Polycarbonate resin composition and molded article made therefrom

Abstract

The present invention provides a conductive polycarbonate resin composition that exhibits excellent surface smoothness, rigidity, and dimensional stability during molding. [Solution] A polycarbonate resin composition comprising (A) 100 parts by weight of polycarbonate resin (component A), (B) 20 to 120 parts by weight of glass flakes (component B) having a number average particle size of 5 to 160 μm and an average thickness of 0.1 to 1.5 μm, (C) 20 to 60 parts by weight of polyester resin (component C), (D) 1 to 30 parts by weight of conductive carbon black (component D), and (E) 0.001 to 1 part by weight of at least one phosphate ester (component E) selected from the group consisting of phosphonic acid esters (component E-1) with an acid value of 0.01 to 0.30 mg KOH / g, acidic phosphate esters (component E-2) with an acid value of 10 to 200 mg KOH / g, and stearyl acid phosphate zinc salt (component E-3).

Description

[Technical Field]

[0001] The present invention relates to a conductive polycarbonate resin composition and a molded article made therefrom, which exhibits excellent surface smoothness, rigidity, and dimensional stability during molding. [Background technology]

[0002] Generally, polycarbonate resins are electrically insulating materials, but conductivity is often required in certain electrical and electronic component applications, as well as for antistatic and electromagnetic shielding properties. It is common practice to impart conductivity to polycarbonate resins by compounding conductive agents, and the compounding of conductive carbon as such an agent has been disclosed (see Patent Document 1). However, in order to impart practically effective conductivity by compounding conductive carbon, a large amount of conductive carbon must be added, resulting in a decrease in mechanical properties and other impairments to the original properties of the polycarbonate resin, often causing practical problems. This problem can be avoided to some extent by using fibrous conductive fillers in combination. However, when fibrous conductive fillers are compounded, even with sufficient mold temperature control, the anisotropy during molding shrinkage due to the orientation of the fibrous conductive fillers causes extremely large warping in thin-walled molded products. To address this requirement for low warping, a method has been disclosed in which plate-like fillers, such as glass flakes, are compounded to reduce anisotropy during molding shrinkage and thereby reduce warping. (See Patent Document 2) However, when glass flakes are added, there is a problem that the appearance of the molded product is impaired due to the generation of silver and the lifting of fillers during retention at high temperatures. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] JP-A-4-342758 [Patent Document 2] Japanese Patent Publication No. 2012-207075 [Overview of the Initiative]

Problems to be Solved by the Invention

[0004] An object of the present invention is to provide a polycarbonate resin composition having excellent conductivity, surface smoothness, rigidity, and dimensional stability during retention molding, and a molded article made therefrom.

Means for Solving the Problems

[0005] As a result of intensive studies to solve such problems, the present inventors have found that by blending a polycarbonate resin with glass flakes having specific average thickness and particle size, a polyester resin, conductive carbon black, and a specific phosphate ester, a polycarbonate resin composition having excellent conductivity, surface smoothness, rigidity, and dimensional stability during retention molding can be provided, and thus the present invention has been achieved.

[0006] That is, the present invention is as follows. 1. A polycarbonate resin composition containing 20 to 120 parts by weight of (B) glass flakes (component B) having a number average particle size of 5 to 160 μm and an average thickness of 0.1 to 1.5 μm, 20 to 60 parts by weight of (C) a polyester resin (component C), 1 to 30 parts by weight of (D) conductive carbon black (component D), and 0.001 to 1 part by weight of at least one phosphate ester (component E) selected from the group consisting of (E-1) a phosphonic acid ester having an acid value of 0.01 to 0.30 mgKOH / g, (E-2) an acidic phosphate ester having an acid value of 10 to 200 mgKOH / g, and (E-3) a zinc salt of stearyl acid phosphate, based on 100 parts by weight of (A) a polycarbonate resin (component A). 2. The polycarbonate resin composition according to item 1 above, wherein component C is a polyethylene terephthalate resin. 3. The polycarbonate resin composition according to item 1 or 2 above, wherein component D is conductive carbon black having a dibutyl phthalate (DBP) absorption amount of 200 cm 3 / 100 g or more. 4. The polycarbonate resin composition according to any one of the preceding items 1 to 3, characterized in that it contains 0.001 to 1 part by weight of (F) phosphite (F component) with respect to 100 parts by weight of component A. 5. A molded article comprising the polycarbonate resin composition according to any one of the preceding items 1 to 4.

[0007] Hereinafter, the present invention will be specifically described.

[0008] <Component A: Polycarbonate-based resin> The polycarbonate-based 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.

[0009] 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.

