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

Abstract

To provide a flame-retardant aromatic polycarbonate resin masterbatch that can easily and uniformly disperse a specific silicone resin in an aromatic polycarbonate resin. 【Solution means】(A) Aromatic polycarbonate resin (B) An organohydrogenpolysiloxane having a weight average molecular weight of 700 to 7,000 represented by the formula (1), (C) (i) An additive selected from a phosphorus-based antioxidant, etc. A flame-retardant aromatic polycarbonate resin masterbatch containing an aromatic polycarbonate resin having an MVR measured at 300 °C and a load of 1.2 kg in accordance with ISO 1133-1 of 2 to 8 cm 3 / 10 minutes, and containing 20% by mass or more based on the total mass of the 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 (1) (R 1 ~R 7 are an alkyl group, etc., Ar is an aryl group, x is 1 or 2, a is 0​​​​​​

Description

[Technical Field]

[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. [Background technology]

[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 levels of flame retardancy in addition to the above-mentioned properties. Conventionally, flame-retardant aromatic polycarbonate resin compositions with the addition of 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, it had problems 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 obtained by adding an organic alkali metal salt and poly(methylhydrogen siloxane) to an aromatic polycarbonate resin. However, this resin composition itself became cloudy, and dispersion defects such as peeling occurred 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] In the aforementioned patent documents, polytetrafluoroethylene, which has fibril-forming ability, is often used 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 sulfonates, specifically potassium perfluorobutanesulfonate, are commonly used as flame retardants, they also have the drawback of becoming cloudy due to their incompatibility with aromatic polycarbonate resins.

[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 perfluoro and polyfluoroalkyl compounds (PFAS), such as 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 for 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 specific to silicone resins and can impart flame retardancy easily and uniformly through mixing. However, the only silicone resins used here that are solid at room temperature have been found, and there were limitations to using silicone resins that have a relatively low molecular weight and are liquid at room temperature. [Prior art documents] [Patent Documents]

[0014] [Patent Document 1] Japanese Patent Application Publication No. 6-306265 [Patent Document 2] Japanese Patent Application Publication No. 6-336547 [Patent Document 3] Japanese Patent Application Publication No. 9-169914 [Patent Document 4] Japanese Patent Application Publication No. 10-139964 [Patent Document 5] Special Publication No. 60-38419 [Patent Document 6] Patent No. 3779623 [Patent Document 7] Patent No. 3779624 [Patent Document 8] Japanese Patent Publication No. 2019-19191 [Patent Document 9] Patent No. 3608607 [Overview of the project] [Problems that the invention aims to solve]

[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. [Means for solving the problem]

[0018] As a result of diligent research to achieve the above objective, the inventors have discovered that a flame-retardant aromatic polycarbonate resin masterbatch containing an aromatic polycarbonate resin, a specific organohydrogen polysiloxane, and a specific additive allows for easy and uniform dispersion of a specific silicone resin within the aromatic polycarbonate resin, providing a flame-retardant aromatic polycarbonate resin composition with excellent transparency after curing and resistance to resin dripping during combustion. This led to the completion of the present invention.

