands were extruded under conditions of a barrel temperature setting of 280°C, cooled in a water bath, and then cut in a pelletizer to form pellets. The obtained pellets were dried at 120°C for 6 hours in a hot air circulation dryer, and molded products with a thickness of 1.6 mm or 2 mm were formed using an electric injection molding machine (J100ADS-110, manufactured by Japan Steel Works Ltd.) at a cylinder temperature of 280-300°C and a mold temperature of 83°C. The injection conditions were as follows. Filling speed: 30 mm / s, Injection pressure: 155-165 MPa, Injection time: 0.7 seconds, Holding pressure: 140 MPa, Holding pressure speed: 30 mm / s, Injection holding pressure time: 3 seconds, Holding pressure time: 2.3 seconds, Clamping force: 1000 kN.

[0157] [4] Characterization of molded products The following characterizations were performed on the obtained molded products with a thickness of 1.6 mm. The results are shown in Table 4. (9) Transparency (haze) The transparency of the molded products was measured by measuring the haze value in accordance with JIS K7105. (10) UL Standard 94 Vertical Combustion Test A UL Standard 94 vertical combustion test was performed using a rectangular molded product measuring 127 mm in length, 13 mm in width, and 2 mm in thickness, manufactured in accordance with the US UL standard. Specifically, the flame retardancy was evaluated based on the flaming time and dripping (cotton ignition by drip) after indirectly flaming the lower end of a vertically held test piece for 10 seconds, according to the criteria shown in Table 3. Here, flaming time is the length of time that the test piece continues to burn in flame after the ignition source has been removed. Cotton ignition by drip is determined by whether the cotton used for marking, located approximately 300 mm below the lower end of the test piece, is ignited by the dripping material from the test piece. For each molded material, five test pieces were used, and the flaming burning time was evaluated as the total time of all five pieces. For cotton ignition by dripping, "no ignition" was evaluated if no ignition was observed in any of the five pieces.

[0158]

[0159]

[0160] As shown in Table 4, the flame-retardant aromatic polycarbonate resin compositions of Examples 2-1 to 2-4 exhibited excellent flame retardancy with a V-0 rating. On the other hand, the MVR contained in component (A) ranged from 2 to 8 cm². 3 In Comparative Example 2-1, which used a masterbatch MBR-3 containing less than 20% by mass (15% by mass) of aromatic polycarbonate resin for 10 minutes, although there was no cotton ignition, the total burning time exceeded 50 seconds and received a V-1 rating. Also, component (B) was [(R 1 O) (R 2 ) 2SiO 1 / 2 ] Unit (R 1 and R 2 The same applies as above.) In Comparative Example 2-2, which used a masterbatch MBR-4 that was changed to BR-1 without ), the total burning time exceeded 100 seconds and was rated V-1. Furthermore, component (B) was changed to [(H)(R 4 )SiO 2 / 2] Unit (R 4 In Comparative Example 2-3, which used masterbatch MBR-5 with BR-2 changed to BR-2 which does not have the above, the total burning time exceeded 200 seconds, and cotton ignition due to drip was also observed, resulting in a V-2 rating. In addition, in Comparative Example 2-4, which used masterbatch MBR-6 with component (B) changed to organohydrogenpolysiloxane BR-3 with a weight-average molecular weight of over 10,000, the total burning time exceeded 100 seconds, resulting in a V-1 rating.

[0161] As is clear from the above, the flame-retardant aromatic polycarbonate masterbatches of Examples 1-1 to 1-4, by containing organohydrogenpolysiloxane and additives as flame retardants, provide compositions that form cured products with good drip prevention performance and excellent transparency. The flame-retardant aromatic polycarbonate masterbatches of the present invention have the advantage of being substantially free of fluorinated organic compounds. Furthermore, the resin compositions of Examples 2-1 to 2-4 also possess high thermal stability even when melted at high temperatures such as injection molding. Therefore, they are extremely useful not only for lighting covers and protective covers for transparent displays, but also for various industrial applications in the fields of office automation equipment and electrical and electronic equipment, and the industrial effects they have are extremely large.

