Polycarbonate resin composition and molded articles formed therefrom

Abstract

This enables the use of recycled polycarbonate resin without compromising its properties such as thermal stability during storage, recyclability, and flame retardancy. [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) 0.001 to 25 parts by weight of flame retardant (component B) and (C) 0.001 to 2 parts by weight of phosphate-based stabilizer (component C), wherein 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.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition that enables high-level property maintenance, containing recycled polycarbonate resin having a specific ashing residual amount and weight loss temperature, non-recycled polycarbonate resin, a flame retardant, and a phosphate-based stabilizer, and molded articles formed therefrom. [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 properties of polycarbonate resin deteriorate significantly upon recycling, making the use of recycled polycarbonate resin difficult. When recycled, a decrease in transparency is a problem, and the increase in defects due to the inclusion of foreign matter is particularly fatal for transparent polycarbonate resin, making it crucial to solve this problem. A 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 a specific phosphorus-based compound in a resin consisting of polycarbonate-based resin and polyester resin. Patent Document 2 discloses the use of phosphorus-based compounds in combination. However, existing methods have not yet reached a level that enables the use of recycled polycarbonate resin, and there is a strong desire to satisfy the requirements for the use of recycled polycarbonate resin and for the flame retardancy of recycled polycarbonate resin. [Prior art documents] [Patent Documents]

[0004] Japanese Patent Document 1 Japanese Patent No. 4983427 Japanese Patent Document 2 Japanese Patent No. 5640734 Summary of the Invention Problems to be Solved by the Invention

[0005] An object of the present invention is to enable the use of recycled polycarbonate resin without degrading properties such as thermal stability during residence, recyclability, and flame retardancy. Means for Solving the Problems

[0006] As a result of intensive research to achieve the above object, the present inventors have found that by selecting a polycarbonate resin having a specific ash residue amount and weight loss temperature, even when using recycled polycarbonate resin, it is possible to maintain high properties (excellent thermal stability during residence, recyclability, flame retardancy, etc.), and thus have reached the present invention.

[0007] That is, the present invention is as follows. 1. A polycarbonate resin composition containing 0.001 to 30 parts by weight of a flame retardant (component B) and 0.001 to 2 parts by weight of a phosphate stabilizer (component C) with respect to 100 parts by weight of a polycarbonate resin (component A) composed of 1 to 99 parts by weight of a recycled polycarbonate resin (component A-1) and 99 to 1 part by weight of an unrecycled polycarbonate resin (component A-2), wherein the component (A-1) has an ash residue amount of 0 to 0.4% by weight after 3 hours at 600 °C, and the component (A-1) has a temperature of 5% weight loss 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 item 1 above, wherein component B is at least one flame retardant selected from the group consisting of (B-1) phosphate ester compounds (component B-1), (B-2) halogenated carbonate compounds (component B-2), (B-3) phosphazene compounds (component B-3), (B-4) metal sulfonate salts (component B-4), and (B-5) silicone compounds (component B-5). 3. A polycarbonate resin composition according to item 1 or 2 above, 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. A polycarbonate resin composition according to any one of paragraphs 1 to 3 above, wherein the recycled polycarbonate resin (component A-1) is obtained by a manufacturing process that includes (i) a step of crushing a recovered polycarbonate resin molded product equipped with one or more magnetic separation steps (crushing step), (ii) a step of washing the crushed material obtained in the crushing step (washing step), and (iii) an extrusion step of pelletizing the crushed and washed material obtained in the washing step by melt kneading (extrusion step). 5. A polycarbonate resin composition according to any one of items 1 to 4 above, containing 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 polycarbonate resin composition according to any one of items 1 to 5 above, containing 0.05 to 3 parts by weight of (E) drip inhibitor (component E) per 100 parts by weight of component A. 7. A molded article formed from a polycarbonate resin composition as described in any of items 1 to 6 above. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a polycarbonate resin composition and a molded product having excellent thermal stability during residence time, recyclability, flame retardancy, etc. by using a recycled polycarbonate resin having a specific amount of ash residue 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 effects they exhibit are extremely great.