[0019] That is, the present invention is 1. (A) Aromatic polycarbonate resin: 100 parts by mass, (B) An organohydrogenpolysiloxane represented by the following formula (1) and having 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) 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 A flame-retardant aromatic polycarbonate resin masterbatch containing 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 the 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 (1) (In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 2 and R<o:p>< / o:p> 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, independently of each other, an aryl group having 6 to 12 carbon atoms, R 5 and R 6 are, independently of each other, an alkyl group having 1 to 6 carbon atoms, R 7 is, independently of each other, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms or an alkyl group having 1 to 8 carbon atoms which may be substituted with an epoxy group, an amino group, an acryloyl group, a methacryloyl group or a thiol group. x represents 1 or 2, a is a number satisfying 0 < a ≦ 0.03, b is a number satisfying 0 < b ≦ 0.30, c is a number satisfying 0 ≦ c ≦ 0.45, d is a number satisfying 0.20 ≦ d ≦ 0.70, e is a number satisfying 0 ≦ e ≦ 0.20, f is a number satisfying 0 ≦ f ≦ 0.70, a + b + c + d + e + f is 1. However, when c is 0, one or more of R 2 and R 3 are hydrogen atoms.) 2. The flame-retardant aromatic polycarbonate resin masterbatch according to 1, wherein in the formula (1), Ar is a phenyl group, x is 2, and f is 0, 3. The flame-retardant aromatic polycarbonate resin masterbatch according to 1, wherein the weight-average molecular weight of the component (A) is 700 to 3,000, 4. The flame-retardant aromatic polycarbonate resin masterbatch according to 1, wherein the component (C) contains an alkali metal salt of an aromatic sulfonic acid containing no fluorine or an alkaline earth metal salt of an aromatic sulfonic acid containing no fluorine, [ 5. A method for producing the flame-retardant aromatic polycarbonate resin masterbatch according to any one of 1 to 4, (I) A step of 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) A step of supplying component (A) into the barrel from the first feeder, component (C) from the second feeder, and component (B) from the third feeder. (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, 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 by vacuum venting, (IV) A step of passing the kneaded material through the die to obtain strands, (V) A step of cooling the strand, (VI) The process of cutting the cooled strand to obtain a masterbatch pellet. A method for producing a flame-retardant aromatic polycarbonate resin masterbatch containing 6. (A') 100 parts by mass of aromatic polycarbonate resin, (B') Flame-retardant aromatic polycarbonate resin masterbatch as described in any of 1 to 4: 2 to 70 parts by mass, (C') At least one selected from fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts: 0 to 2.0 parts by mass Flame-retardant aromatic polycarbonate resin composition containing 7. Molded articles made from the flame-retardant aromatic polycarbonate resin composition described in 6. To provide. [Effects of the Invention]

[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. [Brief explanation of the drawing]

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

[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] [(A) component] Component (A) in the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is an aromatic polycarbonate resin, and can be, for example, one obtained by reacting a divalent phenol with a carbonate precursor by interfacial polycondensation or molten transesterification, or one obtained by polymerizing a carbonate prepolymer by solid-phase transesterification, or one obtained 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, and 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 branched polycarbonate resin contains a polyfunctional compound, 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, branched structures may be formed as a side reaction, but the amount of such branched structures 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. 1 It can be calculated by 1H-NMR measurement.

[0031] Reactions by interfacial polycondensation typically involve the reaction of divalent phenol with 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. Furthermore, 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 be used to accelerate the reaction. 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 is preferably maintained at 9 or higher during the reaction.

[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] [ka] (In the formula, D is a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, or a phenyl-substituted alkyl group, and r is an integer 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] [ka] (In the formula, n represents an integer between 10 and 50.)

[0037] [ka] (In the formula, E is -RO-, -RC(=O)-O-, or -ROC(=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 -RC(=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-stop agents may be used individually or in combination of two or more.

[0040] The molten transesterification reaction 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 then 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 alcohol or phenol produced, 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 of the alcohol or phenol produced. The reaction time is generally preferred to be about 1 to 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, polymerization catalysts can be used to accelerate the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds such as sodium hydroxide, potassium hydroxide, and sodium 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—catalysts commonly used in esterification and transesterification reactions. Catalysts may be used individually or in combination of two or more types. The amount of these polymerization catalysts used is preferably 1 × 10⁻⁸ to 1 × 10⁻⁸ per mole of divalent phenol used as a raw material. -3 Equivalent, more preferably 1 × 10 -7 ~5×10 -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 a deactivator to neutralize the activity of the catalyst in the polymerization reaction. Specific examples of such deactivators 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 individually 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, more preferably 0.01 to 300 ppm, and even more preferably 0.01 to 100 ppm relative to the polycarbonate resin after polymerization.

