Polycarbonate resin composition and molded article produced therefrom

Abstract

To provide a polycarbonate resin composition that exhibits superior fluidity, heat resistance, and heat stability.SOLUTION: A polycarbonate resin composition comprises, based on 100 pts.wt. of a polycarbonate resin (component A), 10-200 pts.wt. of a styrene resin (component B) including a recycled ABS resin (component B-1) recovered from used automobiles, and 0.001-1 pt.wt. of at least one phosphorus compound (component C) selected from the group consisting of a phosphonic acid compound, a phosphonic acid ester compound, an acid phosphate compound, and a hydrogen phosphite compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article made thereof. More specifically, the present invention relates to a polycarbonate resin composition and a molded article made thereof, which have improved flowability, heat resistance, and thermal stability by adding a styrene resin containing recycled ABS resin recovered from end-of-life automobiles and at least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphonate ester compounds, acid phosphate compounds, and hydrogen phosphite compounds to the polycarbonate resin. [Background technology]

[0002] Polycarbonate resins are widely used industrially due to their excellent mechanical and thermal properties. However, polycarbonate resins have the drawback of poor flowability and moldability due to their high melt viscosity. To improve the flowability of polycarbonate resins, many polymer alloys with other thermoplastic resins have been developed. Polymer alloys with styrene-based resins, such as ABS resin, are a representative example and are widely used in the fields of office automation equipment, electrical and electronic equipment, and automobiles.

[0003] On the other hand, from the perspective of reducing the burden on the global environment, recycling of used home appliances, automobiles, etc. is being promoted, but compared to metals such as iron, recovered plastics often do not have physical properties suitable for use as molding materials, so they are often thermally recycled or disposed of in landfills rather than material recycled. As recovered recycled ABS resin also often does not have physical properties suitable for use as a molding material on its own, resin compositions with physical properties suitable for use as molding materials have been developed by blending recycled ABS resin with unused thermoplastic resins and various additives.

[0004] For example, patent documents 1 and 2 disclose resin compositions in which recycled ABS resin is blended with a graft copolymer, a rigid copolymer, and a flame retardant, resulting in a high recycled ABS resin usage rate and improved chemical resistance, fluidity, impact resistance, and flame retardancy. Patent document 3 also discloses a method of blending recycled ABS resin with other thermoplastic resins to stabilize the physical properties of a composition using recycled ABS resin. Patent document 4 also discloses a resin composition in which ABS resin recovered from discarded home appliances is blended with a resin fluidity modifier, a phosphorus-based flame retardant, and a heat stabilizer, resulting in improved fluidity, impact resistance, and flame retardancy. However, because the recycled ABS resins described in these patent documents are ABS resins recovered by manual disassembly, they contain only small amounts of other resins, metals, minerals, etc., making them relatively easy to use as recycled materials. On the other hand, ABS resin recovered from end-of-life vehicles is a mixture (mixed plastic) obtained by sorting Automobile Shredder Residue (ASR) generated by crushing end-of-life vehicles, and therefore contains various impurities, including metal components that have a negative effect on the resin. Therefore, when ABS resin recovered from end-of-life vehicles is blended with polycarbonate resin, there are problems such as the occurrence of appearance defects such as silver in the molded product and a significant decrease in the molecular weight of the molded product. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6623494 [Patent Document 2] Patent No. 6678689 [Patent Document 3] Patent No. 4035336 [Patent Document 4] Japanese Patent Application Laid-Open No. 2014-159501 Summary of the Invention [Problem to be solved by the invention]

[0006] In view of the above, an object of the present invention is to provide a polycarbonate resin composition excellent in flowability, heat resistance and thermal stability, and a molded article made from the same. [Means for solving the problem]

[0007] As a result of intensive research conducted by the present inventors to solve the above-mentioned problems, they have found that a resin composition having excellent fluidity, heat resistance, and thermal stability can be obtained by incorporating a polycarbonate resin, a styrene resin including recycled ABS resin recovered from end-of-life automobiles, and a predetermined amount of at least one phosphorus-based compound selected from the group consisting of phosphonic acid compounds, phosphonate ester compounds, acid phosphate compounds, and hydrogen phosphite compounds, and have thus completed the present invention.

[0008] That is, the present invention is as follows. 1. A polycarbonate resin composition characterized by containing, relative to 100 parts by weight of (A) a polycarbonate resin (component A), 10 to 200 parts by weight of (B) a styrene resin (component B) containing recycled ABS resin (component B-1) recovered from end-of-life automobiles, and 0.001 to 1 part by weight of (C) at least one phosphorus-based compound (component C) selected from the group consisting of phosphonic acid compounds, phosphonic acid ester compounds, acid phosphate compounds, and hydrogen phosphite compounds. 2. The polycarbonate resin composition according to item 1 above, wherein the content of recycled ABS resin (B-1 component) recovered from end-of-life automobiles in component B is 5 to 100% by weight. 3. A polycarbonate resin composition according to item 1 or 2 above, characterized in that component B is a styrene-based resin consisting of recycled ABS resin (component B-1) recovered from end-of-life automobiles and a styrene-based resin (component B-2) containing acrylonitrile and a styrene-based compound as copolymerization components. The polycarbonate resin composition according to any one of Items 1 to 3 above, characterized in that it contains 0.1 to 5 parts by weight of (D) polyester resin (D component) relative to 100 parts by weight of Component A. A molded article comprising the polycarbonate resin composition according to any one of Items 1 to 4 above.