Mode for Carrying Out the Invention

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

[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 divalent phenols 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, and 4,4'-(p-phenyl Examples include bis(4-hydroxyphenyl)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 divalent phenols are bis(4-hydroxyphenyl)alkanes, among which bisphenol A is particularly preferred and widely used in terms of impact resistance.

[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 In addition, the viscosity-average molecular weight of the polycarbonate resin in the present invention is calculated in the following manner. 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 Celite filtration. Then, the solvent in the resulting solution is removed. The solid after solvent removal is dried thoroughly 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] As the polycarbonate resin in the present invention, a polycarbonate-polydiorganosiloxane copolymer resin can also be used. 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. 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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]. 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.

[0054] 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.

[0055] 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, a simulation is performed using commercially available analysis software with a hypothetical particle size and a hypothetical particle size distribution model to determine the average size and particle size distribution (normalized variance) of the polydiorganosiloxane domains. The small-angle X-ray scattering method 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).

[0056]

number

[0057] The terms "average domain size" and "normalized dispersion" used in relation to the present invention refer to the measured values obtained by measuring the 1.0 mm thick part of the three-layer 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).

[0058] <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 above-mentioned polycarbonate resins (A component). Recycling means recovering products or materials that have once been put on the market as products and have been used and become used by consumers and using them again as products. Usually, it means post-consumer recycled (PCR) materials.

[0059] 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, and flame retardancy during residence in the obtained polycarbonate resin composition decrease.

[0060] 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, 420 °C or higher, 430 °C or higher, 440 °C or higher, 450 °C or higher, 460 °C or higher, 470 °C or higher, and the upper limit is preferably 500 °C or lower, 490 °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, it is not preferable because the thermal stability, recyclability, and flame retardancy during residence time deteriorate. Also, those higher than the upper limit can be used, but it is not realistic for recycled polycarbonate resins.

[0061] 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 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).

[0062] 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 and recyclability during residence time are good.

[0063] <Component A-2: Non-recycled polycarbonate resin> The virgin polycarbonate resin (Component A-2) used as Component A-2 of the present invention is generally 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 produced from these pulverized materials using an extruder.

[0064] 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 and recyclability during residence time are good.

[0065] <Component B: Flame Retardant> In the present invention, a flame retardant is used. The flame retardant is preferably at least one flame retardant selected from the group consisting of (B-1) phosphate ester compounds (Component B-1), (B-2) halogenated carbonate compounds (Component B-2), (B-3) phosphazene compounds (Component B-3), (B-4) metal sulfonate salts (Component B-4), and (B-5) silicone compounds (Component B-5).

[0066] The content of the flame retardant is 0.001 to 30 parts by weight, preferably 0.01 to 25 parts by weight, and more preferably 0.05 to 20 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 recyclability and flame retardancy cannot be obtained, and when it exceeds the upper limit, the thermal stability, recyclability, and flame retardancy during residence time decrease.

[0067] <Component B-1: Phosphate Ester Compound> As the phosphate ester compound used in the present invention, phosphate compounds, particularly aryl phosphate compounds, are preferred. The phosphate compound preferably has a molecular weight of 300 or more. If the molecular weight is less than 300, the difference between the boiling point of the phosphate compound and the combustion temperature of the resin composition becomes large, and volatilization of the phosphate compound may increase during combustion, so the effect as a flame retardant may decrease.

[0068] As such phosphate compounds, various phosphate compounds known as flame retardants can be used, but more preferably, one or more phosphate compounds represented by the following general formula (4) can be mentioned.

[0069] [Chemical formula]

[0070] (In general formula (4), X is a divalent phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide, n is an integer from 0 to 5, or in the case of a mixture of phosphate esters with different n numbers, it is their average value, and R 1 , R 2 , R 3 , and R 4 are each a monovalent phenol residue derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol)

[0071] <B - Component: Halogenated carbonate compound> In the present invention, halogenated carbonate compounds are preferably those in which the constituent unit represented by the following general formula (5) accounts for at least 60 mol% of the total constituent units and the specific viscosity is 0.015 to 0.1.

[0072] [ka]

[0073] [In general formula (5), X is a halogen atom, and R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or -SO2-.] In formula (5), R is preferably a methylene group, an ethylene group, an isopropylidene group, or -SO2-, and is particularly preferably an isopropylidene group. Furthermore, X is preferably a bromine atom.