[0046] The molecular weight of the aromatic polycarbonate resin of component (A) is not particularly limited, but from the viewpoint of mechanical properties at high temperatures and moldability, a viscosity-average molecular weight of 10,000 to 50,000 is preferred, 14,000 to 45,000 is more preferred, and 14,000 to 40,000 is even more preferred. 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 × 10⁻⁶). -5 It can be calculated from (×Mv0.83). Furthermore, 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 polymer-type and branched-type aromatic polycarbonate resins are preferred because they tend to have low melt volume flow rate (MVR), an indicator of fluidity and moldability. In the flame-retardant aromatic polycarbonate resin composition of the present invention, component (A) has an MVR of 2 to 8 cm at 300°C and a 1.2 kg load according to ISO 1133-1. 3The aromatic polycarbonate resin, which is 1 / 10 min, is contained in an amount of 20% by mass or more relative to the total mass of component (A), 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, MVR is 2cm 3 Less than 10 minutes results in insufficient fluidity and poor moldability, and 8cm 3 If the performance exceeds a certain limit per minute, impact resistance and other properties will decrease.

[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) is an aromatic polycarbonate resin recycled from used products (so-called material-recycled polycarbonate resin). ), or may include aromatic polycarbonate resin manufactured from aromatic polycarbonate resin that has been chemically decomposed and returned to its raw materials (so-called chemically recycled polycarbonate resin).

[0051] [(B) Component] 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 [(R6 )2SiO 2 / 2 e [(R 7 )SiO 3 / 2 f (1)

[0052] In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and 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, and R 5 and R 6 are each independently an alkyl group having 1 to 6 carbon atoms, and R 7 is each independently an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 8 carbon atoms which may be substituted with epoxy, amino, acryloyl, methacryloyl or thiol. x represents 1 or 2, a is a number satisfying 0 < a ≤ 0.03, b is a number satisfying 0 < b ≤ 0.30, c is a number satisfying 0 ≤ c ≤ 0.45, d is a number satisfying 0.20 ≤ d ≤ 0.70, e is a number satisfying 0 ≤ e ≤ 0.20, f is a number satisfying 0 ≤ f ≤ 0.70, and a + b + c + d + e + f = 1. However, when c is 0, one or more of R 2 and R 3 are hydrogen atoms.

[0053] R 1 Specific examples of the alkyl group having 1 to 3 carbon atoms of R 1 include a methyl group, an ethyl group, a propyl group, etc. Among them, R 1 is preferably a hydrogen atom or a methyl group.

[0054] R 2 and R 3As the alkyl group having 1 to 6 carbon atoms, those having 1 to 3 carbon atoms are preferred, and specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl groups, etc. As the aryl group having 6 to 12 carbon atoms, those having 6 to 10 carbon atoms are preferred, and specific examples thereof include phenyl, tolyl, xylyl, naphthyl groups, etc. Among them, R 2 and R 3 are preferably a hydrogen atom, a methyl group, or a phenyl group, and 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 of R 2 and R 3 are the same as the groups exemplified by R 4 Among them, R

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

[0057] R 5 and R 6 As the alkyl group having 1 to 6 carbon atoms of R 2 and R <x 3 are the same as the groups exemplified by R

[0058] R 7 As the alkenyl group having 2 to 8 carbon atoms of R, those having 2 to 6 carbon atoms are preferred, 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 by 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 and the like. Among them, R 7 is preferably a methyl group, a glycidoxypropyl group, an aminopropyl group, a (meth)acryloylpropyl group, a mercaptopropyl group, or a phenyl group, more preferably a methyl group or a phenyl group, and still more preferably a phenyl group.