[0009] Hereinafter, the details of the present invention will be described.

[0010] <Component A: Polycarbonate-based resin> The polycarbonate-based resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include interfacial polymerization method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of cyclic carbonate compound, etc.

[0011] Representative examples of dihydric phenols used herein include hydroquinone, resorcinol, 4,4'-biphenol, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)pentane, 4,4'-(p-phenylene) Examples of suitable dihydric phenols include 4,4'-(m-phenylenediisopropylidene)diphenol, 4,4'-(m-phenylenediisopropylidene)diphenol, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ester, bis(4-hydroxy-3-methylphenyl)sulfide, 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Preferred dihydric phenols are bis(4-hydroxyphenyl)alkanes, and among these, bisphenol A is particularly preferred and widely used in terms of impact resistance.

[0012] In the present invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, special polycarbonate resins produced using other dihydric phenols can be used as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as part or all of the dihydric phenol component are suitable for applications where dimensional change due to water absorption and shape stability are particularly strict requirements. These dihydric phenols other than BPA are preferably used in an amount of 5 mol % or more, particularly 10 mol % or more, of the total dihydric phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is particularly suitable that component A constituting the resin composition is a copolymer polycarbonate resin of the following (1) to (3). (1) A copolymerized polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and BCF accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%). (2) A copolymerized polycarbonate resin in which, based on 100 mol% of the dihydric phenol components constituting the polycarbonate resin, BPA accounts for 10 to 95 mol% (more preferably 50 to 90 mol%, and even more preferably 60 to 85 mol%) and BCF accounts for 5 to 90 mol% (more preferably 10 to 50 mol%, and even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, based on 100 mol% of the dihydric phenol component constituting the polycarbonate resin system, BPM accounts for 20 to 80 mol% (more preferably 40 to 75 mol%, and even more preferably 45 to 65 mol%) and Bis-TMC accounts for 20 to 80 mol% (more preferably 25 to 60 mol%, and even more preferably 35 to 55 mol%).

[0013] These special polycarbonate resins may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with a commonly used bisphenol A polycarbonate resin. The production methods and properties of these special polycarbonate resins are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580.

[0014] Among the various polycarbonate resins mentioned above, those in which the copolymer composition and the like are adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges have good hydrolysis resistance of the polymer itself and are remarkably excellent in terms of low warpage after molding, and are therefore particularly suitable in fields where dimensional stability is required. (i) a polycarbonate resin having a water absorption rate of 0.05 to 0.15%, preferably 0.06 to 0.13%, and a Tg of 120 to 180°C; or (ii) A polycarbonate resin having a Tg of 160 to 250°C, preferably 170 to 230°C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

[0015] Here, the water absorption rate of a polycarbonate resin is a value measured by using a disk-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm and immersing it in water at 23°C for 24 hours in accordance with ISO 62-1980, and then measuring the moisture content. Also, Tg (glass transition temperature) is a value determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0016] Carbonate precursors that can be used include carbonyl halides, carbonic acid diesters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0017] When producing a polycarbonate resin by interfacial polymerization of the dihydric phenol and carbonate precursor, a catalyst, a terminal stopper, an antioxidant to prevent oxidation of the dihydric phenol, etc. may be used as needed. The polycarbonate resin of the present invention also includes branched polycarbonate resins copolymerized with a trifunctional or higher polyfunctional aromatic compound, polyester carbonate resins copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, copolymerized polycarbonate resins copolymerized with a bifunctional alcohol (including alicyclic), and polyester carbonate resins copolymerized with such bifunctional carboxylic acid and bifunctional alcohol. The resulting polycarbonate resins may also be a mixture of two or more of the resulting polycarbonate resins.

[0018] The branched polycarbonate resin can impart anti-drip properties to the resin composition of the present invention. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4 Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)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 acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0019] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate resin are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0020] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0021] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0022] In producing the polycarbonate resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.6 × 10 4 ~4.0×10 4 and more preferably 1.7 × 10 4 ~3.5×10 4 , and more preferably 1.8 × 10 4 ~3.0×10 4 The viscosity average molecular weight is 1.6 × 10 4 On the other hand, polycarbonate resins with a viscosity average molecular weight of less than 4.0 × 10 may not be able to provide good mechanical properties. 4 Resin compositions obtained from polycarbonate resins exceeding this range are inferior in terms of fluidity during injection molding and therefore are inferior in versatility.

[0023] The polycarbonate resin may be a mixture of resins having a viscosity average molecular weight outside the above range. 4), the entropy elasticity of the resin is improved. As a result, good molding processability is exhibited in gas-assisted molding and foam molding, which are sometimes used when molding reinforced resin materials into structural members. Such improvement in molding processability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A has a viscosity average molecular weight of 7×10 4 ~3×10 5 Polycarbonate resin (A-1-1 component) and viscosity average molecular weight 1 × 10 4 ~3×10 4 The viscosity-average molecular weight of the aromatic polycarbonate resin (A-1-2 component) is 1.6 × 10 4 ~3.5×10 4 A polycarbonate resin (component A-1) (hereinafter, sometimes referred to as a "polycarbonate resin containing a high molecular weight component") can also be used.