[0162] 100, 200, 300 Vented twin-screw melt-mixing extruder 110, 210, 310 Twin-screw extruder 111, 211, 311 Water tank 112, 212, 312 Pelletizer 140, 240, 340 Cylinder 150, 250, 350 Barrel 152, 252, 352 Screw

Claims

1. (A) Aromatic polycarbonate resin: 100 parts by mass, (B) Organohydrogenpolysiloxane represented by the following formula (1) with a weight average molecular weight of 700 to 7,000: 5 to 30 parts by mass, and (C) At least one additive selected from the group consisting of (i) phosphorus-based antioxidant, (ii) phenolic antioxidant, (iii) lubricant not containing fluorine, (iv) organic alkali metal salt not containing fluorine, and (v) organic alkaline earth metal salt not containing fluorine: 0.001 to 10 parts by mass. A flame-retardant aromatic polycarbonate resin masterbatch, wherein the melt volume flow rate (MVR) measured at 300 °C and a load of 1.2 kg in accordance with ISO 1133-1 is 2 to 8 cm 3 / 10 min, and the flame-retardant aromatic polycarbonate resin masterbatch contains 20% by mass or more of the aromatic polycarbonate resin based on the total mass of component (A). [(R 1 O)(R 2 )2SiO 1 / 2 ] a [(R 3 )3SiO 1 / 2 ] b [(H)(R 4 )SiO 2 / 2 ] c [(Ar) x (R 5 ) 2-x SiO 2 / 2 ] d [(R 6 )2SiO 2 / 2 ] e [(R 7 )SiO 3 / 2 ] f (wherein, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, 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 Each of these is an alkyl group having 1 to 6 carbon atoms, and R 7 Each of these is an alkyl group having 1 to 8 carbon atoms, which may be substituted with an alkenyl group having 2 to 8 carbon atoms, an aryl or epoxy group having 6 to 12 carbon atoms, 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, and f is a number satisfying 0 ≤ f ≤ 0.70, and a + b + c + d + e + f is 1. However, when c is 0, R 2 and R 3 (One or more of them are hydrogen atoms.) 2. The flame-retardant aromatic polycarbonate resin masterbatch according to claim 1, wherein in formula (1), Ar is a phenyl group, x is 2, and f is 0.

3. The flame-retardant aromatic polycarbonate resin masterbatch according to claim 1 or 2, wherein the weight-average molecular weight of component (B) is 700 to 3,000.

4. The flame-retardant aromatic polycarbonate resin masterbatch according to any one of claims 1 to 3, wherein component (C) comprises an alkali metal salt of an aromatic sulfonic acid that does not contain fluorine or an alkaline earth metal salt of an aromatic sulfonic acid that does not contain fluorine.

5. A method for producing a flame-retardant aromatic polycarbonate resin masterbatch according to any one of claims 1 to 4, comprising: (I) preparing a twin-screw extruder comprising a first feeder installed at the uppermost part of a raw material flow path, a second feeder installed at the same position as the first feeder or downstream thereof, a third feeder installed downstream of the second feeder, a barrel having an outlet equipped with a vacuum vent and a die, and a screw housed in the barrel; (II) supplying component (A) from the first feeder, component (C) from the second feeder, and component (B) from the third feeder into the barrel; (III) heating components (A), (B), and (C) supplied into the barrel at a temperature of 200 to 290°C in the barrel, and transporting the mixture from upstream to downstream in the barrel while kneading it with the screw while adjusting the vacuum level to -0.01 to -0.05 MPa using a vacuum vent, A method for producing a flame-retardant aromatic polycarbonate resin masterbatch, comprising the steps of (IV) passing the kneaded material through the die to obtain strands, (V) cooling the strands, and (VI) cutting the cooled strands to obtain masterbatch pellets.

6. A flame-retardant aromatic polycarbonate resin composition comprising: (A') 100 parts by mass of aromatic polycarbonate resin; (B') 2 to 70 parts by mass of a flame-retardant aromatic polycarbonate resin masterbatch according to any one of claims 1 to 4; and (C') 0 to 2.0 parts by mass of at least one selected from organic alkali metal salts that do not contain fluorine and organic alkaline earth metal salts that do not contain fluorine.

7. A molded article formed from the flame-retardant aromatic polycarbonate resin composition described in claim 6.

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