[0059] a is a number satisfying 0 < a ≤ 0.03, but a number satisfying 0.005 ≤ a ≤ 0.025 is preferred. b is a number satisfying 0 < b ≤ 0.30, but a number satisfying 0.01 ≤ b ≤ 0.25 is preferred. c is a number satisfying 0 ≤ c ≤ 0.45, but a number satisfying 0.1 ≤ c ≤ 0.40 is preferred. d is a number satisfying 0.20 ≤ d ≤ 0.70, but a number satisfying 0.22 ≤ d ≤ 0.40 is preferred. e is a number satisfying 0 ≤ e ≤ 0.20, but a number satisfying 0.02 ≤ e ≤ 0.15 is preferred. f is a number satisfying 0 ≤ f ≤ 0.70, but a number satisfying 0 ≤ f ≤ 0.60 is preferred. x is 1 or 2, but 2 is preferred. However, when c is 0, one or more of R 2 and R 3 are hydrogen atoms, and it is preferred that 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. (B) Specific examples of component (B) include, but are not limited to, those shown in 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) can be reduced, resulting in a lack of flame retardancy. On the other hand, if Mw 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 the manufacturing process. -) 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 equipment 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, (R1 O) Bridges between groups or (R 1 It is presumed that dripping is suppressed by increasing the formation of structures through bridging 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 determined by the following calculation formula. Aryl group content = [Ar / Mw] × 100 (mass%) Ar: (B) Total formula weight of aryl groups per molecule 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 (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] The organohydrogenpolysiloxane of component (B) can be obtained, for example, by co-hydrolyzing and condensing organochlorosilanes and removing the 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 units, silanes having Si-H groups, such as dimethylchlorosilane (H(CH3)2SiCl), are used as raw materials, and the hydrochloric acid produced as a by-product during the reaction removes the hydrogen atoms of the Si-H groups. 1 It can be easily converted to an oxygen group.

[0071] Furthermore, when linear siloxanes, cyclic siloxanes, or alkoxysilanes are used as starting materials, the equilibration and condensation reactions can be carried out using acid catalysts such as sulfuric acid and methanesulfonic acid. After that, the used acid catalysts and low-boiling point components can be removed to obtain the organohydrogenpolysiloxane of component (B). In this case, hexamethyldisiloxane or the like is used as the terminal component, and an 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 oxygen group.

[0072] [(C) component] 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 also have an effect on 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 using a lubricant, 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 sulfonates of monomeric or polymeric aromatic ethers include calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, poly(2,6-dimethylphenylene oxide)polysulfonate, poly(1,3-phenylene oxide)polysulfonate, poly(1,4-phenylene oxide)polysulfonate, 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 sulfonsulfonic 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 may be used. 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, and molding defects will occur.

[0101] [Other ingredients] 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 the objectives of the present invention are not impaired.

[0102] Specific examples of thermoplastic resins other than component (A) include, for example, general-purpose plastics such as polyethylene resin, polypropylene resin, polystyrene resin, polyacrylic styrene 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] Examples of additives other than component (C) 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 such as 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), 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'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 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, 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 a flame-retardant aromatic polycarbonate resin masterbatch The method for producing the flame-retardant aromatic polycarbonate resin masterbatch of the present invention is not particularly limited, and any method can be employed. For example, components (A) to (C) and other components as needed are thoroughly mixed using pre-mixing means such as a hand mixer, V-type blender, Henschel mixer, mechanochemical device, or extruder mixer, then granulated using an extruder granulator or briquetting machine, and then melt-kneaded in a melt-kneader such as a vented twin-screw kneader, and pelletized using 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 two or more components of components (A) to (C) can be 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 process 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 process to obtain a mixture by heating components (A), (B), and (C) supplied into the barrel at a temperature of 200 to 290°C in the barrel, and kneading them with the screw while transporting them from upstream to downstream in the raw material flow path within the barrel, while adjusting the vacuum level to -0.01 to -0.05 MPa using a vacuum vent. (IV) A step of passing the kneaded material through the die to obtain strands. (V) A step of cooling the strand. (VI) The process of cutting the cooled strand to obtain a masterbatch pellet.

[0116] As a specific example, schematic diagrams of a vented twin-screw molten compounding and extrusion apparatus (hereinafter also referred to as "apparatus") used to manufacture 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 the 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 cylinders 140 and dies 141 composed of C1 to C15, a heater 151 configured to heat the barrel 150, a screw mechanism 152 rotatably housed within 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 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 the die 141 to form strands, cooled in the cooling water tank 111, and cut into pellets by the 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, 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 dispensing the supplied raw materials and a kneading disc for kneading. In Figure 1, the screws in cylinders C4, C8, C11, C12, and C13 are kneading discs (not shown) for mixing purposes, while the screws in the other cylinders are full-flight screws (also not shown) for feeding. 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] [(A') component] In the flame-retardant aromatic polycarbonate resin composition of the present invention, component (A') is the same as that exemplified as component (A) above, and the preferred range is also the same.