[0024] In the polycarbonate resin containing such a high molecular weight component (component A-1), the molecular weight of component A-1-1 is 7 × 10 4 ~2×10 5 is preferable, and more preferably 8×10 4 ~2×10 5 , and more preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10 4 ~2.5×10 4 is preferable, and more preferably 1.1 × 10 4 ~2.4×10 4 , and more preferably 1.2 × 10 4 ~2.4×10 4 , particularly preferably 1.2 × 10 4 ~2.3×10 4 is.

[0025] The high-molecular-weight component-containing polycarbonate resin (component A-1) can be obtained by mixing components A-1-1 and A-1-2 in various ratios and adjusting the ratio to satisfy a predetermined molecular weight range. Preferably, component A-1-1 accounts for 2 to 40% by weight, more preferably 3 to 30% by weight, even more preferably 4 to 20% by weight, and particularly preferably 5 to 20% by weight, of 100% by weight of component A-1.

[0026] Methods for preparing component A-1 include: (1) a method in which component A-1-1 and component A-1-2 are polymerized independently and then mixed; (2) a method in which an aromatic polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart obtained by GPC, such as the method disclosed in Japanese Patent Laid-Open No. 5-306336, is produced in the same system, and the polycarbonate resin is produced so as to satisfy the conditions for component A-1 of the present invention; and (3) a method in which a polycarbonate resin obtained by such a production method (production method (2)) is mixed with component A-1-1 and / or component A-1-2 that have been produced separately.

[0027] The viscosity average molecular weight in the present invention is determined by first calculating the specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of polycarbonate resin dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and calculate the viscosity average molecular weight M using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c=0.7

[0028] The polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, which is preferably prepared by copolymerizing a dihydric phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3):

[0029] [ka]

[0030] [In the above general formula (1), R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0031] [ka]

[0032] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0033] [ka]

[0034] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0035] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0036] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0037] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0038] [ka]

[0039] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0040] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0041] The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0042] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0043] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0044] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0045] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0046] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0047] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0048] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0049] As the solvent, various solvents inert to reactions, such as those used in the production of known polycarbonate resins, may be used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0050] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0051] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0052] [ka]

[0053] (In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0054] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0055] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0056] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0057] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0058] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0059] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 Examples include trisphenols such as {1,1-bis(4-hydroxyphenyl)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 acid chlorides thereof, and among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0060] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0061] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of formula [ / c].

[0062] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification).

[0063] The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. This average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. If the domain size is below the lower limit of this preferred range, sufficient impact resistance may not be exhibited, and if the domain size exceeds the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0064] The average domain size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded articles of the present invention was evaluated by small-angle X-ray scattering (SAXS). Small-angle X-ray scattering is a method for measuring diffuse scattering and diffraction occurring in the small-angle region of scattering angles (2θ) less than 10°. In this method, if a substance contains regions with different electron densities of approximately 1 to 100 nm in size, the diffuse scattering of X-rays is measured based on the electron density difference. The particle size of the object being measured is determined based on the scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resins, which form an aggregate structure in which polydiorganosiloxane domains are dispersed within a polycarbonate polymer matrix, the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains causes diffuse scattering of X-rays. The scattering intensity I at each scattering angle (2θ) within a range of scattering angles (2θ) less than 10° is measured to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variation in particle size distribution, a simulation is performed using commercially available analytical software based on a hypothetical particle size and a hypothetical particle size distribution model to determine the average size of the polydiorganosiloxane domains. Small-angle X-ray scattering allows for accurate, simple, and reproducible measurement of the average size of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by observation with a transmission electron microscope. The average domain size refers to the number average of the individual domain sizes.

[0065] As the polycarbonate resin of the present invention, a recycled polycarbonate resin can also be used. The recycled polycarbonate resin is preferably a recycled polycarbonate resin obtained from the recovered materials of molded articles containing a polycarbonate resin. The molded articles may be used products. Examples of the used products include various glazing materials typified by sound insulation walls, automobile windows, translucent roofing materials, and automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, light guide plates, spectacle lenses, and optical recording media. In addition, defective products, sprues, runners, etc. of the products can also be used.

[0066] <Component B: Styrene resin containing recycled ABS resin recovered from used automobiles> The resin composition of the present invention contains, as Component B, a styrene resin containing a recycled ABS resin recovered from used automobiles. The styrene resin preferably consists of a recycled ABS resin (Component B-1) recovered from used automobiles and a styrene resin (Component B-2) containing acrylonitrile and a styrene-based compound as copolymerization components.

[0067] The content of Component B is 10 to 200 parts by weight, preferably 15 to 150 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of Component A. When the content of Component B is less than 10 parts by weight, the fluidity deteriorates, and when it exceeds 200 parts by weight, the heat resistance deteriorates.

