Polycarbonate resin composition and method for producing same

Abstract

One embodiment of the present invention provides a polycarbonate resin composition which comprises: a polycarbonate resin that includes a constituent unit (A) derived from a monomer represented by formula (1) and also includes a constituent unit (B) derived from a monomer represented by formula (2) or a constituent unit (C) derived from a monomer represented by formula (3), wherein the formulae (1), (2) and (3) are described in the description; a compound represented by general formula (I); and a compound represented by general formula (II). In the polycarbonate resin composition, the abundance ratio of the compound represented by general formula (II) to the compound represented by general formula (I) (i.e., [the compound represented by general formula (II)] / [the compound represented by general formula (I)]) is 1.0 to 10.0.

Description

Polycarbonate resin composition and method for producing same

[0001] The present invention relates to a polycarbonate resin composition and a method for producing the same.

[0002] Patent Document 1 discloses a method for producing a polymer, which includes a step of improving the deterioration over time of the color of an organic solvent solution of a polymer having a 9,9-bis(4-oxy-3-methylphenyl)fluorene structural unit.

[0003] Patent Document 2 discloses a resin composition containing a polycarbonate resin containing structural units derived from 2,2'-bis(hydroxymethoxy)-1,1'-binaphthalene and structural units derived from 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and an antioxidant and / or a mold release agent.

[0004] JP 2002-80734 A JP 2020-45492 A

[0005] Traditionally, additives such as mold release agents have been added to polycarbonate resin during injection molding to improve the mold release properties of the resin. However, these additives can cause deposits (mold deposits) to form on the molds of the injection molding machine. One of the causes of mold deposits is thought to be the accumulation of chemical components contained in the resin, or chemicals or oils applied to the surface of the mold.

[0006] Therefore, an object of the present invention is to provide a polycarbonate resin composition that can reduce the occurrence of mold deposits during production without sacrificing the inherent efficacy of additives added to the polycarbonate resin, and a method for producing the same.

[0007] The present invention includes a polycarbonate resin composition according to the following embodiment: [1] A polycarbonate resin composition comprising: a polycarbonate resin containing a structural unit (A) derived from a monomer represented by the following formula (1), a structural unit (B) derived from a monomer represented by the following formula (2), or a structural unit (C) derived from a monomer represented by the following formula (3); a compound represented by the following general formula (I); and a compound represented by the following general formula (II), wherein the abundance ratio of the compound represented by the general formula (II) to the compound represented by the general formula (I) ([compound represented by the general formula (II)] / [compound represented by the general formula (I)]) is 1.0 to 10.0. [2] The polycarbonate resin composition according to [1], wherein the terminal structure of the polycarbonate resin contains a structure derived from a terminal terminator represented by the following formula (Z-1) and / or the following formula (Z-2): [3] The polycarbonate resin composition according to [1] or [2], wherein the compound represented by general formula (I) is represented by the following formula (I-1), or a combination of the following formulas (I-1) and (I-2): [4] The polycarbonate resin composition according to any one of [1] to [3], wherein the compound represented by general formula (II) is represented by the following formula (II-1), or a combination of the following formulas (II-1) and (II-2): [5] The polycarbonate resin composition according to any one of [1] to [4], wherein the compound represented by general formula (I) is the following formula (I-1), or a combination of the following formulas (I-1) and (I-2), and the compound represented by general formula (II) is the following formula (II-1), or a combination of the following formulas (II-1) and (II-2). [6] The polycarbonate resin composition according to any one of [1] to [5], wherein the abundance ratio is 1.0 to 7.5. [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polycarbonate resin contains 10 to 80 mol % of the structural unit (A) and 20 to 90 mol % of the structural unit (B) or the structural unit (C). [8] The polycarbonate resin composition according to any one of [1] to [7], wherein the polycarbonate resin composition contains 20 to 1500 ppm of the compound represented by general formula (I). [9] A method for producing the polycarbonate resin composition according to any one of [1] to [8], comprising a step of melt-mixing the polycarbonate resin and the compound represented by general formula (I) under conditions where the cylinder temperature is 280°C or higher and the ratio (Q / Ns) of the discharge rate Q to the screw rotation speed Ns is 0.1 to 1.0.