[0010] 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-1. 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%).

[0011] 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.

[0012] 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%.

[0013] 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.

[0014] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0015] 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 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.

[0016] Branched polycarbonate resins can impart properties such as drip prevention to the polycarbonate 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, and 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.

[0017] 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. 1It can be calculated by 1H-NMR measurement.

[0018] 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.

[0019] The reaction methods used to produce the polycarbonate resin of the present invention, 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.

[0020] In producing the polycarbonate resin composition of 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.

[0021] 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 resin 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) SPCalculate the viscosity-average molecular weight M 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 polycarbonate resin composition of 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 obtained solution is removed. The solid after solvent removal is thoroughly dried to obtain a solid of the component 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.

[0022] It is also possible to use a polycarbonate-polydiorganosiloxane copolymer resin as the polycarbonate resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a divalent phenol represented by the following general formula (1) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3).

[0023]

Chemical formula

[0024] [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.

[0025] [ka]

[0026] [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.

[0027] [ka]

[0028] [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.

[0029] 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.

[0030] 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.

[0031] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0032] [ka]

[0033] 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.

[0034] 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.

[0035] The polydiorganosiloxane content in the total weight of the polycarbonate-polydiorganosiloxane copolymer resin 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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).

[0041] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonate resins, 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.

[0042] 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.

[0043] 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.

[0044] [ka]

[0045] (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.

[0046] 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).

[0047] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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).

[0055]

number

[0056] The terms "average domain size" and "normalized dispersion" used in connection with the present invention refer to measured values obtained by measuring the 1.0 mm thick portion of a three-layer plate prepared by the method described in the Examples by such a small-angle X-ray scattering method. Further, analysis was performed using an isolated particle model that does not consider inter-particle interaction (inter-particle interference).

[0057] <Component B: Glass flakes> The glass flakes used as Component B in the polycarbonate resin composition of the present invention are glass flakes having an average thickness of 0.1 to 1.5 μm, preferably 0.2 to 1.0 μm, more preferably 0.3 to 0.4 μm. When glass flakes having an average thickness greater than 1.5 μm are used, the surface smoothness during retention molding deteriorates. Further, when the average thickness becomes less than 0.1 μm, the glass flakes are significantly cracked during kneading with the polycarbonate resin, and a sufficient reinforcing effect and suppression of molding shrinkage are not exhibited. Here, the average thickness is measured by the following method. That is, using a scanning electron microscope (SEM), the thickness of each of 100 or more glass flakes is measured, and the measured values are averaged. In this case, the glass flakes alone may be observed and measured with a scanning electron microscope, or the glass flakes may be filled into a resin, molded, broken, and the fracture surface may be observed and measured. In any measurement method, it is necessary to adjust the sample stage of the scanning electron microscope with a sample stage fine adjustment device so that the glass flake cross-section (thickness plane) is perpendicular to the irradiation electron beam axis of the scanning electron microscope.

[0058] The glass flakes are preferably glass flakes that have been surface-treated with a surface treatment agent. The amount of surface treatment agent is preferably 1.5 to 5 parts by weight, more preferably 1.7 to 5 parts by weight, even more preferably 2 to 5 parts by weight, and particularly preferably 2.5 to 4.5 parts by weight per 100 parts by weight of glass flakes. If the amount of surface treatment agent is less than 1.5 parts by weight, the mechanical strength may decrease, and if the amount of surface treatment agent is more than 5 parts by weight, the thermal stability during extrusion and molding will be poor, and the resin may become discolored, impairing the appearance of the molded product. The surface treatment agent is preferably one or more resins selected from the group consisting of polyvinyl acetate resins, polyacrylate resins, polyurethane resins, epoxy resins, copolymers thereof and modified products thereof, and coupling agents such as silane coupling agents, titanium coupling agents, aluminate coupling agents and zirconia coupling agents as coupling agents for these resins, more preferably a combination of epoxy resin and silane coupling agent. The surface treatment is carried out by mixing one or more resins selected from the group consisting of polyvinyl acetate resins, polyacrylate resins, polyurethane resins, epoxy resins, copolymers thereof, and modified products thereof, and coupling agents such as silane-based coupling agents, titanium-based coupling agents, aluminate-based coupling agents, and zirconia-based coupling agents in a predetermined ratio, further diluting the mixture with water or an organic solvent to about 2 to 100 times, preparing a treatment solution, spraying the treatment solution onto glass flakes, and then drying it.