[0068] <Component B-1: Recycled ABS resin recovered from used automobiles> Recycled ABS resin recovered from used automobiles is selected from automobile shredder dust (ASR: Automobile Shredder Residue) obtained by crushing used automobiles. The selection method is not particularly limited, and methods such as specific gravity separation, electrostatic separation, near-infrared separation, and air separation can be used. Also, these separation methods may be combined and used. Since the recycled ABS resin recovered by separation is a mixed plastic, unlike manually disassembled plastics, various impurities such as metals and minerals remain relatively more. The amount of metals and minerals in the recycled ABS resin recovered from used automobiles can be quantified by the residue ratio (ash residue amount) when the recycled ABS resin is treated in an electric furnace at 600 °C for 3 hours. The ash residue amount in the recycled ABS resin is preferably 5% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less. If the ash residue amount exceeds 5% by weight, the thermal stability may be inferior, and when blended with a polycarbonate-based resin, it may lead to the generation of silver and a significant decrease in molecular weight. The lower limit of the ash residue amount is not particularly limited, but it is preferably 0.05% by weight or more.

[0069] The content of component B-1 in component B is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, and even more preferably 15 to 100% by weight. If the content of component B-1 is less than 5% by weight, the amount of recycled ABS resin in the composition may be small, and it may not be suitable as an environmentally friendly material.

[0070] <Component B-2: A styrene-based resin containing acrylonitrile and a styrene-based compound as copolymerization components> Styrenic resins containing acrylonitrile and a styrene compound as copolymerization components are polymers obtained by copolymerizing a copolymer of acrylonitrile and a styrene resin and a rubbery polymer copolymerizable therewith. Styrene and α-methylstyrene are preferred as styrene compounds, with styrene being particularly preferred. When the total amount of acrylonitrile and the styrene compound is taken as 100% by weight, the acrylonitrile content is preferably 5 to 50% by weight, more preferably 15 to 35% by weight, and the styrene compound content is preferably 95 to 50% by weight, more preferably 85 to 65% by weight. Furthermore, various known initiators, chain transfer agents, etc., can be used in the reaction as needed, and may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization. Copolymerizable rubbery polymers include polybutadiene, polyisoprene, diene copolymers (e.g., random copolymers and block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, and copolymers of (meth)acrylic acid alkyl esters and butadiene, etc.), copolymers of ethylene and α-olefins (e.g., ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, etc.), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers, ethylene-butyl acrylate copolymers, etc.), copolymers of ethylene and aliphatic vinyls (e.g., ethylene-acetic acid copolymers, Examples of such rubbers include ethylene-propylene and non-conjugated diene terpolymers (e.g., ethylene-propylene-hexadiene copolymers), acrylic rubbers (e.g., polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate), and silicone rubbers (e.g., polyorganosiloxane rubbers, IPN rubbers consisting of a polyorganosiloxane rubber component and a polyalkyl(meth)acrylate rubber component; i.e., rubbers in which the two rubber components are intertwined so that they cannot be separated, and IPN rubbers consisting of a polyorganosiloxane rubber component and a polyisobutylene rubber component).Specific examples of the styrenic resin containing the acrylonitrile and styrenic compounds as copolymerization components include, for example, AS resin, non-recycled ABS resin, AES resin, and ASA resin. Among these, AS resin and non-recycled ABS resin are preferred. Also, it is possible to use a mixture of two or more of these.

[0071] <Component C: At least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphonic acid ester compounds, acid phosphate compounds, and hydrogen phosphite compounds> The resin composition of the present invention contains, as component C, at least one phosphorus compound selected from the group consisting of phosphonic acid compounds, phosphonic acid ester compounds, acid phosphate compounds, and hydrogen phosphite compounds. When a compound other than these compounds is used as the phosphorus compound, the thermal stability deteriorates.

[0072] Examples of the phosphonic acid compound include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, benzylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and nitrilotris(methylenephosphonic acid). Among them, phenylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and nitrilotris(methylenephosphonic acid) are preferred.

[0073] Examples of the phosphonic acid ester compound include phosphonic acid monoester, phosphonic acid diester, and phosphonic acid triester. Among them, phosphonic acid triester is preferred.

[0074] Examples of the acid phosphate compounds include monostearyl acid phosphate, distearyl acid phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, isodecyl acid phosphate, dioctadecyl phosphate, and salts thereof such as zinc distearyl acid phosphate and metal salts of monostearyl acid phosphate. Among them, monostearyl acid phosphate, distearyl acid phosphate, zinc monostearyl acid phosphate, and zinc distearyl acid phosphate are preferred.

[0075] Examples of the hydrogen phosphite compounds include diethyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, and diphenyl hydrogen phosphite.

[0076] Among these phosphorus compounds, phosphonic acid compounds and phosphonic acid ester compounds are preferred, and phosphonic acid compounds are more preferred.

[0077] The content of Component C is 0.001 to 1 part by weight, preferably 0.01 to 0.7 part by weight, and more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of Component A. When the content of Component C is less than 0.001 part by weight or exceeds 1 part by weight, the thermal stability deteriorates.

