Polycarbonate resin composition and molded articles formed therefrom

Abstract

This enables the use of recycled polycarbonate resin without degrading its mechanical properties, thermal conductivity, thermal stability during retention, or recyclability. [Solution] A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A) consisting of (A-1) 1 to 99 parts by weight of recycled polycarbonate resin (component A-1) and (A-2) 99 to 1 part by weight of non-recycled polycarbonate resin (component A-2), wherein (B) 1 to 100 parts by weight of inorganic filler (component B) and (C) 0.001 to 2 parts by weight of phosphate-based stabilizer (component C), wherein the ashing residue amount of component (A-1) after 3 hours at 600°C is 0 to 0.4% by weight, and the temperature of the 5% weight loss of component (A-1), measured under a temperature increase of 20°C / min in a nitrogen atmosphere, is 405°C to 505°C.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition that enables high-level property maintenance and molded articles formed therefrom, comprising recycled polycarbonate resin having a specific ashing residual amount and weight loss temperature, non-recycled polycarbonate resin, an inorganic filler, and a phosphate-based stabilizer. [Background technology]

[0002] Thermoplastic resin compositions are used in a wide range of fields, including casings and components for electrical, electronic, and office automation equipment, interior and exterior parts for automobiles, furniture, musical instruments, and general merchandise. In recent years, in particular, high recyclability of thermoplastic resin compositions has become desirable for the realization of a sustainable society. Polycarbonate resin, in particular, is an expensive material, and recycling it can reduce the consumption of new resources and promote sustainable resource use. Therefore, the use of recycled polycarbonate resin has become an important social responsibility.

[0003] On the other hand, the use of recycled polycarbonate resin has been difficult due to the significant degradation of its properties upon recycling. When recycled, the deterioration of material properties when inorganic fillers are included is a problem, which is fatal for polycarbonate resins containing inorganic fillers where mechanical properties are required, making it crucial to solve this problem. The decrease in thermal stability is also a major issue. Furthermore, the use of phosphorus-based compounds as thermal stabilizers in polycarbonate resin compositions is widely known. Patent Document 1 discloses the use of specific phosphorus-based compounds in resins consisting of polycarbonate-based resins and polyester resins. Patent Document 2 discloses the use of phosphorus-based compounds in combination. However, existing methods have not yet reached a level that makes it possible to use recycled polycarbonate resin, and the use of recycled polycarbonate resin is strongly desired. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 4983427 [Patent Document 2] Patent No. 5640734 [Overview of the project] [Problems that the invention aims to solve]

[0005] The objective of the present invention is to enable the use of recycled polycarbonate resin without degrading its properties such as mechanical properties, thermal conductivity, thermal stability during retention, and recyclability. [Means for solving the problem]

[0006] As a result of diligent research aimed at achieving the above objective, the inventors of the present invention have discovered that by selecting a polycarbonate resin having a specific ashing residue amount and weight loss temperature, it is possible to maintain high levels of properties (mechanical properties, thermal conductivity, thermal stability during retention, recyclability, etc.) even when using recycled polycarbonate resin, leading to the present invention.

[0007] In other words, the present invention is as follows. 1. A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), consisting of (A-1) 1 to 99 parts by weight of recycled polycarbonate resin (component A-1) and (A-2) 99 to 1 part by weight of non-recycled polycarbonate resin (component A-2), wherein (B) inorganic filler (component B) and (C) phosphate-based stabilizer (component C) are present, and component (A-1) has an ashing residue of 0 to 0.4% by weight after 3 hours at 600°C, and component (A-1) has a 5% weight loss temperature of 405°C to 505°C measured under a temperature increase of 20°C / min in a nitrogen atmosphere. 2. The polycarbonate resin composition according to item 1 above, wherein component (B) is at least one inorganic filler selected from the group consisting of (B-1) glass fiber (component (B-1)), (B-2) plate-shaped glass filler (component (B-2)), (B-3) fibrous carbon filler (component (B-3)), (B-4) non-fibrous carbon filler (component (B-4)), and (B-5) silicate mineral (component (B-5)). 3. The polycarbonate resin composition according to item 1 or 2 above, wherein component (C) is at least one phosphate stabilizer selected from the group consisting of (C-1) phosphonate ester (component (C-1)), (C-2) acidic phosphate ester (component (C-2)), and metal salt of acidic phosphate ester (component (C-3)). 4. The recycled polycarbonate resin (component (A-1)) is obtained by a production process including (i) a step of pulverizing a recovered polycarbonate resin molded product provided with at least one magnetic separation step (pulverization step), (ii) a step of washing the pulverized product obtained by the pulverization step (washing step), and (iii) an extrusion step of pelletizing the pulverized and washed product obtained by the washing step by melt-kneading (extrusion step). The polycarbonate resin composition according to any one of items 1 to 3 above. 5. The polycarbonate resin composition according to any one of items 1 to 4 above, containing 0.001 to 1 part by weight of (D) phosphite stabilizer (component (D)) with respect to 100 parts by weight of component (A). 6. A molded product formed from the polycarbonate resin composition according to any one of items 1 to 5 above.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a polycarbonate resin composition and a molded product having excellent mechanical properties, thermal conductivity, thermal stability during residence time, and recyclability by using a recycled polycarbonate resin having a specific ash residue amount and weight loss temperature. Such polycarbonate resin compositions and molded products can be suitably used in a wide range of fields such as casings and parts of electric, electronic, and OA equipment, interior and exterior parts for automobiles, furniture, musical instruments, sundries, etc., and the industrial effect they exhibit is extremely great.

Embodiments for Carrying Out the Invention

[0009] The following will describe the details of the present invention.

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

[0011] Typical examples of the dihydric phenol used here 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-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. A preferred dihydric phenol is bis(4-hydroxyphenyl)alkane, and among them, bisphenol A is particularly preferred from the viewpoint of impact resistance and is widely used.