[0121] [(B') component] 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 that do not contain (C')fluorine and organic alkaline earth metal salts that do not contain fluorine.

[0124] The fluorine-free organic alkali metal salts and fluorine-free organic alkaline earth metal salts of component (C') are the same as those exemplified as components (iv) and (v) above, and the preferred ranges are 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 and additives other than component (A'), as long as the objectives of the present invention are not impaired. 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 finally 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 product 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, various injection molding methods such as gas-assisted injection molding, injection compression molding, and ultra-high-speed injection molding can be used.

[0130] Further, by extrusion molding the flame-retardant aromatic polycarbonate resin composition of the present invention, it can also be molded into various shaped extruded products, sheets, films, etc. Also, for the molding of sheets and films, an inflation method, a casting method, etc. can also be used.

[0131] Furthermore, the transparent flame-retardant aromatic polycarbonate resin composition of the present invention can also be molded into a heat-shrinkable tube by a stretching operation, 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 particularly preferably injection-molded at 80 - 120°C. At this time, the resin temperature in injection molding is preferably, for example, 250 - 360°C, and more preferably 280 - 330°C.

Examples

[0132] Hereinafter, synthesis examples, comparative synthesis examples, examples, and comparative examples will be shown to explain the present invention in more detail, but the present invention is not limited to these examples. In addition, the physical properties of the organohydrogenpolysiloxane in the following synthesis examples and comparative synthesis examples were measured by the following methods.

[0133] (1) Weight average molecular weight (Mw) It was measured by gel permeation chromatography (GPC) based on standard polystyrene. <GPC measurement conditions> Apparatus: HLC-8320GPC manufactured by Tosoh Corporation Column: TSKgel G4000HXL + G3000HXL + G2000HXL + G2000HXL manufactured by Tosoh Corporation (each inner diameter 6 mm, length 150 mm) 00HXL + G2000HXL (each inner diameter 6 mm, length 150 mm) Developing solution: Tetrahydrofuran Column tank temperature: 40°C Flow rate: 1 mL / min Detector: Refractive index (RI) Standard: Monodisperse polystyrene (2) Volatile content The mass loss (mass %) was calculated as the mass reduction when heated at 150°C for 30 minutes at 1 atmosphere. (3) Chloride ions (Cl - ) and sulfate ions (SO4 2- )amount 20 g of the obtained organohydrogenpolysiloxane was dissolved in 20 mL of toluene, 20 g of pure water was added, and the mixture was shaken for 2 hours to extract the ions into the aqueous layer. Chloride ions and sulfate ions in the aqueous layer were measured by ion chromatography. (4) Amount of hydrogen gas generated The 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 was quantified using a gas burette, and the amount of hydrogen gas generated was calculated using the following formula. Hydrogen gas generation rate (mL / g) = [Amount of hydrogen gas quantified by gas burette (mL)] / [Sample amount (g)] (5) Average unit ratio 29 The peak areas derived 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 organohydrogenpolysiloxanes [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 mixed with 25.0 g of p-toluenesulfonic acid while stirring. 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 perform the equilibrium reaction. Subsequently, the toluene layer was repeatedly washed with water until it became neutral, and the resulting toluene solution was concentrated under reduced pressure to obtain organohydrogenpolysiloxane B-1, a colorless, transparent liquid. Organohydrogenpolysiloxane B-1 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 [C6H5SiO3 / 2 ] 0.485 (R 11 (Methyl group or hydrogen atom)

[0136] [Comparative Synthesis Example 1] In Synthesis Example 1, the same procedure was followed except that p-toluenesulfonic acid was replaced with 15 g of sulfuric acid to obtain the colorless, transparent liquid organohydrogenpolysiloxane BR-1. Organohydrogenpolysiloxane BR-1 has a Mw of 890, volatile content of 1.9% by mass, chloride ion and sulfate ion content of less than 1 ppm by mass each, hydrogen gas generation rate of 49.0 mL / g, and the average constituent unit ratio is [(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. That was the case.