[0078] <Component D: Polyester resin> The resin composition of the present invention preferably contains a polyester resin as component D. Preferred polyester resins are aromatic polyester resins such as aromatic polybutylene terephthalate resins, aromatic polyethylene terephthalate resins, and aromatic polyarylate resins. The aromatic polybutylene terephthalate resins and aromatic polyethylene terephthalate resins preferably used in the present invention are aromatic polybutylene terephthalate resins and aromatic polyethylene terephthalate resins in which, of the dicarboxylic acid components and diol components that form the polyester, 70 mol % or more of 100 mol % of the dicarboxylic acid components are aromatic dicarboxylic acids, more preferably 90 mol % or more, and most preferably 99 mol % or more. Examples of dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5-Na sulfoisophthalic acid, and ethylene-bis-p-benzoic acid. These dicarboxylic acids can be used alone or in combination. In addition to the aromatic dicarboxylic acids described above, the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention can also contain less than 30 mol% of an aliphatic dicarboxylic acid component copolymerized therein. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.Examples of diol components of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used alone or in combination. The dihydric phenol content in the diol component is preferably 30 mol% or less.

[0079] The aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention are produced by conventional methods, such as by polymerizing a dicarboxylic acid component and a diol component under heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, or the like, and then discharging the by-product water or lower alcohol from the system. Examples of germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, and phenolates. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, and tetramethoxygermanium can be used. In the present invention, compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction that precedes polycondensation, can also be used in combination. After the transesterification reaction, the catalyst can be deactivated with a phosphoric acid or phosphorous acid compound before polycondensation. Furthermore, the production of aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin can be carried out by either a batch or continuous polymerization method.

[0080] The molecular weight of the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 25°C using o-chlorophenol as a solvent is preferably 0.4 to 1.5, and more preferably 0.5 to 1.2.

[0081] The amount of terminal carboxy groups in the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq / ton, more preferably 5 to 70 eq / ton, and even more preferably 7 to 65 eq / ton.

[0082] The aromatic polyarylate resin preferably used in the present invention is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative. The aromatic dicarboxylic acid used in preparing the aromatic polyarylate resin may be any one that reacts with the dihydric phenol to give a satisfactory polymer, and may be used alone or in combination of two or more.

[0083] Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid, and mixtures thereof may also be used.

[0084] Specific examples of dihydric phenol components include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, and hydroquinone. These dihydric phenol components are para-substituted, but other isomers may also be used. Furthermore, the dihydric phenol components may be used in combination with ethylene glycol, propylene glycol, neopentyl glycol, or the like.

[0085] Among the above, preferred aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the dihydric phenol component is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9 / 1 to 1 / 9 (molar ratio), and particularly from the viewpoint of melt processability and performance balance, it is desirable to be 7 / 3 to 3 / 7.

[0086] Other typical aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and the dihydric phenol component is bisphenol A and hydroquinone. The ratio of bisphenol A to hydroquinone is preferably bisphenol A / hydroquinone = 50 / 50 to 70 / 30 (molar ratio), more preferably 55 / 45 to 70 / 30, and even more preferably 60 / 40 to 70 / 30.

[0087] In the present invention, the aromatic polyarylate resin preferably has a viscosity average molecular weight in the range of 7,000 to 100,000 in terms of physical properties and extrusion processability. The aromatic polyarylate resin can be produced by either the interfacial polycondensation method or the transesterification method.

[0088] The content of component D is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4 parts by weight, and even more preferably 0.3 to 3 parts by weight, per 100 parts by weight of component A. If the content of component D is less than 0.1 part by weight, it may not be possible to prevent a decrease in molecular weight of the molded article. On the other hand, if it exceeds 5 parts by weight, poor appearance such as silver may occur.

[0089] <Other ingredients> The resin composition of the present invention may also contain phenolic stabilizers, mold release agents, ultraviolet absorbers, core-shell type graft polymers other than component B, dyes and pigments (carbon black, titanium oxide, etc.), and the like.

[0090] (i) Phenolic stabilizers The resin composition of the present invention can be blended with a phenolic stabilizer such as a hindered phenol compound. Various compounds typically blended into resins can be used as the hindered phenol compound. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl- 4-Hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol) phenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5 -methyl-2-hydroxybenzyl)phenyl] terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5- Di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methyl phenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. Particularly preferred is 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane. The above hindered phenol compounds can be used alone or in combination of two or more.

[0091] The content of the phenolic stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 part by weight, relative to 100 parts by weight of the component A.

[0092] (ii) Mold release agent The polycarbonate resin composition of the present invention can be blended with a mold release agent to improve productivity during molding and reduce distortion of molded products. Known mold release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc.; those modified with functional group-containing compounds, such as acid-modified waxes, can also be used), silicone compounds, fluorine compounds (fluorinated oils, such as polyfluoroalkyl ethers), paraffin wax, and beeswax. Fatty acid esters are preferred mold release agents. Fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohols may be monohydric alcohols or polyhydric alcohols (dihydric or higher). The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred for the fatty acid ester of the present invention. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and more preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among these, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are preferred.Stearic acid and palmitic acid are particularly preferred. The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are typically produced from natural oils and fats, such as animal oils and fats (e.g., beef tallow and lard) and vegetable oils and fats (e.g., palm oil and sunflower oil). Therefore, these aliphatic carboxylic acids are typically mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural oils and fats and in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used. The fatty acid ester may be either a partial ester or a full ester (full ester). However, partial esters typically have a high hydroxyl value, which can easily induce resin decomposition at high temperatures. Therefore, full esters are more preferred. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0093] The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, relative to 100 parts by weight of component A.