[0012] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols 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 some or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. It is preferable that these divalent phenols other than BPA be used in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin. In particular, when high rigidity and better hydrolysis resistance are required, it is especially preferable that component A constituting the resin composition be one of the following copolymer polycarbonate resins (1) to (3). (1) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and BCF is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%) and BCF is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, of 100 mol% of the divalent phenol component constituting the polycarbonate resin, BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%) and Bis-TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0013] These special polycarbonate resins may be used individually or mixed in appropriate combinations of two or more types. They can also be mixed with commonly used bisphenol A type polycarbonate resins. The manufacturing methods and properties of these special polycarbonate resins are described in detail in, for example, Japanese Patent Publication No. 6-172508, Japanese Patent Publication No. 8-27370, Japanese Patent Publication No. 2001-55435, and Japanese Patent Publication No. 2002-117580.

[0014] Furthermore, among the various polycarbonate resins mentioned above, those whose copolymerization composition and other properties have been adjusted to bring the water absorption rate and Tg (glass transition temperature) within the following ranges exhibit excellent hydrolysis resistance of the polymer itself, as well as significantly superior low warping after molding. Therefore, they are particularly suitable for fields requiring morphological stability. (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 rate 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 the polycarbonate resin was measured using a disc-shaped test piece with a diameter of 45 mm and a thickness of 3.0 mm, after immersion in water at 23°C for 24 hours in accordance with ISO 62-1980. The glass transition temperature (Tg) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0016] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

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

[0018] Branched polycarbonate resins can impart properties such as drip prevention to the thermoplastic resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 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 include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0019] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds 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%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but 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%, of the total 100 mol% of structural units derived from divalent phenols. 1 It can be calculated by 1H-NMR measurement.

[0020] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0021] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0022] In the present invention, the viscosity-average molecular weight of the polycarbonate resin is preferably 12,500 to 32,000, more preferably 16,000 to 28,000, and even more preferably 18,000 to 26,000. Polycarbonate resins with a viscosity-average molecular weight of less than 12,500 may not yield good mechanical properties. On the other hand, resin compositions obtained from polycarbonate resins with a viscosity-average molecular weight exceeding 32,000 may have poor moldability.

[0023] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (η SP The viscosity of the solution was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight M is calculated from 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 Furthermore, the viscosity-average molecular weight of the polycarbonate resin in the present invention is calculated as follows. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble components in the composition. Such soluble components are collected by filtration through Celite. Then, the solvent in the resulting solution is removed. The solid after solvent removal is thoroughly dried to obtain a solid of the components dissolved in methylene chloride. From a solution obtained by dissolving 0.7 g of such solid in 100 ml of methylene chloride, the specific viscosity at 20°C is determined in the same manner as above, and the viscosity-average molecular weight M is calculated from the specific viscosity in the same manner as above.

[0024] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin in the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a dihydric phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0025] [Chemical formula]

[0026] [In the above general formula (1), R 1 and R 2Each of the following groups 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 carboxyl group. If there are multiple groups, they may be the same or different. e and f are integers from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the general formula (2) below.

[0027] [ka]

[0028] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 Each of these 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 of these 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 carboxyl group. If there are multiple groups, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0029] [ka]

[0030] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0031] Examples of divalent phenols (I) represented by 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-H 1,1-bis(4-hydroxyphenyl)fluorene, 2,2-diphenylmethane, 3,1-bis(4-hydroxyphenyl)cyclohexane, 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.

[0032] 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, with 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 being particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0033] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0034] [ka]

[0035] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends 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, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such a 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 suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0036] Furthermore, to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane(II) is appropriately set to 10-300. This degree of diorganosiloxane polymerization (p+q) is preferably 10-200, more preferably 12-150, and even more preferably 14-100. Below the lower limit of this preferred range, the impact resistance characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this preferred range, appearance defects appear.

[0037] The polydiorganosiloxane content in the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. More preferably, the polydiorganosiloxane content is 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of this preferred range, a stable appearance less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and polydiorganosiloxane content are: 1 It can be calculated by 1H-NMR measurement.

[0038] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane(II) may be used, or two or more may be used. Furthermore, to the extent that it does not interfere with the present invention, other comonomers other than the above-mentioned divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in a range of 10% by weight or less relative to the total weight of the copolymer.

[0039] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of divalent phenol(I) with a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution.

[0040] In producing the divalent phenol(I) oligomer, the entire amount of divalent phenol(I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed. The method of this oligomer formation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0041] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0042] Examples of acid binders 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, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol(I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0043] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. 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.

[0044] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, 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 polymerization is often exothermic, water cooling or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as for known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0045] In this invention, a mixed solution containing an oligomer of divalent phenol (I) having terminal chloroformate groups is obtained, and while stirring the mixed solution, 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, is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0046] [ka]

[0047] (In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R 9 and R 10 Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number between 10 and 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0048] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders 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, or mixtures thereof. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane(II) or divalent phenol(I) as described above as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol(I) and hydroxyaryl-terminated polydiorganosiloxane(II) (usually 1 mole corresponds to 2 equivalents).

[0049] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0050] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0051] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, and more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0052] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1 Examples include trisphenols such as 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, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of polyfunctional compounds 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%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by 1H-NMR measurement.

[0053] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general terms, but it is usually carried out in 0.5 to 10 hours.

[0054] Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking, partial decomposition, etc.) to obtain the desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0055] The resulting reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification) by various post-treatment methods, such as known separation and purification methods.

[0056] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 40 nm. More preferably, this average size is 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0057] The average domain size and normalized dispersion of polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded product of this invention were 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 with a scattering angle (2θ) < 10° or less. In this small-angle X-ray scattering method, if there are regions with different electron densities of about 1 to 100 nm in size in the material, diffuse scattering of X-rays is measured due to the difference in electron density. The particle size of the object to be measured is determined based on this scattering angle and scattering intensity. In the case of polycarbonate-polydiorganosiloxane copolymer resin, which has an aggregated structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix, diffuse scattering of X-rays occurs due to the difference in electron density between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I is measured at each scattering angle (2θ) in the range of less than 10° to obtain a small-angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical and that there is variability in the particle size distribution, the average size and particle size distribution (normalized variance) of the polydiorganosiloxane domains are determined by simulating with commercially available analysis software using a hypothetical particle size and a hypothetical particle size distribution model. Small-angle X-ray scattering allows for accurate, simple, and reproducible measurement of the average size and particle size distribution of polydiorganosiloxane domains dispersed in a polycarbonate polymer matrix, which cannot be accurately measured by transmission electron microscopy. The average domain size refers to the numerical average of the individual domain sizes. Normalized variance refers to a parameter that normalizes the spread of the particle size distribution by the average size. Specifically, it is the value obtained by normalizing the variance of the polydiorganosiloxane domain size by the average domain size, and is expressed by the following equation (1).