[0008] By using the polycarbonate resin composition of the present invention, it is possible to reduce the occurrence of mold deposits during production without sacrificing the inherent efficacy of the additive.

[0009] 1 shows the results of GC-MS measurement of the polycarbonate resin composition of Example 1.

[0010] [Polycarbonate Resin Composition] The polycarbonate resin composition of the present invention comprises a polycarbonate resin containing a structural unit (A) derived from a monomer represented by the following formula (1), and a structural unit (B) derived from a monomer represented by the following formula (2) or a structural unit (C) derived from a monomer represented by the following formula (3), a compound represented by the following general formula (I), and a compound represented by the following general formula (II), wherein the abundance ratio of the compound represented by formula (II) to the compound represented by formula (I) ([compound represented by formula (II)] / [compound represented by formula (I)]) is 1.0 to 10.0.

[0011] The monomer represented by formula (1) is 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCFL).

[0012] The monomer represented by formula (2) is bisphenol M (ie, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene) (BPM).

[0013] The monomer represented by formula (3) is bisphenol AP (ie, 4,4'-(1-phenylethylidene)bisphenol) (BPAP).

[0014] The compound represented by general formula (I) is a fatty acid ester of glycerin and a fatty acid having an alkyl group having 10 to 20 carbon atoms, which may be branched. Preferably, the compound represented by general formula (I) is glycerin monostearate represented by the following formula (I-1). Alternatively, the compound represented by general formula (I) may be a combination of glycerin monostearate represented by the following formula (I-1) and glycerin monopalmitate represented by the following formula (I-2).

[0015] The compound represented by general formula (II) is a fatty acid ester of a fatty acid having an alkyl group having 10 to 20 carbon atoms, which may be branched, and a cyclic carbonate. Preferably, the compound represented by general formula (II) is (2-oxo-1,3-dioxolan-4-yl)methyl monostearate represented by the following formula (II-1). Alternatively, the compound represented by general formula (II) may be a combination of (2-oxo-1,3-dioxolan-4-yl)methyl monostearate represented by the following formula (II-1) and (2-oxo-1,3-dioxolan-4-yl)methyl monopalmitate represented by the following formula (II-2).