[0137] [Comparative Synthesis Example 2] In Synthesis Example 2, the same procedure was followed except that dimethylchlorosilane was replaced with 21.5 g of trimethylchlorosilane to obtain the white powder organopolysiloxane BR-2. Organopolysiloxane BR-2 has 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 an average constituent unit ratio of [(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] In Synthesis Example 2, the procedure was carried out in the same manner as in Synthesis Example 2, except that the amount of water was changed to 188.9 g and the amount of dimethylchlorosilane to 11.6 g, to obtain the white powder organohydrogenpolysiloxane BR-3. Organohydrogenpolysiloxane BR-3 has 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 is [(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 masterbatches 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)], the following components were mixed according to the composition ratio (parts by mass) shown in Table 1 to produce a polycarbonate resin masterbatch.

[0140] (A) component A-1: Branched polycarbonate resin (Novarex M-7027U pellets manufactured by Mitsubishi Engineering Plastics Corporation, MVR 2.9cm) 3 / 10 minutes) A-2: High-molecular-weight polycarbonate resin (Teijin Limited's 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 (MVR14cm) 3 / 10 minutes) A-5: Standard polycarbonate resin (Toughlon FN-2200 flakes manufactured by Idemitsu Kosan Co., Ltd., MVR 12cm) 3 / 10 minutes)

[0141] (B) Component B-1: Organohydrogenpolysiloxane obtained in Synthesis Example 1 B-2: Organohydrogenpolysiloxane obtained in Synthesis Example 2 BR-1: Organohydrogenpolysiloxane obtained in Comparative Synthesis Example 1 BR-2: Organopolysiloxane obtained in comparative synthesis example 2 BR-3: Organohydrogenpolysiloxane obtained in comparative synthesis example 3

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

[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 circulating dryer. Next, component A-1 was supplied to 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 the 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 then kneaded in the barrel 250 (cylinder 240) with the 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 the kneaded material. The resulting mixture was passed through a die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut in a pelletizer 212 to obtain pellet MB-1. Discharge rate: 22.6 kg / h, screw rotation speed: 250 rpm, resin temperature: 283℃, torque: 40.4~48.8%, resin pressure: 0.8~1.2 MPa.

[0144] [Examples 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 circulating dryer. Next, components A-2 and A-3 were supplied to barrel 350 (cylinder 340) from the first feeder 320 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 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 the 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 then kneaded in the barrel 350 (cylinder 340) with the 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 the kneaded material. The resulting mixture was passed through a die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut in a pelletizer 312 to obtain pellet MB-2. Discharge rate: 22.9 kg / h, screw rotation speed: 250 rpm, resin temperature: 281℃, torque: 35.8~42.4%, resin pressure: 0.5~1.5 MPa.

[0145] [Examples 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 circulating dryer. Next, components A-1 and A-3 were supplied to barrel 350 (cylinder 340) from the first feeder 320 at a rate of 18 kg / h. In addition, a mixture of components A-5 and 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 the 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 then kneaded in the barrel 350 (cylinder 340) with the 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 the kneaded material. The resulting mixture was passed through a die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut in a pelletizer 312 to obtain pellet MB-3. Discharge rate: 23.0 kg / h, screw rotation speed: 250 rpm, resin temperature: 284℃, torque: 36.4~43.7%, resin pressure: 0.7~1.6 MPa.

[0146] [Examples 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 circulating dryer. Next, components A-2 and A-4 were supplied to 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-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 the 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 then kneaded in the barrel 250 (cylinder 240) with the 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 the kneaded material. The resulting mixture was passed through a die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut in a pelletizer 212 to obtain pellet MB-4. Discharge rate: 22.8 kg / h, screw rotation speed: 250 rpm, resin temperature: 282℃, torque: 33.8~40.1%, resin pressure: 0.3~1.2 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 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 then kneaded in the barrel 250 (cylinder 240) using 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 the kneaded product. The resulting mixture was passed through a die 241 under the following conditions to extrude strands, cooled in a water tank (water bath) 211, and then the strands were cut in a pelletizer 212 to obtain pellets MBR-1. Discharge rate: 20.3 kg / h, screw rotation speed: 250 rpm, resin temperature: 282℃, torque: 40.2~50.7 N·m, resin pressure: 0.6~1.0 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 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 the 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 then kneaded in the barrel 350 (cylinder 340) with the 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 the kneaded material. The resulting mixture was passed through a die 341 under the following conditions to extrude strands, cooled in a water tank (water bath) 311, and then the strands were cut in a pelletizer 312 to obtain pellets MBR-2. Discharge rate: 20.0 kg / h, screw rotation speed: 250 rpm, resin temperature: 282℃, torque: 37.4~40.1 N·m, resin pressure: 0.1~0.3 MPa.