[0058]

number

[0059] The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to the measured values obtained by measuring the 1.0 mm thick portion of the three-stage plate prepared by the method described in the Examples by such a small-angle X-ray scattering method. Further, analysis can be performed using an isolated particle model that does not consider the particle-particle interaction (particle-particle interference).

[0060] <A-1 component: Recycled polycarbonate resin> The recycled polycarbonate resin (A-1 component) used as the A-1 component of the present invention is a recycled one among the aforementioned polycarbonate resins (A component). Recycling means collecting products or materials that have once been put into the market as products and have been used by consumers and then using them again as products. Usually, it means post-consumer recycled (PCR) materials.

[0061] The recycled polycarbonate resin (A-1 component) in the present invention has an ashing residue amount of 0 to 0.4% by weight after 3 hours at 600 °C, more preferably 0 to 0.3% by weight, still more preferably 0 to 0.2% by weight, and particularly preferably 0 to 0.1% by weight. When the ashing residue amount is more than the upper limit, it is not preferable because the thermal stability, recyclability, mechanical properties, and thermal conductivity during residence in the molded product formed from the obtained polycarbonate resin composition deteriorate.

[0062] In addition, the recycled polycarbonate resin (Component A-1) in the present invention has a temperature at 5% weight loss measured under a temperature increase of 20 °C / min in a nitrogen atmosphere of 405 °C to 505 °C. The lower limit is preferably 410 °C or higher, 415 °C or higher, 420 °C or higher, 425 °C or higher, 430 °C or higher, and the upper limit is preferably 503 °C or lower, 500 °C or lower, 495 °C or lower, 490 °C or lower, 485 °C or lower, 480 °C or lower, 475 °C or lower, 470 °C or lower, 465 °C or lower, 460 °C or lower, 455 °C or lower, 450 °C or lower. When the temperature at 5% weight loss is lower than the lower limit, the thermal stability during residence time and the recyclability are significantly reduced, and the mechanical properties and thermal conductivity also decrease, which is not preferable. Also, those higher than the upper limit can be used, but it is not realistic for recycled polycarbonate resins.

[0063] The recycled polycarbonate resin (Component A-1) in the present invention is preferably obtained by a production process including (i) a step of pulverizing a recovered polycarbonate resin molded product provided with one or more magnetic separation steps (pulverization step), (ii) a step of washing the pulverized product obtained by the pulverization step (washing step), and (iii) an extrusion step of pelletizing the pulverized and washed product obtained by the washing step by melt kneading (extrusion step).

[0064] The content of Component A-1 is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, still more preferably 15 to 85 parts by weight, and still more preferably 20 to 80 parts by weight per 100 parts by weight of Component A. When the content of Component A-1 is within the above range, the thermal stability during residence time, recyclability, mechanical properties, and thermal conductivity are good.

[0065] <Component A-2: Non-recycled polycarbonate resin> The virgin polycarbonate resin (Component A-2) used as Component A-2 of the present invention is usually the virgin polycarbonate resin manufactured in a factory among the aforementioned polycarbonate resins (Component A), and may contain a part of post-industrial recycled (PIR) materials. Examples of PIR materials include injection molded products containing polycarbonate resin or pulverized materials of sprues or runners generated during injection molding, extrusion molded products such as films and sheets or pulverized materials of end materials generated during extrusion molding, and pellets etc. produced from these pulverized materials using an extruder.

[0066] The content of Component A-2 is 1 to 99 parts by weight, preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, still more preferably 15 to 85 parts by weight, and still more preferably 20 to 80 parts by weight per 100 parts by weight of Component A. When the content of Component A-2 is within the above range, the thermal stability, recyclability, mechanical properties and thermal conductivity during residence time are good.

[0067] <Component B: Inorganic filler> As the inorganic filler of Component B, conventionally known inorganic fillers can be used, among which at least one inorganic filler selected from the group consisting of (B-1) glass fiber (Component B-1), (B-2) plate-like glass filler (Component B-2), (B-3) fibrous carbon filler (Component B-3), (B-4) non-fibrous carbon filler (Component B-4) and (B-5) silicate mineral (Component B-5) is preferable.

[0068] The content of Component B is 1 to 150 parts by weight, preferably 3 to 140 parts by weight, and more preferably 5 to 130 parts by weight with respect to 100 parts by weight of Component A. When the content of Component B is less than the lower limit, sufficient rigidity cannot be obtained, and when it exceeds the upper limit, the thermal stability and recyclability during residence time decrease.

[0069] <Component B-1: Glass fiber> As the glass fibers used in the present invention, the glass compositions such as A glass, C glass, E glass, etc. are not particularly limited, and they may contain components such as TiO2, SO3, P2O5, etc. in some cases. However, E glass (alkali-free glass) is more preferable when blended with a thermoplastic resin. Furthermore, it is also possible to use two or more of these glass fibers in combination. The glass fibers are obtained by rapidly cooling molten glass while stretching it by various methods to form a predetermined fibrous or milled shape. The rapid cooling and stretching conditions in such cases are not particularly limited either. In addition to a circular cross-section, glass fibers with non-circular cross-sectional shapes such as elliptical, mayu-shaped, and three-lobed shapes may also be used. Furthermore, a mixture of circular glass fibers and glass fibers with non-circular shapes may also be used. Among these, more preferable ones are circular glass fibers. Also, it is preferable to pretreat these glass fibers with a coupling agent such as an isocyanate-based compound, an organosilane-based compound, an organotitanate-based compound, an organoborane-based compound, and an epoxy compound, or an organic onium ion in a swellable layered silicate in order to obtain more excellent mechanical strength. The glass fibers used in the present invention preferably have a diameter (D) in the range of 6 to 13 μm, a cut length (L) in the range of 30 μm to 9 mm, and an L / D in the range of 2.3 to 1500.