[0016] The abundance ratio of the compound represented by general formula (II) to the compound represented by general formula (I) is the value obtained by dividing the peak intensity (abundance) of the compound represented by general formula (II) by the peak intensity (abundance) of the compound represented by general formula (I) measured by gas chromatography mass spectrometry (GC-MS) ([compound represented by general formula (II)] / [compound represented by general formula (I)]). The abundance ratio is 1.0 to 10.0. The abundance ratio is 1.0 to 9.5, 1.0 to 9.0, 1.0 to 8.5, 1.0 to 8.0, 1.0 to 7.5, 1.0 to 7.0, 1.0 to 6.5, 1.0 to 6.0, 1.0 to 5.5, 1.0 to 5.0, 1.0 to 4.5, 1.0 to 4.0, 1.0 to 3.5, 1.0 to 3.0, 1.0 to 2.5, 1.0 to 2.0, 1.2 to 9.5, 1.2 to 9.0, 1.2 to 8.5, 1.2 to 8.0, 1.2 to 7.5, 1.2 to 7.0, 1.2 to 6.5, 1.2 to 6.0, 1.2-5.5, 1.2-5.0, 1.2-4.5, 1.2-4.0, 1.2-3.5, 1.2-3.0, 1.2-2.5, 1.2-2.0, 1.5-9.5, 1.5-9.0, 1.5-8.5, 1.5-8.0, 1.5-7.5, 1.5-7.0, 1.5-6.5, 1.5-6.0, 1.5-5.5, 1.5-5.0, 1.5-4.5, 1.5-4.0, 1.5-3.5, 1.5-3.0, 1.5-2.5, 1.5-2.0, 2.0 ~9.5, 2.0~9.0, 2.0~8.5, 2.0~8.0, 2.0~7.5, 2.0~7.0, 2.0~6.5, 2.0~6.0, 2.0~5.5, 2.0~5.0, 2.0~4.5, 2.0~4.0, 2.0~3.5, 2.0~3.0, 2.0~2.5, 3.0~9.5, 3.0~9.0, 3.0~8.5, 3.0~8.0, 3.0~7.5, 3.0~7.0, 3.0~6.5, 3.0~6.0, 3.0~5.5, 3.0~5.0, 3 . 0-4.5, 3.0-4.0, 3.0-3.5, 4.0-9.5, 4.0-9.0, 4.0-8.5, 4.0-8.0, 4.0-7.5, 4.0-7.0, 4.0-6.5, 4.0-6.0, 4.0-5.5, 4.0-5.0, 4.0-4.5, 5.0-9.5, 5.0-9.0, 5.0-8.5, 5.0-8.0, 5.0-7.5, 5.0-7.0, 5.0-6.5, 5.0-6.0, 5.0-5.5, 6.0-9.5, 6.0-9.0,It may be 6.0 to 8.5, 6.0 to 8.0, 6.0 to 7.5, 6.0 to 7.0, 6.0 to 6.5, 1.5 to 6.7, 1.5 to 6.3, 1.5 to 5.5, 1.5 to 5.0, 1.5 to 4.1, 1.5 to 3.0, 3.0 to 6.7, 3.0 to 6.3, 3.0 to 5.5, 3.0 to 5.0, 3.0 to 4.1, 4.1 to 6.7, 4.1 to 6.3, 4.1 to 5.5, 4.1 to 5.0, 5.0 to 6.7, 5.0 to 6.3, 5.0 to 5.5, 5.5 to 6.7, 5.5 to 6.3, or 6.3 to 6.7.

[0017] Preferably, the abundance ratio is the value obtained by dividing the peak intensity (abundance) of the compound represented by formula (II-1) by the peak intensity (abundance) of the compound represented by formula (I-1) measured by gas chromatography mass spectrometry (GC-MS) ([compound represented by formula (II-1)] / [compound represented by formula (I-1)]), and the abundance ratio is 1.0 to 10.0. The abundance ratio is 1.0 to 9.5, 1.0 to 9.0, 1.0 to 8.5, 1.0 to 8.0, 1.0 to 7.5, 1.0 to 7.0, 1.0 to 6.5, 1.0 to 6.0, 1.0 to 5.5, 1.0 to 5.0, 1.0 to 4.5, 1.0 to 4.0, 1.0 to 3.5, 1.0 to 3.0, 1.0 to 2.5, 1.0 to 2.0, 1.2 to 9.5, 1.2 to 9.0, 1.2 to 8.5, 1.2 to 8.0, 1.2 to 7.5, 1.2 to 7.0, 1.2 to 6.5, 1.2 to 6.0, 1.2 to 5.5, 1.2-5.0, 1.2-4.5, 1.2-4.0, 1.2-3.5, 1.2-3.0, 1.2-2.5, 1.2-2.0, 1.5-9.5, 1.5-9.0, 1.5-8.5, 1.5-8.0, 1.5-7.5, 1.5-7.0, 1.5-6.5, 1.5-6.0, 1.5-5.5, 1.5-5.0, 1.5-4.5, 1.5-4.0, 1.5-3.5, 1.5-3.0, 1.5-2.5, 1.5-2.0, 2.0-9.5, 2.0-9.0, 2.0 ~8.5, 2.0-8.0, 2.0-7.5, 2.0-7.0, 2.0-6.5, 2.0-6.0, 2.0-5.5, 2.0-5.0, 2.0-4.5, 2.0-4.0, 2.0-3.5, 2.0-3.0, 2.0-2.5, 3.0-9.5, 3.0-9.0, 3.0-8.5, 3.0-8.0, 3.0-7.5, 3.0-7.0, 3.0-6.5, 3.0-6.0, 3.0-5.5, 3.0-5.0, 3.0-4.5, 3.0-4.0, 3.0-3.5, 4 . 0-9.5, 4.0-9.0, 4.0-8.5, 4.0-8.0, 4.0-7.5, 4.0-7.0, 4.0-6.5, 4.0-6.0, 4.0-5.5, 4.0-5.0, 4.0-4.5, 5.0-9.5, 5.0-9.0, 5.0-8.5, 5.0-8.0, 5.0-7.5, 5.0-7.0, 5.0-6.5, 5.0-6.0, 5.0-5.5, 6.0-9.5, 6.0-9.0, 6.0-8.5, 6.0-8.0, 6.0-7.5, 6.0-7.0,It may be 6.0 to 6.5, 1.5 to 6.7, 1.5 to 6.3, 1.5 to 5.5, 1.5 to 5.0, 1.5 to 4.1, 1.5 to 3.0, 3.0 to 6.7, 3.0 to 6.3, 3.0 to 5.5, 3.0 to 5.0, 3.0 to 4.1, 4.1 to 6.7, 4.1 to 6.3, 4.1 to 5.5, 4.1 to 5.0, 5.0 to 6.7, 5.0 to 6.3, 5.0 to 5.5, 5.5 to 6.7, 5.5 to 6.3, or 6.3 to 6.7.