[0074] The halogenated carbonate compound preferably has a small amount of residual chloroformate groups at the end, with a terminal chlorine content of 0.3 ppm or less, and more preferably 0.2 ppm or less. This terminal chlorine content can be determined by dissolving the sample in methylene chloride, adding 4-(p-nitrobenzyl)pyridine to react with the terminal chlorine (terminal chloroform), and measuring the result using a UV-Vis spectrophotometer (Hitachi U-3200). When the terminal chlorine content is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition is improved, allowing for molding at even higher temperatures, and as a result, a resin composition with superior moldability may be provided.

[0075] Furthermore, it is preferable that the halogenated carbonate compound has a small number of remaining hydroxyl groups at the end. More specifically, it is preferable that the amount of terminal hydroxyl groups is 0.0005 moles or less, and more preferably 0.0003 moles or less, per mole of constituent units of the halogenated carbonate compound. The amount of terminal hydroxyl groups is determined by dissolving the sample in deuterated chloroform. 1 This can be determined by measurement using 1H-NMR. Such a terminal hydroxyl group content may further improve the thermal stability of the polycarbonate resin composition.

[0076] The specific viscosity of the halogenated carbonate compound is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the halogenated carbonate compound is calculated according to the calculation formula used when calculating the viscosity average molecular weight of the polycarbonate resin which is the component A-1 of the present invention described above.

[0077] Moreover, such halogenated carbonate compounds are commercially available. For example, tetrabromobisphenol A carbonate oligomers (trade names FG-7000, FG-8500) manufactured by Teijin Limited can be mentioned, and these can be used in the present invention.

[0078] <Component B-3: Phosphazene compound> The phosphazene compound used in the present invention is not particularly limited as long as it is a compound that does not contain a halogen atom and has a phosphazene structure in the molecule. The phosphazene structure referred to here represents a structure represented by the formula: -P(R2)=N- [wherein, R2 represents an organic group]. Phosphazene is represented by general formulas (6) and (7).

[0079]

Chemical formula

[0080] (In general formulas (6) and (7), X1, X2, X3, and X4 represent hydrogen, a hydroxyl group, an amino group, or an organic group that does not contain a halogen atom. Also, n represents an integer of 3 to 10.) In the above general formulas (6) and (7), examples of the organic group that does not contain a halogen atom represented by X1, X2, X3, and X4 include an alkoxy group, a phenyl group, an amino group, an allyl group, etc. Among them, cyclic phenoxyphosphazene represented by the following general formula (8) is preferable.

[0081]

Chemical formula

[0082] 〔In general formula (8), m represents an integer from 3 to 25. Ph represents a phenyl group.〕 Examples of commercially available phosphazene compounds include SPS-100, SPR-100, SA-100, SPB-100, SPB-100L (all manufactured by Otsuka Chemical Co., Ltd.), FP-100, and FP-110 (both manufactured by Fushimi Pharmaceutical Co., Ltd.).

[0083] <B-4 Component: Metal Sulfonate> The metal used in the metal sulfonate used in the present invention is preferably an alkali metal or an alkaline earth metal, and more preferably an alkali metal. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Particularly preferred are lithium, sodium, and potassium.

[0084] The sulfonic acid used in the metal sulfonate used in the present invention is preferably an organic sulfonic acid, and more preferably an aliphatic sulfonic acid or an aromatic sulfonic acid.

[0085] The aliphatic sulfonic acid is preferably an alkyl sulfonic acid, more preferably a fluoroalkyl sulfonic acid in which part or all of the alkyl group is substituted with fluorine atoms, and most preferably a perfluoroalkyl sulfonic acid in which all are substituted with fluorine atoms. Preferred examples of perfluoroalkyl sulfonic acids include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonate, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. Particularly preferred are those having 1 to 8 carbon atoms. These can be used alone or in combination of two or more.

[0086] Aromatic sulfonic acids can include at least one acid selected from the group consisting of sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfonesulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids by methylene-type bonds. These can be used alone or in combination of two or more.