[0094] (iii) UV absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridobenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Benzotriazoles include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as azole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer.Examples of hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol.Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

[0095] Examples of cyanoacrylates include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0096] Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0097] The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 part by weight, relative to 100 parts by weight of the A component.

[0098] (iv) Core-shell type graft polymer other than component B The polycarbonate resin composition of the present invention may contain a core-shell type graft polymer other than component B. The core-shell type graft polymer is a graft copolymer in which a rubber component having a glass transition temperature of 10°C or less is used as the core and one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith are copolymerized as the shell.

[0099] Examples of rubber components for core-shell graft polymers include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to the unsaturated bonds. However, due to concerns about the release of harmful substances during combustion, halogen-free rubber components are preferred in terms of environmental impact. The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower. Butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferred. Composite rubber refers to rubber obtained by copolymerizing two types of rubber components or rubber obtained by polymerizing them to form an IPN structure in which the components are inseparably intertwined. In the core-shell type graft polymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.15 to 0.5 μm, in terms of weight average particle size. If it is in the range of 0.05 to 0.8 μm, better impact resistance can be achieved.

[0100] Examples of aromatic vinyl compounds in the vinyl compounds copolymerized with the rubber component as the shell of the core-shell graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is preferable to contain a methacrylic acid ester such as methyl methacrylate as an essential component. This is because the core-shell graft polymer has excellent affinity with aromatic polycarbonate resins, resulting in a larger amount of rubber component present in the resin, which more effectively utilizes the excellent impact resistance of the aromatic polycarbonate resin, resulting in improved impact resistance of the resin composition. More specifically, the methacrylic acid ester content is preferably 10% by weight or more, more preferably 15% by weight or more, based on 100% by weight of the graft component (100% by weight of the shell in the case of a core-shell polymer). Elastic polymers containing a rubber component with a glass transition temperature of 10°C or less may be produced by any of the following polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be either single-stage or multi-stage grafting. They may also be a mixture with a copolymer of only the graft component, which is a by-product of production. Polymerization methods include, in addition to standard emulsion polymerization, soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. In addition, suspension polymerization may involve separately maintaining the aqueous phase and the monomer phase and accurately feeding them into a continuous disperser, controlling the particle size by adjusting the rotation speed of the disperser. Alternatively, continuous production methods may involve feeding the monomer phase into an aqueous liquid with dispersibility through a small orifice or porous filter with a diameter of several to several tens of micrometers, thereby controlling the particle size. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

[0101] Such polymers are commercially available and easily available. For example, those containing butadiene rubber as the main component of the rubber component include Kane Ace M series manufactured by Kaneka Corporation (e.g., M-711 whose shell component is mainly methyl methacrylate, M-724 whose shell component is mainly methyl methacrylate-styrene, etc.), Metablen C series manufactured by Mitsubishi Chemical Corporation (e.g., C-223A whose shell component is mainly methyl methacrylate-styrene, etc.), and E series (e.g., E-870A whose shell component is mainly methyl methacrylate-styrene, etc.), and those containing acrylic rubber or butadiene-acrylic composite rubber as the main component are also available. Examples of such rubbers include those sold under the trade names Metablen W series (for example, W-600A, whose shell component is primarily methyl methacrylate) manufactured by Mitsubishi Chemical Corporation and Paraloid EXL series (for example, EXL-2390, whose shell component is primarily methyl methacrylate) manufactured by Dow Chemical Corporation, and those whose main rubber component is acrylic-silicone composite rubber include those sold under the trade names Metablen S-2030 and S-2130, whose shell component is primarily methyl methacrylate, manufactured by Mitsubishi Chemical Corporation.

[0102] (v) Other resins and elastomers The resin composition of the present invention can also contain small amounts of other resins or elastomers as long as the effects of the present invention are achieved. Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polyolefin resins such as polyethylene and polypropylene, polymethacrylate resins, phenolic resins, and epoxy resins. Examples of elastomers include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

[0103] (vi) Dyes and pigments The polycarbonate resin composition of the present invention contains dyes and pigments, enabling molded articles to exhibit a variety of designs. By incorporating fluorescent brighteners or other luminescent fluorescent dyes, even better design effects can be achieved by utilizing the luminescent color. It is also possible to provide polycarbonate resin compositions that are colored with extremely small amounts of dyes and pigments and have vivid color development. Examples of fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred, as they have good heat resistance and are less susceptible to degradation during molding and processing of polycarbonate resins. Examples of dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Suitable metallic pigments include those having a metal coating or a metal oxide coating on various plate-like fillers.

[0104] The content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the component A.

[0105] (vii) Flame retardants The polycarbonate resin composition of the present invention can contain various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins. Among these, preferred are (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt-based flame retardants (e.g., alkali (earth) metal organic sulfonates, borate metal salt-based flame retardants, and stannate metal salt-based flame retardants), and (iv) silicone-based flame retardants consisting of silicone compounds. The incorporation of the compounds used as flame retardants not only improves flame retardancy, but also, depending on the properties of each compound, improves antistatic properties, fluidity, rigidity, and thermal stability, among other things.