[0018] The terminal structure of the polycarbonate resin contains a structure derived from a terminal terminator represented by the following formula (Z-1) and / or the following formula (Z-2).

[0019] The polycarbonate resin contains 1 to 99 mol % of structural units (A) derived from a monomer represented by formula (1), and 1 to 99 mol % of structural units (B) derived from a monomer represented by formula (2) or structural units (C) derived from a monomer represented by formula (3).

[0020] The polycarbonate resin contains the structural unit (A) in an amount of 10 to 99 mol%, 10 to 90 mol%, 10 to 80 mol%, 10 to 70 mol%, 10 to 60 mol%, 10 to 50 mol%, 10 to 40 mol%, 10 to 30 mol%, 10 to 20 mol%, 20 to 99 mol%, 20 to 90 mol%, 20 to 80 mol%, 20 to 70 mol%, 20 to 60 mol%, 20 to 50 mol%, 20 to 40 mol%, 20 to 30 mol%, 30 to 99 mol%, 30 to 90 mol%, 30 to 80 mol%, 30 to 70 mol%, 30 to 60 mol%. %, 30 to 50 mol%, 30 to 40 mol%, 40 to 99 mol%, 40 to 90 mol%, 40 to 80 mol%, 40 to 70 mol%, 40 to 60 mol%, 40 to 50 mol%, 50 to 99 mol%, 50 to 90 mol%, 50 to 80 mol%, 50 to 70 mol%, 50 to 60 mol%, 60 to 99 mol%, 60 to 90 mol%, 60 to 80 mol%, 60 to 70 mol%, 70 to 99 mol%, 70 to 90 mol%, 70 to 80 mol%, 80 to 99 mol%, 80 to 90 mol%, or 90 to 99 mol%.