[0087] <B-5 Component: Silicone Compound> The silicone compound used in the present invention preferably has a highly active group, and preferred examples thereof include an alkoxy group or a Si-H group. The content ratio of such a group is preferably in the range of 0.1 to 1.2 mol / 100 g, more preferably in the range of 0.12 to 1 mol / 100 g, and still more preferably in the range of 0.15 to 0.6 mol / 100 g. Such a ratio is determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by an alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

[0088] Generally, the structure of the silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is, M unit: (CH3)3SiO 1 / 2 , H(CH3)2SiO 1 / 2 , H2(CH3)SiO 1 / 2 , (CH3)2(CH2=CH)SiO 1 / 2 , (CH3)2(C6H5)SiO 1 / 2 , (CH3)(C6H5)(CH2=CH)SiO 1 / 2 and other monofunctional siloxane units, D unit: (CH3)2SiO, H(CH3)SiO, H2SiO, H(C6H5)SiO, (CH3)(CH2=CH)SiO, (C6H5)2SiO and other difunctional siloxane units, T unit: (CH3)SiO3 / 2 (C3H7)SiO 3 / 2 , HSiO 3 / 2 (CH2=CH)SiO 3 / 2 (C6H5)SiO 3 / 2 These are trifunctional siloxane units, and tetrafunctional siloxane units represented by the Q unit: SiO2.

[0089] The structures of silicone compounds used in silicone-based flame retardants include, specifically, Dn, Tp, MmDn, MmTp, MmQq, MmDnTp, MmDnQq, MmTpQq, MmDnTpQq, DnTp, DnQq, and DnTpQq as structural formulas. Among these, preferred structures of silicone compounds are MmDn, MmTp, MmDnTp, and MmDnQq, and even more preferred structures are MmDn or MmDnTp.

[0090] Here, the coefficients m, n, p, and q in the structural formula are integers of 1 or more that represent the degree of polymerization of each siloxane unit, and the sum of the coefficients in each structural formula is the average degree of polymerization of the silicone compound. This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, even more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The closer the compound is to this preferred range, the better its flame retardancy becomes. Furthermore, as will be described later, silicone compounds containing a predetermined amount of aromatic groups also exhibit excellent transparency and hue. As a result, good reflected light is obtained.

[0091] Furthermore, if any of m, n, p, or q is a value of 2 or greater, the siloxane unit with that coefficient can be two or more different siloxane units with different hydrogen atoms or organic residues attached.

[0092] The silicone compound may be linear or have a branched structure. Further, the organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such organic residues include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, and decyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group, and aralkyl groups such as tolyl group. More preferably, it is an alkyl group, alkenyl group or aryl group having 1 to 8 carbon atoms. As the alkyl group, in particular, an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, and propyl group is preferable.

[0093] Furthermore, the silicone compound used as the silicone-based flame retardant preferably contains an aryl group. On the other hand, silane compounds and siloxane compounds as organic surface treatment agents for titanium dioxide pigments are clearly distinguished from silicone-based flame retardants in their preferred embodiments in that better effects are obtained when they do not contain an aryl group. A more preferable silicone-based flame retardant is a silicone compound in which the proportion of the aromatic group contained (amount of aromatic group) is 10 to 70% by weight (more preferably 15 to 60% by weight).

[0094] <Component C: 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 preferable. 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 (Component A). When the content of Component C is less than the lower limit or exceeds the upper limit, both the thermal stability and recyclability during residence are inferior, and there is a decrease in strength such as impact resistance, which is not preferable.

[0095] <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. For the esters, various combinations of carbon numbers from 1 to 22 can be used, and triethyl phosphonoacetate is most preferred.

[0096] 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, based on 100 parts by weight of the polycarbonate resin (A component). When the content of the C-1 component is within the above range, it has excellent thermal stability during residence and recyclability, and excellent strength such as impact resistance.

[0097] <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, or a mixture, but a mixture of a monoester and a diester is preferred. For the esters, various combinations of carbon numbers from 1 to 22 can be used, and stearyl acid phosphate is most preferred.

[0098] 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, based on 100 parts by weight of the polycarbonate resin (A component). When the content of the C-2 component is within the above range, it has excellent thermal stability during residence and recyclability, and excellent strength such as impact resistance.