[0070] <B-2; Plate-like glass filler> Examples of the plate-like glass filler include glass flakes, metal-coated glass flakes, and metal oxide-coated glass flakes.

[0071] The glass flakes that form the base of the plate-shaped glass filler are plate-shaped glass fillers manufactured by methods such as the cylindrical blow method or the sol-gel method. The size of the raw material for such glass flakes can be selected in various ways depending on the degree of crushing and classification. The average particle size of the glass flakes used as raw material is preferably 10 to 1000 μm, more preferably 20 to 500 μm, and even more preferably 30 to 300 μm. This is because the above range offers excellent balance between handling and moldability. Normally, plate-shaped glass fillers crack during melt-kneading with resin, and their average particle size decreases. The number-average particle size of the plate-shaped glass filler in the thermoplastic resin composition is preferably 10 to 200 μm, more preferably 15 to 100 μm, and even more preferably 20 to 80 μm. The number-average particle size is calculated by an image analysis device from images obtained by observing the residue of the plate-shaped glass filler collected after processing such as high-temperature ashing of the molded product, dissolution with solvents, and decomposition with chemicals using an optical microscope. Furthermore, when calculating these values, the flake thickness is used as a guideline, and flakes shorter than this length are not counted. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 8 μm, and even more preferably 1.5 to 6 μm. Plate-shaped glass fillers having the above number-average particle size and thickness may achieve good mechanical strength, appearance, and moldability.

[0072] The glass composition of the plate-shaped glass filler is not particularly limited and can be any of the various glass compositions represented by A glass, C glass, and E glass. Such glass fillers may contain components such as TiO2, SO3, and P2O5 as needed. Among these, E glass (alkali-free glass) is more preferred. Furthermore, plate-shaped glass fillers that have been surface-treated with well-known surface treatment agents, such as silane coupling agents, titanate coupling agents, or aluminate coupling agents, are preferred from the viewpoint of improving mechanical strength. In addition, plate-shaped glass fillers that have been bundled with olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, and urethane resins are preferably used. The amount of bundling agent adhering to the bundled plate-shaped glass filler is preferably 0.5 to 8% by weight, more preferably 1 to 4% by weight, of 100% by weight of the plate-shaped glass filler.

[0073] Furthermore, the plate-shaped glass filler includes those coated with different materials on the surface. Preferred examples of such different materials include metals and metal oxides. Examples of the metal include silver, copper, nickel, and aluminum. Examples of the metal oxide include titanium oxide, cerium oxide, zirconium oxide, iron oxide, aluminum oxide, and silicon oxide. The method of surface coating of such different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electroplating, electroless plating, hot dipping, etc.), vacuum evaporation method, ion plating method, CVD method (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD method, and sputtering method.

[0074] <B-3 Component: Fibrous Carbon Filler> Examples of the fibrous carbon filler include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber, and carbon nanotube. The carbon nanotube may have a fiber diameter of 0.003 to 0.1 μm and may be monolayer, bilayer, or multilayer, with multilayer (so-called MWCNT) being preferred. Among these, carbon fiber and metal-coated carbon fiber are preferred in terms of excellent mechanical strength and the ability to impart good conductivity. Good conductivity has become one of the important properties required for resin materials in recent digital precision equipment (e.g., represented by digital still cameras).

[0075] Any type of carbon fiber can be used, including cellulose-based, polyacrylonitrile-based, and pitch-based types. Furthermore, carbon fibers obtained by spinning without an infusibility process, such as by forming or molding a raw material composition consisting of a polymer of aromatic sulfonic acids or their salts bonded to a methylene type, and then carbonizing it, can also be used. In addition, general-purpose, medium modulus, and high modulus types are all usable. Among these, the high modulus type of polyacrylonitrile is particularly preferred. The average fiber diameter of the carbon fiber is not particularly limited, but is usually 3 to 15 μm, preferably 5 to 13 μm. Carbon fibers with an average fiber diameter in this range may exhibit good mechanical strength and fatigue properties without impairing the appearance of the molded product. The preferred fiber length of the carbon fiber is 60 to 500 μm, preferably 80 to 400 μm, and particularly preferably 100 to 300 μm, as the number average fiber length in the thermoplastic resin composition. The average fiber length is calculated using an image analysis device based on optical microscope observation of carbon fiber residues collected during processes such as high-temperature ashing, solvent dissolution, and chemical decomposition of molded products. Furthermore, in calculating this value, fibers shorter than the fiber length are not counted. The aspect ratio of the carbon fiber is preferably in the range of 10 to 200, more preferably in the range of 15 to 100, and even more preferably in the range of 20 to 50. The aspect ratio is defined as the average fiber length divided by the average fiber diameter.

[0076] Furthermore, the surface of the carbon fiber is preferably oxidized to improve adhesion with the matrix resin and enhance mechanical strength. The oxidation treatment method is not particularly limited, but suitable examples include (1) treating the fibrous carbon filler with an acid or alkali or a salt thereof, or an oxidizing gas; (2) firing fibers or fibrous carbon fillers that can be made into fibrous carbon fillers at a temperature of 700°C or higher in the presence of an inert gas containing an oxygen-containing compound; and (3) oxidizing the fibrous carbon filler and then heat-treating it in the presence of an inert gas.

[0077] The metal-coated carbon fiber is obtained by coating a metal layer on the surface of a carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum, etc., and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. As the method of metal coating, various methods described above for the surface coating with different materials in the plate-shaped glass filler can be adopted. Among them, the plating method is preferably used. Also, in the case of such metal-coated carbon fibers, the carbon fibers mentioned above as the original carbon fibers can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm, and even more preferably 0.2 to 0.35 μm.