[0106] The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, relative to 100 parts by weight of Component A. If the content of the flame retardant is less than 0.01 part by weight, sufficient flame retardancy may not be obtained, whereas if it exceeds 30 parts by weight, mechanical properties may be significantly reduced.

[0107] (viii) Highly reflective white pigment The polycarbonate resin composition of the present invention can be blended with a highly light-reflecting white pigment to impart a light-reflecting effect. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such highly light-reflecting white pigment is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, per 100 parts by weight of Component A. Two or more types of highly light-reflecting white pigments can be used in combination.

[0108] (ix) Other additives In addition, the resin composition of the present invention can contain small amounts of known additives to impart various functions to molded articles or improve their properties. These additives can be added in conventional amounts as long as they do not impair the objectives of the present invention. Such additives include sliding agents (e.g., PTFE particles), light diffusing agents (e.g., acrylic cross-linked particles, silicon cross-linked particles, ultrathin glass flakes, calcium carbonate particles), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., fine particle titanium oxide, fine particle zinc oxide), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents.

[0109] <Method for preparing polycarbonate resin composition> The polycarbonate resin composition of the present invention is prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Melt-kneading using a twin-screw extruder is preferred as the mixer. If necessary, any component may be fed into the other melt-mixed components through a second feed port using a side feeder or the like. The extruded resin as described above is either directly cut and pelletized, or formed into strands, which are then cut and pelletized using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The resulting pellets may have common shapes such as cylinders, prisms, and spheres, but cylinders are preferred. The diameter of the cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. The length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0110] <Molded articles made from polycarbonate resin compositions> The polycarbonate resin composition of the present invention can be used to produce various products by injection molding the pellets obtained by the above-mentioned method. In such injection molding, molded articles can be obtained using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, either a cold runner system or a hot runner system can be used for molding. [Effects of the Invention]

[0111] The polycarbonate resin composition of the present invention has excellent fluidity, heat resistance, and thermal stability, making it useful in a wide range of applications, including housing equipment, building materials, daily necessities, infrastructure equipment, automobiles, office equipment and cleaning equipment, outdoor equipment, and various other fields. In addition, the ABS resin recovered from end-of-life automobiles is recycled, which contributes to reducing the burden on the global environment. Therefore, the industrial effects of the present invention are extremely significant. DETAILED DESCRIPTION OF THE INVENTION

[0112] The present inventors currently consider the best mode of the invention to be a combination of the preferred ranges of each of the above-mentioned requirements, and representative examples thereof are described in the following examples, although the present invention is not limited to these modes. [Example]

[0113] The present invention will be further explained below with reference to examples, which were evaluated by the following methods.

[0114] (1) Thermal stability (i) Viscosity average molecular weight Three grams of pellets obtained using the method described below were dissolved in 60 ml of methylene chloride and filtered. The filtrate was transferred to a stainless steel dish, and the methylene chloride was evaporated. The filtrate was then vacuum-dried at 120°C for 1 hour to produce a film. The viscosity-average molecular weight of the resulting film was measured using the method described herein. After obtaining an ISO tensile test specimen using the method described below, the molding machine was stopped for 10 minutes under the same conditions, allowing the molten resin to remain in the molding machine cylinder. Ten minutes after stopping the molding machine, molding was restarted. An ISO tensile test specimen was obtained from the second shot after remolding, and the viscosity-average molecular weight was measured using the same method. The molecular weight of the pellets minus the molecular weight of the ISO tensile test specimen from the second shot after remolding was evaluated as ΔMv. A smaller ΔMv indicates better thermal stability.

[0115] (ii) Appearance of molded product After obtaining ISO tensile test specimens using the method described below, the molding machine was stopped under the same conditions for 10 minutes, allowing the molten resin to remain in the molding machine cylinder. 10 minutes after stopping the molding machine, molding was restarted, and five consecutive shots were obtained from the restart. The appearance of the second to fifth shots was visually evaluated, and the number of specimens with appearance defects such as silver spots was counted. The number of specimens with appearance defects such as silver spots must be two or fewer out of four shots.

[0116] (2) Heat resistance (deflection temperature under load) Using the ISO bending test specimens obtained by the method described below, the deflection temperature under load (load 1.80 MPa) was measured in accordance with ISO 75-1 and ISO 75-2. The deflection temperature under load must be 85°C or higher.

[0117] (3) Liquidity Using pellets obtained by the method described below, the length of an Archimedes-type spiral flow with a channel thickness of 2 mm and a channel width of 8 mm was measured using an injection molding machine (SE130EV-A manufactured by Sumitomo Heavy Industries, Ltd.). The measurement was performed at a cylinder temperature of 260°C, a mold temperature of 70°C, and an injection pressure of 98 MPa. The spiral flow length must be 20 cm or more.