[0149] [Comparative Examples 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 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 the 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 then kneaded in the barrel 250 (cylinder 240) with the 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 the kneaded material. The resulting mixture was extruded from the die 241 under the following conditions, cooled in a water tank (water bath) 211, and then 212 strands were cut in a pelletizer to obtain pellets MBR-3. Discharge rate: 22.6 kg / h, screw rotation speed: 250 rpm, resin temperature: 280℃, torque: 40.2~50.7 N·m, resin pressure: 0.5~1.0 MPa.

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

[0151] [Table 1]

[0152] The following property evaluations were performed on the obtained polycarbonate resin masterbatch. The results are shown in Table 2.

[0153] (6) Melting extrusion state The state when extruding the strand was visually confirmed and evaluated according to the following indicators. Good: (No clogging of the feeder, no vent up, and no pulsation of the strand) Bad: (Clogging of the feeder, vent up, or pulsation of the strand) (7) Melt volume rate (MVR) The following equipment was used for measurement at 300°C and 1.2 kg. Equipment: Melt indexer L220 manufactured by Tateyama Science Industry Co., Ltd. (8) Siloxane adoption rate 1 g of masterbatch was weighed out, 10 g of concentrated sulfuric acid was added, and the mixture was heated at 160°C for 16 hours. After cooling to room temperature, it was transferred to a platinum dish and treated by sulfuric acid ashing to dryness. The total mass was weighed, and the mass of SiO2 (measured SiO2 content) was determined by subtracting the mass of the platinum dish. The siloxane introduction rate (%) was calculated as the percentage of the measured SiO2 content relative to the theoretical SiO2 content per gram of masterbatch, which was calculated from the blending amount and set as 100%.

[0154] [Table 2]

[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] The resin composition was 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 according to the composition ratio (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 formulation 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, K-Tron), and the resin composition was prepared using a co-rotating twin-screw extruder (OMega30H, STEER). The strands were extruded under barrel temperature settings 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, Hold 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 characteristics were evaluated for the obtained molded product with a thickness of 1.6 mm. The results are shown in Table 4. (9) Transparency (haze) The transparency of the molded product was measured by the haze value in accordance with JIS K7105. (10) UL Standard 94 Vertical Combustion Test A vertical combustion test (UL 94) was conducted using a rectangular molded product measuring 127 mm in length, 13 mm in width, and 2 mm in thickness, manufactured in accordance with US UL standards. Specifically, the flame retardancy was evaluated based on the flammability time and drip (cotton ignition due to dripping) after indirectly applying a burner flame to the lower end of a vertically held test piece for 10 seconds, according to the criteria shown in Table 3. Here, flaming combustion time refers to the length of time the test specimen 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 bottom of the test specimen, is ignited by the dripping material from the specimen. Five test specimens were used for each molding material, and the flaming combustion time was evaluated as the total time for all five specimens. For cotton ignition by drip, "no ignition" was evaluated if no ignition was observed in any of the five specimens.