[0078] Such carbon fibers and metal-coated carbon fibers are preferably those subjected to a bundling treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, etc. In particular, the fibrous carbon filler treated with a urethane resin or an epoxy resin is suitable in the present invention because of its excellent mechanical strength.

[0079] <B - 4 Components: Non-Fibrous Carbon Filler> Examples of the non-fibrous carbon filler include carbon black, graphite, fullerene, etc. Among these, carbon black and graphite are preferable from the viewpoints of mechanical strength, heat and humidity resistance, and thermal stability. As the carbon black, carbon black having a DBP oil absorption of 100 ml / 100 g to 500 ml / 100 g is preferable from the viewpoint of conductivity. Such carbon black is generally acetylene black or ketjen black. Specifically, for example, Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd., Vulcan XC-72 and BP-2000 manufactured by Cabot Corporation, Ketjen Black EC and Ketjen Black EC-600JD manufactured by Lion Corporation, etc. can be mentioned.

[0080] As for graphite, either natural graphite, known by its mineral name sekkyaku, or various types of artificial graphite can be used. Natural graphite can be any of the following: earthy graphite, scaly graphite (also called lump graphite, or vein graphite), or flake graphite. Artificial graphite is produced by heat-treating amorphous carbon to artificially create an orientation of irregularly arranged minute graphite crystals. This includes not only the artificial graphite used in general carbon materials, but also quiche graphite, decomposed graphite, and pyrolysis graphite. Artificial graphite used in general carbon materials is usually produced by graphitization treatment using petroleum coke or coal-based pitch coke as the main raw material.

[0081] The graphite of the present invention may include expanded graphite that has been made thermally expandable by a treatment such as acid treatment, or graphite that has undergone such expansion treatment. The particle size of the graphite is preferably in the range of 2 to 300 μm. More preferably, the particle size is 5 to 200 μm, even more preferably 7 to 100 μm, and particularly preferably 7 to 50 μm. By satisfying this range, good mechanical strength and molded product appearance may be achieved. On the other hand, if the average particle size is less than 2 μm, the effect of improving rigidity may be small, and if the average particle size exceeds 300 μm, the impact resistance decreases significantly, and so-called graphite floating may become noticeable on the surface of the molded product, which is undesirable.

[0082] The fixed carbon content of the graphite of the present invention is preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 98% by weight or more. Furthermore, the volatile content of the graphite of the present invention is preferably 3% by weight or less, more preferably 1.5% by weight or less, and even more preferably 1% by weight or less.

[0083] In this invention, the average particle size of graphite refers to the particle size of the graphite itself before it becomes part of the resin composition, and such particle size is determined by laser diffraction and scattering. Furthermore, the surface of the graphite may be subjected to surface treatments such as epoxy treatment, urethane treatment, silane coupling treatment, and oxidation treatment, in order to increase its affinity with thermoplastic resins, provided that the properties of the composition of the present invention are not impaired.

[0084] <B-5 Component: Silicate Mineral> Examples of the silicate mineral in the present invention include silicate minerals composed of at least a metal oxide component and a SiO2 component, and orthosilicates, disilicates, cyclic silicates, chain silicates, etc. are preferable. The silicate mineral takes a crystalline state, and further, the crystal may be in any form that each silicate mineral can take, and the shape of the crystal can also take various shapes such as fibrous and plate-like.

[0085] The silicate mineral may be any of a composite oxide, an oxygen acid salt (consisting of an ionic lattice), and a solid solution. Further, the composite oxide may be any of a combination of two or more single oxides and a combination of two or more single oxides and oxygen acid salts. Further, in the solid solution, it may be any of a solid solution of two or more metal oxides and a solid solution of two or more oxygen acid salts. It may also be a hydrate. The form of the crystal water in the hydrate may be any of those that enter as hydrogen silicate ions as Si-OH, those that enter ionically as hydroxide ions (OH - ) with respect to metal cations, and those that enter as H2O molecules in the gaps of the structure.

[0086] As the silicate mineral, an artificial synthetic product corresponding to a natural product can also be used. As the artificial synthetic product, silicate minerals obtained from various conventionally known methods, such as various synthesis methods using solid reaction, hydrothermal reaction, and ultrahigh pressure reaction, can be used.

[0087] Specific examples of the silicate mineral in each metal oxide component include the following. Here, the notation in parentheses is the name of a mineral or the like having such a silicate mineral as the main component, and it means that the compound in parentheses can be used as the exemplified metal salt.

[0088] Those containing K2O in its components include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (calcilite), K2O·Al2O3·4SiO2 (leucite), and K2O·Al2O3·6SiO2 (orthoclase), etc.

[0089] Examples of substances containing Na2O include Na2O·SiO2 and its hydrate, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (jadeite), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2, and Na2O·Al2O3·6SiO2 (albite).

[0090] Examples of substances containing Li2O include Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite), and Li2O·Al2O3·4SiO2 (spodumene).

[0091] Examples of substances containing BaO include BaO·SiO2, 2BaO·SiO2, BaO·Al2O3·2SiO2 (cerucyan), and BaO·TiO2·3SiO2 (bentite).

[0092] Minerals containing CaO include 3CaO·SiO2 (alite, a cement clinker mineral), 2CaO·SiO2 (belite, a cement clinker mineral), 2CaO·MgO·2SiO2 (okermanite), 2CaO·Al2O3·SiO2 (gehlenite), a solid solution of okermanite and gehlenite (merilite), CaO·SiO2 (wollonite (including both α- and β-types)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (magnesium olivine), 3CaO·MgO·2SiO2 (merwinite), CaO·Al2O3·2SiO2 (anorthite), and tobermorite, such as 5CaO·6SiO2·5H2O (tobermorite, and others like 5CaO·6SiO2·9H2O). Examples include group hydrates, wollastonite group hydrates such as 2CaO·SiO2·H2O (hirebrandite), xonotlite group hydrates such as 6CaO·6SiO2·H2O (xonotlite), gyrolite group hydrates such as 2CaO·SiO2·2H2O (gyrolite), lawsonite (CaO·Al2O3·2SiO2·H2O), hedenkiite (CaO·FeO·2SiO2), chilcoanite (3CaO·2SiO2), grossula (3CaO·Al2O3·3SiO2), andradite (3CaO·Fe2O3·3SiO2), pleochroite (6CaO·4Al2O3·FeO·SiO2), as well as clinozoisite, rhodochroite, celandine, vesuvianite, onoite, scoutite, and augite.