[0021] The polycarbonate resin contains the structural unit (B) or the structural unit (C) in an amount of 10 to 99 mol%, 10 to 90 mol%, 10 to 80 mol%, 10 to 70 mol%, 10 to 60 mol%, 10 to 50 mol%, 10 to 40 mol%, 10 to 30 mol%, 10 to 20 mol%, 20 to 99 mol%, 20 to 90 mol%, 20 to 80 mol%, 20 to 70 mol%, 20 to 60 mol%, 20 to 50 mol%, 20 to 40 mol%, 20 to 30 mol%, 30 to 99 mol%, 30 to 90 mol%, 30 to 80 mol%, 30 to 70 mol%, 3 The content may be 0 to 60 mol%, 30 to 50 mol%, 30 to 40 mol%, 40 to 99 mol%, 40 to 90 mol%, 40 to 80 mol%, 40 to 70 mol%, 40 to 60 mol%, 40 to 50 mol%, 50 to 99 mol%, 50 to 90 mol%, 50 to 80 mol%, 50 to 70 mol%, 50 to 60 mol%, 60 to 99 mol%, 60 to 90 mol%, 60 to 80 mol%, 60 to 70 mol%, 70 to 99 mol%, 70 to 90 mol%, 70 to 80 mol%, 80 to 99 mol%, 80 to 90 mol%, or 90 to 99 mol%.

[0022] Preferably, the polycarbonate resin contains 10 to 80 mol% of the structural unit (A) and 20 to 90 mol% of the structural unit (B) or the structural unit (C). The polycarbonate resin may contain 40 to 70 mol% or 50 to 60 mol% of the structural unit (A) and 30 to 60 mol% or 40 to 50 mol% of the structural unit (B). Alternatively, the polycarbonate resin may contain 10 to 50 mol% or 16 to 40 mol% of the structural unit (A) and 50 to 90 mol% or 60 to 84 mol% of the structural unit (C).

[0023] The contents of the compound represented by general formula (I) and the compound represented by general formula (II) contained in the polycarbonate resin composition are not particularly limited as long as they are within the range satisfying the above abundance ratio (1.0 to 10.0).

[0024] For example, the polycarbonate resin composition may contain the compound represented by general formula (I) at 10 to 3000 ppm, 10 to 2500 ppm, 10 to 2000 ppm, 10 to 1500 ppm, 10 to 1200 ppm, 10 to 1000 ppm, 10 to 800 ppm, 10 to 700 ppm, 10 to 600 ppm, 10 to 500 ppm, 20 to 2500 ppm, 20 to 2000 ppm, 2 0-1500ppm, 20-1200ppm, 20-1000ppm, 20-800ppm, 20-700ppm, 20-600ppm, 20-500ppm, 50-2500ppm , 50-2000ppm, 50-1500ppm, 50-1200ppm, 50-1000ppm, 50-800ppm, 50-700ppm, 50-600ppm, 50-500p pm, 100-2500ppm, 100-2000ppm, 100-1500ppm, 100-1200ppm, 100-1000ppm, 100-800ppm, 100-700p pm, 100-600ppm, 100-500ppm, 200-2500ppm, 200-2000ppm, 200-1500ppm, 200-1200ppm, 200-1000p The polycarbonate resin composition may contain 20 to 1500 ppm of the compound represented by general formula (I). In this specification, ppm refers to ppm by mass.

[0025] For example, the polycarbonate resin composition contains the compound represented by general formula (II) at 10 to 3000 ppm, 10 to 2500 ppm, 10 to 2000 ppm, 10 to 1500 ppm, 10 to 1200 ppm, 10 to 1000 ppm, 10 to 800 ppm, 10 to 700 ppm, 10 to 600 ppm, 10 to 500 ppm, 20 to 2500 ppm, 20 to 2000 ppm, 20-1500ppm, 20-1200ppm, 20-1000ppm, 20-800ppm, 20-700ppm, 20-600ppm, 20-500ppm, 50-2500ppm m, 50-2000ppm, 50-1500ppm, 50-1200ppm, 50-1000ppm, 50-800ppm, 50-700ppm, 50-600ppm, 50-500p pm, 100-2500ppm, 100-2000ppm, 100-1500ppm, 100-1200ppm, 100-1000ppm, 100-800ppm, 100-700p pm, 100-600ppm, 100-500ppm, 200-2500ppm, 200-2000ppm, 200-1500ppm, 200-1200ppm, 200-1000p The polycarbonate resin composition may contain 20 to 1500 ppm of the compound represented by general formula (II).