[0118] [Examples 1 to 26, Comparative Examples 1 to 6] The components listed in Tables 1 and 2 were weighed and mixed uniformly using a tumbler. The mixture was fed through the first feed port of the extruder. The extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30α-38.5BW-3V, manufactured by The Japan Steel Works, Ltd.) at a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa to obtain pellets. The extrusion temperature from the first feed port to the die was 260°C. The resulting pellets were dried in a hot air circulating dryer at 100°C for 6 hours and then molded into ISO flexural test specimens and ISO tensile test specimens using an injection molding machine (cylinder temperature 260°C, mold temperature 60°C). Evaluations were then performed. The results are shown in Tables 1 and 2.

[0119] The following raw materials were used: (Component A) A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 22,400, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WP) A-2: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 19,800, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WX) A-3: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 16,000, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite CM-1000) A-4: Polycarbonate-polydiorganosiloxane copolymer resin (viscosity average molecular weight 19,800, PDMS content 8.4%, PDMS polymerization degree 37) A-5: Recycled polycarbonate resin (recycled polycarbonate resin with a viscosity average molecular weight of 21,300, recycled from a sheet made of a polycarbonate resin composition) A-6: Recycled polycarbonate resin (a recycled polycarbonate resin with a viscosity average molecular weight of 15,100 recycled from an optical recording medium made of a polycarbonate resin composition)

[0120] (B component) (B-1 component) B-1-1: ABS resin recovered from end-of-life vehicles (ash residue amount 1.5% by weight, product name PLC-EM01 manufactured by Planic Co., Ltd.) (B-2 component) B-2-1: ABS resin (Magnum A371 (product name) manufactured by Trinseo) B-2-2: AS resin (product name: BS-207, manufactured by Nippon A&L Co., Ltd.)

[0121] (C component) C-1: Phenylphosphonic acid (Nissan Chemical Co., Ltd., PPA (product name)) C-2: Nitrilotris(methylenephosphonic acid) (product name: JPCN-300, manufactured by Johoku Chemical Industry Co., Ltd.) C-3: 1-Hydroxyethane-1,1-diphosphonic acid (Chilest PH-210 (product name) manufactured by Chelest Co., Ltd.) C-4: Triethyl phosphonoacetate (JC-224 (product name) manufactured by Johoku Chemical Industry Co., Ltd.) C-5: Stearyl acid phosphate (ADEKA Corporation, AX-71 (trade name)) C-6: Stearyl acid phosphate zinc salt (product name: JP-518Zn, manufactured by Johoku Chemical Industry Co., Ltd.) C-7: Diphenyl hydrogen phosphite (product name: JP-260, manufactured by Johoku Chemical Industry Co., Ltd.) C-8 (Comparative Example): Tris(2,4-di-tert-butylphenyl)phosphite (ADEKA CORPORATION, ADK STAB 2112 (trade name)) C-9 (Comparative Example): Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite (product name: 6260PW, manufactured by SONGWON)

[0122] (D component) D-1: Polyethylene terephthalate resin (Teijin Limited, product name: TRN-MTJ) D-2: Polybutylene terephthalate resin (BASF Japan Ltd., product name B4500)

[0123] (Other ingredients) E-1: Phenolic heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, (ADEKA Corporation, product name AO-50) E-2: Butadiene-based core-shell graft polymer (Kane Ace M-711 (product name) manufactured by Kaneka Corporation) E-3: Benzotriazole-based UV absorber (product name: Tinuvin 234, manufactured by BASF Japan Ltd.) E-4: Pentaerythritol-based release agent (NOF Corporation, Unistar H-476-S (product name)) E-5: Carbon black (Koshigaya Chemical Co., Ltd.: ROYAL BLACK RB90003S (product name))

[0124] [Table 1]

[0125] [Table 2]

[0126] From the above table, it can be seen that resin compositions containing a polycarbonate resin, a styrene resin including recycled ABS resin recovered from end-of-life automobiles, and a predetermined amount of at least one phosphorus-based compound selected from the group consisting of phosphonic acid compounds, phosphonate ester compounds, acid phosphate compounds, and hydrogen phosphite compounds have excellent fluidity, heat resistance, and thermal stability.

Claims

1. A polycarbonate resin composition comprising, relative to 100 parts by weight of (A) a polycarbonate resin (component A), 10 to 200 parts by weight of (B) a styrene resin (component B) containing recycled ABS resin (component B-1) recovered from end-of-life automobiles, and 0.001 to 1 part by weight of (C) at least one phosphorus-based compound (component C) selected from the group consisting of phosphonic acid compounds, phosphonate ester compounds, acid phosphate compounds, and hydrogen phosphite compounds.

2. 2. The polycarbonate resin composition according to claim 1, wherein the content of recycled ABS resin (B-1 component) recovered from end-of-life automobiles in Component B is 5 to 100% by weight.

3. 3. The polycarbonate resin composition according to claim 1, wherein component B is a styrene-based resin comprising recycled ABS resin (component B-1) recovered from end-of-life automobiles and a styrene-based resin (component B-2) containing acrylonitrile and a styrene-based compound as copolymerization components.

4. 3. The polycarbonate resin composition according to claim 1, further comprising 0.1 to 5 parts by weight of a polyester resin (D) (Component D) per 100 parts by weight of Component A.

5. A molded article made from the polycarbonate resin composition according to claim 1 or 2.

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