[0158] [Table 3]

[0159] [Table 4]

[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) is 2-8 cm 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) is [(R 1 O)(R 2 )2SiO 1 / 2 ] Unit (R 1 and R 2In Comparative Example 2-2 using masterbatch MBR-4 modified to BR-1 having no (same as above)), the total combustion time exceeded 100 seconds and it was a V-1 evaluation. Further, in (B) component, [(H)(R 4 )SiO 2 / 2 unit (R 4 is the same as above.) In Comparative Example 2-3 using masterbatch MBR-5 modified to BR-2 having no, the total combustion time exceeded 200 seconds, and ignition of cotton due to dripping was also observed, and it was a V-2 evaluation. In addition, in Comparative Example 2-4 using masterbatch MBR-6 in which the (B) component was changed to organohydrogenpolysiloxane BR-3 having a weight average molecular weight exceeding 10,000, the total combustion time exceeded 100 seconds and it was a V-1 evaluation.

[0161] As is clear from the above, the flame-retardant aromatic polycarbonate masterbatches of Examples 1-1 to 1-4 contain organohydrogenpolysiloxane and additives as flame retardants, have good drip-preventing performance, and give a composition that forms a cured product excellent in transparency. The flame-retardant aromatic polycarbonate masterbatch of the present invention has the advantage of substantially not containing a fluorinated organic compound. In addition, the resin compositions of Examples 2-1 to 2-4 also have high thermal stability even when melted at high temperatures such as injection molding. Therefore, it is extremely useful not only for lighting covers and protective covers for transmissive displays, but also for various industrial applications in the fields of OA equipment, electric and electronic equipment, etc., and the industrial effect it exhibits is extremely large.

Explanation of symbols

[0162] 100, 200, 300 Vent type twin-screw melt kneading 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) 5 to 30 parts by mass of an organohydrogenpolysiloxane represented by the following formula (1) having a weight-average molecular weight of 700 to 7,000, and, (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: 0.001 to 10 parts by mass A flame-retardant aromatic polycarbonate resin masterbatch containing, The melt volume flow rate (MVR) measured at 300°C and a load of 1.2 kg in accordance with ISO 1133-1 was 2-8 cm³. 3 A flame-retardant aromatic polycarbonate resin masterbatch containing 20% ​​by mass or more of an aromatic polycarbonate resin with a ratio of 10 minutes relative to the total mass of component (A). [(R 1 O)(R 2 ) 2 SiO 1 / 2 ] a [(R 3 ) 3 SiO 1 / 2 ] b [ (H) (R). 4 )SiO 2 / 2 ] c [ (Ar) x (R 5 ) 2-x SiO 2 / 2 ] d [(R 6 ) 2 SiO 2 / 2 ] e [(R 7 )SiO 3 / 2 ] f (1) (In the formula, R 1 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R 2 and R 3 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group. R 4 This is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Each Ar is independently an aryl group having 6 to 12 carbon atoms. R 5 and R 6 Each of these is an alkyl group having 1 to 6 carbon atoms, R 7 Each of these is an alkyl group having 1 to 8 carbon atoms, which may be independently 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 either 1 or 2, a is a number that satisfies 0 < a ≤ 0.03, b is a number that satisfies 0 < b ≤ 0.30, c is a number that satisfies 0 ≤ c ≤ 0.45, d is a number that satisfies 0.20 ≤ d ≤ 0.70, e is a number that satisfies 0 ≤ e ≤ 0.20, f is a number that satisfies 0 ≤ f ≤ 0.70, 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, wherein the weight-average molecular weight of component (A) is 700 to 3,000.

4. The flame-retardant aromatic polycarbonate resin masterbatch according to claim 1, 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, (I) A step of 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) A step of supplying component (A) into the barrel from the first feeder, component (C) from the second feeder, and component (B) from the third feeder. (III) A step of obtaining a mixture by 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. (IV) A step of passing the kneaded material through the die to obtain strands, (V) A step of cooling the strand, (VI) The process of cutting the cooled strand to obtain a masterbatch pellet. A method for producing a flame-retardant aromatic polycarbonate resin masterbatch containing [a specific compound / component].

6. (A') 100 parts by mass of aromatic polycarbonate resin, (B') Flame-retardant aromatic polycarbonate resin masterbatch according to any one of claims 1 to 4: 2 to 70 parts by mass, (C') At least one selected from organic alkali metal salts and organic alkaline earth metal salts that do not contain fluorine: 0 to 2.0 parts by mass A flame-retardant aromatic polycarbonate resin composition containing [a specific compound / substance].

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

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