[0026] [Method for Producing Polycarbonate Resin Composition] The method for producing a polycarbonate resin composition of the present invention includes a step of melt-mixing the polycarbonate resin and the compound represented by general formula (I) as an additive in an extruder. The melt-mixing step is carried out under conditions where the cylinder temperature is 280°C or higher and the ratio (Q / Ns) of the discharge rate Q (kg / hr) of the resin discharged from the nozzle of the cylinder to the screw rotation speed Ns (rpm) of the screw in the cylinder is 0.1 to 1.0.

[0027] The polycarbonate resins used in the examples and comparative examples were produced based on the method described in the examples of the applicant's prior application (WO 2023 / 120559).

[0028] Polymerization Example 1 The polymerization method for the polycarbonate resin used in Example 1 was as follows. 160 kg (423.10 mol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCFL: manufactured by Honshu Chemical Industry Co., Ltd.), 145 kg (418.51 mol) of bisphenol M (BPM: manufactured by Honshu Chemical Industry Co., Ltd.), and 1.5 kg of triethylbenzylammonium chloride (TEBAC: manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to 2000 L of a 9% by mass aqueous sodium hydroxide solution, and the solution temperature was set to 20°C with stirring. 117 kg of phosgene was then blown in over 30 minutes. After the phosgene blowing was completed, 5.3 kg (35.282 mol) of 4-tert-butylphenol (PTBP) and 750 mL of triethylamine dissolved in 500 L of dichloromethane were added, and the mixture was allowed to polymerize for 50 minutes. The polymerization solution was separated into an aqueous layer and an organic layer, the organic layer was neutralized with phosphoric acid, and washed with pure water until the pH of the washings reached 7.0, thereby obtaining a polycarbonate resin powder. This polycarbonate resin powder was dried at 120°C for 40 hours to completely remove the solvent, thereby obtaining a polycarbonate resin.

[0029] The polycarbonate resins used in Examples 2 to 6 and Comparative Examples 2 and 3 were prepared by polymerization in the same manner as in Polymerization Example 1, except that the raw materials and contents of BCFL, BPM, and end terminator were as shown in Table 1.

[0030] (Polymerization Example 2) The polymerization method for the polycarbonate resin used in Example 7 is as follows. 176.602 kg (467 mol) of 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (BCFL: manufactured by Honshu Chemical Industry Co., Ltd.), 203.398 kg (700.5 mol) of bisphenol AP (BPAP: manufactured by Honshu Chemical Industry Co., Ltd.), and 1.5 kg of triethylbenzylammonium chloride (TEBAC: manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.) were added to 2700 L of a 9% by mass aqueous sodium hydroxide solution, and the solution temperature was set to 20°C with stirring. 162 kg of phosgene was then blown in over 30 minutes. After the phosgene blowing was completed, 7.3 kg (48.595 mol) of 4-tert-butylphenol (PTBP) and 750 mL of triethylamine dissolved in 500 L of dichloromethane were added, and the mixture was allowed to polymerize for 50 minutes. The polymerization solution was separated into an aqueous layer and an organic layer, the organic layer was neutralized with phosphoric acid, and washed with pure water until the pH of the washings reached 7.0, thereby obtaining a polycarbonate resin powder. This polycarbonate resin powder was dried at 120°C for 40 hours to completely remove the solvent, thereby obtaining a polycarbonate resin.

[0031] The polycarbonate resin used in Example 8 was prepared by polymerization in the same manner as in Polymerization Example 2, except that the raw materials and contents of BCFL, BPAP, and the end-capping agent were as shown in Table 1.

[0032] As the polycarbonate resin in Comparative Example 1, Iupilon H-4000 (manufactured by Mitsubishi Engineering-Plastics Corporation) was used.