[0093] Furthermore, Portland cement can be cited as a silicate mineral containing CaO. The type of Portland cement is not particularly limited; any type can be used, including ordinary, rapid-hardening, ultra-rapid-hardening, medium-heat-resistant, sulfate-resistant, and white cement. Additionally, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component B. Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0094] Minerals containing ZnO include ZnO·SiO2, 2ZnO·SiO2 (trostite), and 4ZnO·2SiO2·H2O (hemipolarite). Minerals containing MnO include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and causerite. Minerals containing FeO include FeO·SiO2 (ferrosilite), 2FeO·SiO2 (iron olivine), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (tetucinoseite).

[0095] Examples of substances containing CoO include CoO·SiO2 and 2CoO·SiO2.

[0096] MgO-containing materials include MgO·SiO2 (steatite, enstatite), 2MgO·SiO2 (forsterite), 3MgO·Al2O3·3SiO2 (byrope), 2MgO·2Al2O3·5SiO2 (cordierite), 2MgO·3SiO2·5H2O, 3MgO·4SiO2·H2O (talc), 5MgO·8SiO2·9H2O (atapulgite), and 4MgO·6SiO2·7H2O (sepiolite). Examples include 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (persimmonite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), Na2O·3MgO·3Al2O3·8SiO2·H2O (lanseneite), as well as magnesium tourmaline, orthosene, cumingtonite, vermiculite, smectite, etc.

[0097] Examples of substances containing Fe2O3 as a component include Fe2O3·SiO2.

[0098] Examples of materials containing ZrO2 include ZrO2·SiO2 (zircon) and AZS refractories.

[0099] Examples of those containing Al2O3 as a component include Al2O3·SiO2 (sillimanite, andalusite, kyanite), 2Al2O3·SiO2, Al2O3·3SiO2, 3Al2O3·2SiO2 (mullite), Al2O3·2SiO2·2H2O (kaolinite), Al2O3·4SiO2·H2O (pyrophyllite), Al2O3·4SiO2·H2O (bentonite), K2O·3Na2O·4Al2O3·8SiO2 (kasumiite), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (fluorophlogopite), and various zeolites, fluorophlogopite, and biotite.

[0100] Among the above silicate minerals, talc, mica, and wollastonite are particularly preferred because they have an excellent balance between rigidity and impact resistance, excellent moisture and heat resistance, heat stability, and appearance, and are also easily available.

[0101] <C component: Phosphate stabilizer> As the phosphate stabilizer used in the present invention, various phosphate stabilizers can be used. Among them, at least one phosphate stabilizer selected from the group consisting of (C-1) phosphonic acid ester (C-1 component), (C-2) acidic phosphate ester (C-2 component), and (C-3) metal salt of acidic phosphate ester (C-3 component) is preferred. The blending amount of the phosphate stabilizer is 0.001 to 2 parts by weight, preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.5 part by weight, still more preferably 0.02 to 0.3 part by weight, and particularly preferably 0.03 to 0.2 part by weight with respect to 100 parts by weight of the polycarbonate resin (A component). When the content of the C component is less than the lower limit or exceeds the upper limit, both the thermal stability during residence and the recyclability are inferior, and there is a decrease in mechanical strength, which is not preferable.

[0102] <C-1 component: Phosphonic acid ester> The phosphonic acid ester (C-1 component) used in the present invention can be a phosphonic acid monoester, a phosphonic acid diester, or a phosphonic acid triester, but a phosphonic acid triester is preferred. The carbon number of the ester can be various combinations from 1 to 22, but triethyl phosphonoacetate is most preferred.

[0103] When using the C-1 component, its content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0.3 part by weight, and particularly preferably 0.02 to 0.2 part by weight with respect to 100 parts by weight of the polycarbonate resin (A component). When the content of the C-1 component is within the above range, it is excellent in thermal stability and recyclability during residence, and excellent in strength such as flexural fracture strength.

[0104] <C-2 component: acidic phosphate ester> The acidic phosphate ester (C-2 component) used in the present invention can be a phosphoric acid monoester, a phosphoric acid diester, a phosphoric acid triester, and a mixture, but a mixture of a monoester and a diester is preferred. The carbon number of the ester can be various combinations from 1 to 22, but stearyl acid phosphate is most preferred.

[0105] When using the C-2 component, its content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0.2 part by weight, and particularly preferably 0.02 to 0.1 part by weight with respect to 100 parts by weight of the polycarbonate resin (A component). When the content of the C-2 component is within the above range, it is excellent in thermal stability and recyclability during residence, and excellent in strength such as flexural fracture strength.

[0106] <C-3 component: metal salt of acidic phosphate ester> The metal salt of acidic phosphate ester (C-3 component) used in the present invention is produced by a dry process obtained by the direct reaction of a fatty acid with a metal oxide or a fatty acid with a metal hydroxide, and a wet process produced by reacting a sodium salt of a fatty acid with a metal salt in an aqueous solution. Various combinations of fatty acids with carbon numbers from 1 to 22 can be used, but those with 18 carbon atoms are more preferred. The metal salt of the acidic phosphate ester is most preferably zinc stearyl acid phosphate.

[0107] When using the C-3 component, its content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, still more preferably 0.01 to 0.2 part by weight, and particularly preferably 0.02 to 0.1 part by weight with respect to 100 parts by weight of the polycarbonate resin (A component). When the content of the C-3 component is within the above range, it has excellent thermal stability and recyclability during residence time, and excellent strength such as flexural fracture strength.