[0099] <C-3 component: metal salt of acidic phosphate ester> The metal salt of acidic phosphate (C-3 component) used in the present invention may be produced by a dry method obtained by a direct reaction of a fatty acid with a metal oxide or a fatty acid with a metal hydroxide, and a wet method in which an aqueous solution of a sodium salt of a fatty acid and a metal salt are reacted. Various combinations of fatty acids having 1 to 22 carbon atoms can be used, but those having 18 carbon atoms are more preferable. It is most preferable that the metal salt of the acidic phosphate is zinc stearyl acid phosphate.

[0100] 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 is excellent in thermal stability and recyclability during residence time, and excellent in strength such as impact resistance.

[0101] <Component D: Phosphite stabilizer> In this invention, phosphite-based stabilizers are used as needed. By using phosphite-based stabilizers, hydrolysis of polycarbonate resin can be suppressed. Examples of phosphite-based stabilizers 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, Examples include tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, 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. Furthermore, other phosphite compounds that react with divalent phenols to form cyclic structures can also be used. Examples 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, 2,2'-methylenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite, and 2,2'-ethylidenebis(4-methyl-6-tert-butylphenyl)(2-tert-butyl-4-methylphenyl) phosphite.

[0102] When component D is used, 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 (component A). When the content of component D is within the above range, it may be excellent in thermal stability during residence time and recyclability, and may be excellent in strength such as impact resistance.

[0103] <Component E: Antidripping agent> In the present invention, examples of the antidripping agent used as component E as needed include fluorine-containing polymers having fibril-forming ability. Examples of such polymers include polytetrafluoroethylene, tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer, etc.), partially fluorinated polymers as shown in U.S. Patent No. 4379910, and polycarbonate resins produced from fluorinated diphenols. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable.

[0104] PTFE having fibril-forming ability has an extremely high molecular weight and tends to be fibrous by bonding PTFE to each other by an external action such as shear force. Its molecular weight is 1 million to 10 million, more preferably 2 million to 9 million in terms of the number average molecular weight determined from the standard specific gravity. Such PTFE can be used not only in a solid form but also in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties.

[0105] Examples of commercially available PTFE products possessing such fibril-forming ability include Teflon® 6-J from Mitsui Chemours Fluoroproducts Co., Ltd., and Polyflon MPAFA500H and F-201 from Daikin Industries, Ltd. Representative examples of commercially available aqueous dispersions of PTFE include the Fullon D series from Daikin Industries, Ltd., and Teflon® 31-JR from Mitsui Chemours Fluoroproducts Co., Ltd.

[0106] As for the mixed form of PTFE, (1) a method of mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitating to obtain a co-aggregated mixture (methods described in Japanese Patent Publication No. 60-258263, Japanese Patent Publication No. 63-154744, etc.), (2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Publication No. 4-272957), (3) a method of uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and simultaneously extracting each medium from the mixture (1) a method of removing (as described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (2) a method of polymerizing monomers that form an organic polymer in an aqueous dispersion of PTFE (as described in Japanese Patent Publication No. 9-95583), and (3) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (as described in Japanese Patent Publication No. 11-29679, etc.) can be used. Examples of commercially available PTFE in these mixed forms include "Metablen A3800" (product name) and "Metablen A3750" from Mitsubishi Chemical Corporation.

[0107] In the mixed form, the proportion of PTFE is preferably 1 to 60% by weight, and more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can sometimes be achieved.

[0108] Examples of styrene monomers used as organic polymers in polytetrafluoroethylene mixtures include, but are not limited to, styrenes that may be substituted with one or more groups selected from the group consisting of C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogens, such as ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, dimethylstyrene, ethylstyrene, para-tert-butylstyrene, methoxystyrene, fluorostyrene, monobromostyrene, dibromostyrene, and tribromostyrene, vinylxylene, and vinylnaphthalene. The styrene monomers can be used individually or in mixtures of two or more types.

[0109] Acrylic monomers used as organic polymers in polytetrafluoroethylene mixtures include substituted (meth)acrylate derivatives. Specifically, the acrylic monomers include (meth)acrylate derivatives that may be substituted with one or more groups selected from the group consisting of C1-C20 alkyl groups, C3-C8 cycloalkyl groups, aryl groups, and glycidyl groups, for example, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl ( Examples of acrylic monomers include, but are not limited to, meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate, dodecyl(meth)acrylate, phenyl(meth)acrylate, benzyl(meth)acrylate, and glycidyl(meth)acrylate, maleimides which may be substituted with C1-C6 alkyl groups or aryl groups, such as maleimide, N-methyl-maleimide, and N-phenyl-maleimide, maleic acid, phthalic acid, and itaconic acid. The acrylic monomers can be used individually or in combination of two or more types. Among these, (meth)acrylonitrile is preferred.