[0033] [Example 1] Using a twin-screw kneading extruder TEM-58SX (manufactured by Shibaura Machinery Co., Ltd.), 200 kg of the polycarbonate resin obtained in Polymerization Example 1, 0.14 kg (700 ppm) of Rikemal (registered trademark) S-100A (manufactured by Riken Vitamin Co., Ltd.), and 0.26 kg of Adekastab (registered trademark) 2112 (manufactured by ADEKA Corporation) were mixed, and the mixture was extruded and pelletized under melt mixing conditions of a cylinder temperature of 300°C, a discharge rate (Q) of 200 kg / hr, and a screw rotation speed (Ns) of 300 rpm, to obtain a pelletized polycarbonate resin composition.

[0034] The analytical evaluation results of the polycarbonate resin composition of Example 1 are shown in Table 1. Also, Fig. 1 shows a chart of the GC-MS measurement results of the polycarbonate resin composition of Example 1. In Fig. 1, the vertical axis represents strength (abundance) and the horizontal axis represents time (minutes).

[0035] [Examples 2 to 8 and Comparative Examples 1 to 3] Pellet-shaped polycarbonate resin compositions were obtained in the same manner as in Example 1, except that the polycarbonate resins and additives shown in Table 1 were used and the melt mixing conditions shown in Table 1 were used. The analytical evaluation results of the polycarbonate resin compositions of Examples 2 to 8 and Comparative Examples 1 to 3 are shown in Table 1.

[0036]

[0037] In Table 1, BCFL is the compound represented by the above formula (1) (9,9-bis(4-hydroxy-3-methylphenyl)fluorene). BPM is the compound represented by the above formula (2) (bisphenol M). BPAP is the compound represented by the above formula (3) (bisphenol AP). BPA is bisphenol A. CEPB is the compound represented by the above formula (Z-1) (hexadecyl-4-hydroxybenzoate). PTBP is the compound represented by the above formula (Z-2) (4-tert-butylphenol). Rikemal S-100A contains glycerin monostearate represented by the above formula (I-1). In addition to glycerin monostearate represented by the above formula (I-1), Rikemal S-100A may also contain glycerin monopalmitate represented by the above formula (I-2). ADK STAB PEP-36 mainly contains a compound represented by the following formula (A): ADK STAB 2112 mainly contains a compound represented by the following formula (B): ADK STAB AO-60 mainly contains a compound represented by the following formula (C):

[0038] (GC-MS measurement conditions) GC: Agilent (registered trademark) 7890 manufactured by Agilent Technologies, Inc. Column: DB-5MUUI (length 30 m, inner diameter 0.25 μm, film thickness 0.25 mm) Carrier gas flow rate: He, 1 ml / min (constant) Injection mode: Split Heating conditions: Heated at 50°C for 5 minutes, then heated from 50°C to 320°C at 20°C / min, and held at 320°C for 10 minutes. Injection port temperature: 300°C Interface temperature: 320°C MS: Agilent (registered trademark) 5977A MSD (mass selective detector) manufactured by Agilent Technologies, Inc. Ion source temperature: 230°C Quadrupole temperature: 150°C Ionization method / energy: EI+, 70 eV Scan range: m / z 33-700

[0039] (Calculation of Abundance Ratio) The abundance ratio of the polycarbonate resin compositions of the Examples and Comparative Examples was calculated as follows. Abundance ratio (GC peak intensity (abundance) ratio) = [Peak intensity of the compound represented by the above formula (II-1)] / [Peak intensity of the compound represented by the above formula (I-1)] = [Peak intensity at RT=19.6] / [Peak intensity at RT=18.5] (RT means retention time). The RTs of the compound represented by formula (I-2) and the compound represented by formula (II-2) are as follows: RT=18.7: formula (II-2) RT=17.7: formula (I-2)