[0108] <Component D: Phosphite stabilizer> In the present invention, the phosphite stabilizers used as required include pentaerythritol type phosphite compounds, phosphite compounds having a cyclic structure by reacting with divalent phenols, and phosphite compounds having other structures.

[0109] Examples of the above-mentioned pentaerythritol-type phosphite compounds include, for example, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite. Among these, distearyl pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite are particularly preferred.

[0110] Examples of phosphite compounds that react with the above-mentioned divalent phenols and have a cyclic structure include 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite. Examples include sphite, 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, 2,2'-methylene-bis-(4,6-di-t-butylphenyl)octylphosphite, and 6-tert-butyl-4-[3-[(2,4,8,10)-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosfepin-6-yl)oxy]propyl]-2-methylphenol.

[0111] Examples of phosphite compounds having the above-mentioned structures include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, and tris(2,6-di-tert-butylphenyl) phosphite.

[0112] Among the phosphite-based stabilizers mentioned above, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite are preferred.

[0113] When component D is used, its content is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 parts by weight, even more preferably 0.01 to 0.2 parts by weight, and particularly preferably 0.02 to 0.1 parts by weight, per 100 parts by weight of polycarbonate resin (component A). When the content of component D is within the above range, it may exhibit excellent thermal stability and recyclability during retention, as well as superior strength such as bending fracture strength.

[0114] <Other ingredients> The polycarbonate resin composition of the present invention may contain other additives such as heat stabilizers, antioxidants, mold release agents, flame retardants, ultraviolet absorbers, and colorants, as long as they do not impair the objectives of the present invention.

[0115] <Other resin components> Furthermore, the polycarbonate resin composition of the present invention may be blended with other resins such as ABS resin, polyester resin, AS resin, PS resin, AAS resin, AES resin, polyamide resin, polyolefin resin, fluororesin, PPS resin, PEEK resin, polyarylate resin, and polyacetal resin, to the extent that it does not impair the objectives of the present invention.

[0116] <Manufacturing of polycarbonate resin compositions> Any method can be used to produce the polycarbonate resin composition of the present invention. For example, components A, B, C, and optionally other components may be thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical device, or extruder mixer, and then the premix may be granulated using an extruder or briquetting machine as needed, followed by melt-kneading in a melt-kneader such as a vented twin-screw extruder, and then pelletized using a pelletizer.

[0117] Other methods include supplying each component independently to a melting and mixing machine, such as a vented twin-screw extruder, or pre-mixing some of the components and then supplying them separately to the melting and mixing machine along with the remaining components. An example of a method for pre-mixing some of the components is to pre-mix the components other than component A beforehand, and then mix them with the polycarbonate resin of component A or supply them directly to the extruder.

[0118] One method of pre-mixing is, for example, if component A is in powder form, a masterbatch of the additive can be produced by blending a portion of the powder with the additive to be blended, and then using this masterbatch. Another method is to supply one component independently from the middle of the melt extruder. If there is a liquid component to be blended, a so-called liquid injection device or liquid additive device can be used to supply it to the melt extruder.

[0119] Preferably, an extruder equipped with a vent capable of removing moisture from the raw material and volatile gases generated from the molten and kneaded resin is used. A vacuum pump is preferably installed in the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to install a screen in the zone in front of the extruder die to remove foreign matter mixed into the extrusion raw material, thereby removing foreign matter from the resin composition. Examples of such screens include wire mesh, screen changers, and sintered metal plates (disc filters, etc.).

[0120] Other types of melting and mixing machines include twin-screw extruders, Banbury mixers, mixing rolls, single-screw extruders, and multi-screw extruders with three or more shafts.

[0121] As described above, the extruded resin is either directly cut and pelletized, or strands are formed and then cut in a pelletizer to form pellets. If it is necessary to reduce the influence of external dust and other contaminants during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs can be used to appropriately narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation or transport, and reduce air bubbles (vacuum bubbles) generated inside the strands and pellets. These formulations can enable high-cycle molding and reduce the rate of defects such as silver. The shape of the pellets can be general shapes such as cylinders, prismatics, and spheres, but cylinders are more preferable. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

[0122] <Manufacturing of molded products> Any method can be used to produce a molded article made from the polycarbonate resin composition of the present invention. For example, the polycarbonate resin composition can be kneaded in an extruder, Banbury mixer, or roll, and then molded by conventionally known methods such as injection molding, extrusion molding, or compression molding to obtain a molded article. [Examples]

[0123] The present inventors consider the best possible form of the present invention to be a combination of the preferred ranges of the above requirements, and a representative example is described in the following embodiments. Of course, the present invention is not limited to these forms. The following items were evaluated:

[0124] (i) flexural modulus The pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours. ISO bending test specimens (compliant with ISO 75-1 and 75-2) were then continuously molded at the temperatures shown in the table using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U·SM IV], and the bending modulus of elasticity was measured using the test specimens.

[0125] (ii) Thermal conductivity A 100mm x 100mm x 4mm thick rectangular plate was formed using the injection molding machine described above. A 50mm x 100mm x 4mm thick molded product was cut from the center of the rectangular plate, and the thermal conductivity of the sample in the flow direction was measured using the laser flash method.