[0110] Furthermore, in the present invention, coated branched PTFE can be used as a drip-preventing agent. Coated branched PTFE is a polytetrafluoroethylene mixture consisting of branched polytetrafluoroethylene particles and an organic polymer, and has a coating layer on the outside of the branched polytetrafluoroethylene consisting of an organic polymer, preferably a polymer containing styrene monomer-derived units and / or acrylic monomer-derived units. The coating layer is formed on the surface of the branched polytetrafluoroethylene. It is also preferable that the coating layer contains a copolymer of styrene monomers and acrylic monomers.

[0111] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dropping effect will be insufficient when the amount of polytetrafluoroethylene added is small. Branched polytetrafluoroethylene is particulate and preferably has a particle size of 0.1 to 0.6 μm, more preferably 0.3 to 0.5 μm, and even more preferably 0.3 to 0.4 μm. When the particle size is smaller than 0.1 μm, the surface appearance of the molded product is excellent, but it is difficult to commercially obtain polytetrafluoroethylene with a particle size smaller than 0.1 μm. Also, when the particle size is larger than 0.6 μm, the surface appearance of the molded product may be poor. The number average molecular weight of the polytetrafluoroethylene used in this invention is 1 × 10⁻⁶ 4 ~1 × 10 7 Preferably, 2 × 10 6 ~9×10 6 Generally, polytetrafluoroethylenes with higher molecular weights are more preferred in terms of stability. They can be used in either powder or dispersion form.

[0112] The branched polytetrafluoroethylene content in coated branched PTFE is preferably 20 to 60 parts by weight, more preferably 40 to 55 parts by weight, even more preferably 47 to 53 parts by weight, particularly preferably 48 to 52 parts by weight, and most preferably 49 to 51 parts by weight, per 100 parts by weight of the total weight of coated branched PTFE. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene can sometimes be achieved.

[0113] When using component E, its content is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.2 to 1.5 parts by weight, per 100 parts by weight of component A. A content greater than this range will lead to increased costs and may result in insufficient extrusion processability. On the other hand, a content smaller than this range may result in insufficient flame retardancy and a decrease in tensile strength. The percentage of component D mentioned above indicates the net amount of drip inhibitor, and in the case of mixed PTFE, it indicates the net amount of PTFE.

[0114] <Other ingredients> The polycarbonate resin composition of the present invention may contain other additives such as stabilizers, antioxidants, mold release agents, fillers, 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.

[0124] The following items were evaluated: (i) Discoloration during retention (evaluation of thermal stability during retention) Pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours. Using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U·SM IV], 100 shots of 150mm × 150mm × 2mmt square plates were continuously molded at the temperatures shown in the table. The operation of the molding machine was then stopped, and the resin was allowed to remain in the cylinder. After 15 minutes, square plates were molded again, and the hue of the square plates before and after the retention period was measured using a Tokyo Denshoku color analyzer TC-1800MKII, and the color difference (ΔE) before and after the retention period was calculated. (ii) Strength retention rate during retention (evaluation of thermal stability during retention) Using the square plates used in "(i) Discoloration during retention," a high-speed surface impact test was conducted, and the fracture energy of the square plates before and after retention was measured. The strength retention rate before and after retention was calculated using the following formula. The measurements were performed using a HydroShot HTM-1 manufactured by Shimadzu Corporation at 23°C and a test speed of 7 m / s. Strength retention rate (%) = [Fracture energy after retention / Fracture energy before retention] × 100 (iii) Recyclability The square plates used in "(i) Discoloration during retention" were left horizontally outdoors in Midori Ward, Chiba City for one year, then crushed and reshaped into square plates. The hue and fracture energy of the square plates before retention and the reshaped square plates were measured using the same method as in "(i) Discoloration during retention" and "(ii) Strength retention rate during retention," and the color difference (ΔE) and strength retention rate of the two were measured. (iv)Flame retardant The pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours. UL test specimens were then continuously molded at the temperatures shown in the table using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U·S-MIV], and a V test (vertical combustion test) was performed at a thickness of 1.5 mm in accordance with UL94.