[0040] (Mold deposit evaluation) Using a small injection molding machine Mini-7 (7t) manufactured by Niigata Machine Techno Co., Ltd., continuous molding was performed using a teardrop mold at a cylinder temperature of 260°C, a mold temperature of 10°C, a cycle time of 7 seconds, and 500 shots, and mold deposits collected on the mold surface were evaluated. The evaluation was performed by visually observing the appearance and was rated on the following four-point scale. A: Almost no change in appearance B: Slight mold deposits C: Mold deposits D: Large amount of mold deposits

[0041] In the polycarbonate resin compositions of Examples 1 to 8, in which the abundance ratio was in the range of 1.0 to 10.0, the mold deposit reduction rating was A or B, confirming the effect of reducing mold deposits without sacrificing the inherent efficacy of the additive (mold release effect, etc.). On the other hand, in the polycarbonate resin compositions of Comparative Examples 1 to 3, in which the abundance ratio was less than 1.0, the mold deposit reduction rating was C or D, resulting in the mold release effect being achieved but mold deposits remaining.

[0042] As a consideration, it is believed that a side reaction of the additive (Rikemal S-100A) occurs during melt-kneading (melt extrusion) of the resin, converting a portion of the compound represented by formula (I-1) to a compound represented by formula (II-1). This side reaction is believed to proceed through a transesterification reaction between the glycerin monostearate represented by formula (I-1) and the remaining DPC (diphenyl carbonate) in the reaction system, the resin terminals, or the carbonate bond sites in the resin skeleton. One of the causes of mold deposits is thought to be the accumulation of chemical components contained in the resin, chemicals applied to the mold surface, oils, etc. In the present invention, a portion of the additive compound is modified, producing a specific amount of cyclic carbonate in a range of abundance ratios of 1.0 to 10.0, which is believed to facilitate melting of the deposits. As a result, the polycarbonate resin composition of the present invention can reduce the occurrence of mold deposits while maintaining the inherent efficacy of the additive (antistatic effect, lubricating effect, release effect, emulsifying effect, dispersing effect, anti-fogging effect, etc.).

Claims

1. A polycarbonate resin composition comprising: a polycarbonate resin containing a structural unit (A) derived from a monomer represented by the following formula (1), a structural unit (B) derived from a monomer represented by the following formula (2), or a structural unit (C) derived from a monomer represented by the following formula (3); a compound represented by the following general formula (I); and a compound represented by the following general formula (II), wherein the abundance ratio of the compound represented by the general formula (II) to the compound represented by the general formula (I) ([compound represented by the general formula (II)] / [compound represented by the general formula (I)]) is 1.0 to 10.

0.

2. The polycarbonate resin composition according to claim 1, wherein the terminal structure of the polycarbonate resin contains a structure derived from a terminal terminator represented by the following formula (Z-1) and / or the following formula (Z-2):

3. The polycarbonate resin composition according to claim 1, wherein the compound represented by general formula (I) is represented by the following formula (I-1), or a combination of the following formulas (I-1) and (I-2):

4. The polycarbonate resin composition according to claim 1, wherein the compound represented by general formula (II) is represented by the following formula (II-1), or a combination of the following formulas (II-1) and (II-2):

5. The polycarbonate resin composition according to claim 1, wherein the compound represented by general formula (I) is the following formula (I-1), or a combination of the following formulas (I-1) and (I-2), and the compound represented by general formula (II) is the following formula (II-1), or a combination of the following formulas (II-1) and (II-2).

6. The polycarbonate resin composition according to claim 1, wherein the abundance ratio is 1.0 to 7.

5.

7. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin comprises 10 to 80 mol % of the structural unit (A) and 20 to 90 mol % of the structural unit (B) or the structural unit (C).

8. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin composition contains 20 to 1500 ppm of the compound represented by general formula (I).

9. A method for producing the polycarbonate resin composition according to any one of claims 1 to 8, comprising a step of melt-mixing the polycarbonate resin and the compound represented by general formula (I) under conditions where the cylinder temperature is 280°C or higher and the ratio (Q / Ns) of the discharge rate Q to the screw rotation speed Ns is 0.1 to 1.0.

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