[0126] (iii) Retention rate of bending fracture strength during retention (thermal stability during retention) In the molding process used to measure (i) the flexural modulus, the operation of the molding machine was interrupted, and the resin was allowed to remain in the cylinder. After 15 minutes, the test specimens were molded again, and test specimens before and after the retention period were obtained. The flexural fracture strength of the test specimens before and after the retention period was measured, and the strength retention rate before and after the retention period was calculated using the following formula. Strength retention rate (%) = [Bending strength after retention / Bending strength before retention] × 100

[0127] (iv) Recyclability The test specimens used in "(i) Strength retention rate during storage" were left horizontally outdoors in Midori Ward, Chiba City for one year, then crushed and reshaped into test specimens. The bending fracture strength of the test specimens before storage and the reshaped test specimens was measured using the same method as in "(i) Strength retention rate during storage," and the strength retention rate before and after outdoor storage was measured using the following formula. Strength retention rate (%) = [Bending strength after re-molding / Bending strength before outdoor storage] × 100

[0128] [Examples 1-12, Comparative Examples 1-5] Resin compositions with the mixing ratios shown in Table 1 were prepared as follows. The explanation will follow the symbols in the table below. Each component in the proportions shown in the table was weighed, uniformly mixed using a tumbler, and the mixture was fed into an extruder to prepare the resin composition. A vented twin-screw extruder (TEX-30α, manufactured by Japan Steel Works Ltd., fully engaged, co-rotating, double-threaded screw) was used. The extrusion conditions were a discharge rate of 20 kg / h, screw rotation speed of 150 rpm, and vent vacuum of 3 kPa, with an extrusion temperature of 300°C. Using the obtained pellets, evaluation test pieces were molded using an injection molding machine in the same manner as described above. The cylinder temperature was set to 320°C. The evaluation results are shown in Table 1. The symbols in Table 1 indicate the following components.

[0129] (Component A-1: ​​Recycled polycarbonate resin) A-1-1: Recycled polycarbonate resin, 0.01% ashing residue after 3 hours at 600°C, measured in a nitrogen atmosphere with a temperature increase of 20°C / min. TGA 5% weight loss 503°C A-1-2: Recycled polycarbonate resin, 0.5% ashing residue after 3 hours at 600°C, measured in a nitrogen atmosphere with a temperature increase of 20°C / min, TGA 5% weight loss 487°C A-1-3: Recycled polycarbonate resin (A-1-2) was washed and re-pelletized at 300°C using a single-screw 80φ extruder with a 300 mesh. Ashing residue of 0.1% after 3 hours at 600°C, TGA 5% weight loss of 499°C measured in a nitrogen atmosphere under a temperature increase of 20°C / min. A-1-4: Recycled polycarbonate resin, 0.1% ashing residue after 3 hours at 600°C, measured in a nitrogen atmosphere with a temperature increase of 20°C / min. TGA 5% weight loss 402°C A-1-5: Recycled polycarbonate resin (A-1-4) was washed and re-pelletized at 300°C using a single-screw 80φ extruder with a 300 mesh. Ashing residue of 0.01% after 3 hours at 600°C, TGA 5% weight loss of 435°C measured in a nitrogen atmosphere under a temperature increase of 20°C / min.

[0130] (Component A-2: Non-recycled polycarbonate resin) A-2: Aromatic polycarbonate resin (polycarbonate resin powder with viscosity-average molecular weight of 20,700, manufactured by conventional methods from bisphenol A and phosgene, Panlite L-1225WS (product name), manufactured by Teijin Limited, with a 0.0% ashing residue after 3 hours at 600°C, measured in a nitrogen atmosphere under a temperature increase of 20°C / min, TGA 5% weight loss 506°C)

[0131] (Component B: Inorganic filler) B-1: Glass fiber (manufactured by Nitto Boseki Co., Ltd., product name 3PE937) B-2: Carbon fiber (Teijin Limited, HT C493 (product name)) B-3: Non-fibrous carbon filler (manufactured by Nishimura Graphite Co., Ltd., product name E-40) B-4: Talc (Victorilite TK-RC (product name) manufactured by Katsumitsuyama Mining Co., Ltd.)

[0132] (Component C: Phosphate-based stabilizer) C-1: Triethylphosphonoacetate (manufactured by Johoku Chemical Industry Co., Ltd., product name JC-224) C-2: Stearyl acid phosphate (ADEKA Corporation, product name AX-71) C-3: Stearyl acid phosphate zinc salt (manufactured by Johoku Chemical Industry Co., Ltd., product name JP-518Zn)

[0133] (Component D: Phosphate stabilizer) D-1: Tris(2,4-di-tert-butylphenyl) phosphite (ADEKA Corporation, ADEKA Stab 2112 (product name))

[0134] [Table 1] [Industrial applicability]

[0135] The polycarbonate resin composition and molded articles of the present invention possess excellent mechanical properties, thermal conductivity, thermal stability during retention, and recyclability, making them suitable for use in a wide range of fields, including housings and components for electrical, electronic, and office automation equipment, interior and exterior components for automobiles, furniture, musical instruments, and general merchandise.

Claims

1. A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A) consisting of (A-1) 1 to 99 parts by weight of recycled polycarbonate resin (component A-1) and (A-2) 99 to 1 part by weight of non-recycled polycarbonate resin (component A-2), wherein (B) inorganic filler (component B) and (C) phosphate stabilizer (component C) are present, and component (A-1) has an ashing residue of 0 to 0.4% by weight after 3 hours at 600°C, and component (A-1) has a 5% weight loss temperature measured under a temperature increase of 20°C / min in a nitrogen atmosphere of 405°C to 505°C.

2. The polycarbonate resin composition according to claim 1, wherein component B is at least one inorganic filler selected from the group consisting of (B-1) glass fiber (component B-1), (B-2) plate-shaped glass filler (component B-2), (B-3) fibrous carbon filler (component B-3), (B-4) non-fibrous carbon filler (component B-4), and (B-5) silicate mineral (component B-5).

3. The polycarbonate resin composition according to claim 1, wherein component C is at least one phosphate-based stabilizer selected from the group consisting of (C-1) phosphonic acid ester (component C-1), (C-2) acidic phosphate ester (component C-2), and (C-3) metal salt of an acidic phosphate ester (component C-3).

4. The polycarbonate resin composition according to claim 1, wherein the recycled polycarbonate resin (component A-1) is obtained by a manufacturing process comprising (i) a step of crushing a recovered polycarbonate resin molded product that has one or more magnetic separation steps (crushing step), (ii) a step of washing the crushed material obtained by the crushing step (washing step), and (iii) an extrusion step of pelletizing the crushed and washed material obtained by the washing step by melt kneading (extrusion step).

5. The polycarbonate resin composition according to claim 1, comprising 0.001 to 1 part by weight of (D) a phosphite-based stabilizer (component D) per 100 parts by weight of component A.

6. A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 5.

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