[0125] [Examples 1-13, Comparative Examples 1-4] Resin compositions consisting of the proportions 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, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa. The extrusion temperature was as shown in the table. Using the obtained pellets, test pieces for evaluation were molded using an injection molding machine in the manner described above. The evaluation results are shown in Table 1. The symbols in Table 1 indicate the following components.

[0126] (Component A-1: ​​Recycled polycarbonate resin) A-1-1: Recycled polycarbonate resin, ashing residue 0.01 wt% after 3 hours at 600°C, TGA 5% weight loss 503°C measured under a temperature increase of 20°C / min. A-1-2: Recycled polycarbonate resin, ashing residue 0.5 wt% after 3 hours at 600°C, TGA 5% weight loss 487°C measured under a temperature increase of 20°C / min. 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 after 3 hours at 600°C was 0.1% by weight, and the TGA 5% weight loss measured under a temperature increase of 20°C / min was 499°C. A-1-4: Recycled polycarbonate resin, ashing residue 0.1 wt% after 3 hours at 600°C, TGA 5% weight loss 402°C measured under a temperature increase of 20°C / min. 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 after 3 hours at 600°C was 0.01% by weight, and the TGA 5% weight loss was 435°C measured under a temperature increase of 20°C / min. (Component A-2: Non-recycled polycarbonate resin) A-2-1: 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; ashing residue of 0.0% by weight after 3 hours at 600°C; TGA 5% weight loss of 506°C measured under a temperature increase of 20°C / min)

[0127] (Component B: Flame retardant) B-1: Phosphate ester with resolol [di(2,6-dimethylphenyl) phosphate] as the main component (PX-200 (product name) manufactured by Daihachi Chemical Industry Co., Ltd.) B-2: Tetrabromobisphenol A carbonate oligomer (FG-7000 (product name) manufactured by Teijin Limited) B-3: Cyclic phenoxyphosphazene (FP-110 (product name) manufactured by Fushimi Pharmaceutical Co., Ltd.) B-4: Potassium perfluorobutanesulfonate (F-Top KSBS (product name) manufactured by Mitsubishi Materials Corporation) B-5: Organosiloxane-based flame retardant containing Si-H groups, methyl groups, and phenyl groups (Shin-Etsu Chemical Co., Ltd., X-40-2600J (product name))

[0128] (Component C: Phosphate-based stabilizer) C-1: Triethylphosphonoacetate (JC-224 (product name) manufactured by Johoku Chemical Industry Co., Ltd.) C-2: Stearyl acid phosphate (AX-71 (product name) manufactured by ADEKA Corporation) C-3: Stearyl acid phosphate zinc salt (JP-518Zn (product name) manufactured by Johoku Chemical Industry Co., Ltd.) (Component D: Phosphate stabilizer) D-1: Tris(2,4-di-tert-butylphenyl) phosphite (Irgfos168 (trade name) manufactured by BASF Japan Ltd.) (Component E: Drip prevention agent) E-1: Polytetrafluoroethylene (Daikin Industries, Ltd.'s Polyflon MPFA500B (product name))

[0129] [Table 1] [Industrial applicability]

[0130] The polycarbonate resin composition and molded articles of the present invention have excellent thermal stability during retention and recyclability, and are therefore suitable for use in a wide range of fields, including housings and parts for electrical, electronic, and office automation equipment, interior and exterior parts 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) 0.001 to 30 parts by weight of flame retardant (component B) and (C) 0.001 to 2 parts by weight of phosphate stabilizer (component C), wherein 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 flame retardant selected from the group consisting of (B-1) phosphate ester compounds (component B-1), (B-2) halogenated carbonate compounds (component B-2), (B-3) phosphazene compounds (component B-3), (B-4) metal sulfonic acid salts (component B-4), and (B-5) silicone compounds (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. The polycarbonate resin composition according to claim 1, comprising 0.05 to 3 parts by weight of (E) drip inhibitor (component E) per 100 parts by weight of component A.

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

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