[0059] Furthermore, it is preferable that the glass flakes are granulated or aggregated with a binder such as an acrylic resin, a urethane resin, an epoxy resin, or an unsaturated polyester resin from the viewpoint of handling. However, the above-described average particle size range and thickness range of the glass flakes do not apply to the granular materials or aggregates obtained by such granulation or aggregation. The glass composition of the above glass flakes is applicable to various glass compositions represented by A glass, C glass, E glass, etc., and is not particularly limited. Further, the number average particle size of the glass flakes is 5 to 160 μm, preferably 10 to 70 μm, more preferably 15 to 50 μm. When the number average particle size is less than 5 μm, the mechanical strength and the effect of suppressing molding shrinkage decrease, while when the number average particle size exceeds 160 μm, the surface smoothness during retention molding deteriorates. Here, the number average particle size is calculated as the median diameter of the weight distribution of the particle size determined by the standard sieve method.

[0060] The content of component B is 20 to 120 parts by weight, preferably 25 to 80 parts by weight, more preferably 30 to 60 parts by weight with respect to 100 parts by weight of component A. When the content of component B is less than 20 parts by weight, the reinforcing effect by the glass flakes such as mechanical strength and suppression of molding shrinkage and the effect of imparting conductivity are not sufficient, and when it exceeds 120 parts by weight, the surface smoothness during retention molding deteriorates.

[0061] <Component C: Polyester resin> The polyester resin used as component C of the present invention is preferably a polyester resin in which 70 mol% or more of 100 mol% of the dicarboxylic acid component forming the polyester is an aromatic dicarboxylic acid, more preferably 90 mol% or more, and most preferably 99 mol% or more is an aromatic dicarboxylic acid.

[0062] Examples of these dicarboxylic acids include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenidicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfisoisophthalic acid, ethylene-bis-p-benzoic acid, etc. These dicarboxylic acids can be used individually or in combination of two or more. In addition to the aromatic dicarboxylic acids mentioned above, the polyester resin of the present invention can be copolymerized with aliphatic dicarboxylic acid components in an amount of less than 30 mol%. Specific examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc.

[0063] Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used individually or in combination of two or more. Preferably, the divalent phenol content in the diol component is 30 mol% or less.

[0064] Specific examples of polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, and copolymerized polyester resins such as polyethylene isophthalate / terephthalate copolymers and polybutylene terephthalate / isophthalate copolymers.

[0065] Furthermore, the end group structure of the polyester resin used in the present invention is not particularly limited, and in addition to cases where the proportion of hydroxyl groups and carboxyl groups in the end groups is approximately equal, the proportion of one may be greater than the other. Moreover, the end groups may be encapsulated by reacting them with a compound that is reactive with them.

[0066] The polyester resin used in the present invention is produced by polymerizing a dicarboxylic acid component and a diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., according to conventional methods, and discharging the by-product water or lower alcohol from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. In addition, the present invention can also use compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction that is a known precursor to polycondensation, and it is also possible to deactivate such catalysts with a phosphoric acid or phosphorous acid compound, etc., after the transesterification reaction is completed and then perform polycondensation. Furthermore, the polyester resin can be produced using either a batch method or a continuous polymerization method.

[0067] Furthermore, among the polyester resins mentioned above, polyethylene terephthalate is particularly preferred. The polyethylene terephthalate of the present invention is a polymer obtained by polycondensation reaction of terephthalic acid or its derivatives and 1,4-ethanediol or its derivatives, and as described above, it includes copolymers with other dicarboxylic acid components and other alkylene glycol components.

[0068] The terminal group structure of polyethylene terephthalate is not particularly limited, as described above, but it is more preferable to have fewer terminal carboxyl groups compared to terminal hydroxyl groups. Regarding the manufacturing method, various methods described above can be used, but continuous polymerization is preferred. This is because it offers high quality stability and is cost-effective. Furthermore, it is preferable to use an organotitanium compound as the polymerization catalyst. This is because it tends to have less impact on transesterification reactions. Preferred examples of such organotitanium compounds include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and reaction products of tetrabutyl titanate and trimellitonic anhydride. The amount of organotitanium compound used is preferably such that its titanium atoms constitute 3 to 12 mg atomic percent relative to the acidic components constituting polyethylene terephthalate.

[0069] The molecular weight of the polyester resin of the present invention is not particularly limited, but it is preferably 0.5 to 1.5, and particularly preferably 0.6 to 1.2, when measured at 35°C with o-chlorophenol as the solvent.

[0070] The content of component C is 20 to 60 parts by weight, preferably 25 to 45 parts by weight, and more preferably 30 to 40 parts by weight, per 100 parts by weight of component A. If the content of component C is less than 20 parts by weight, sufficient conductivity cannot be imparted, and it also leads to deterioration of surface smoothness during stagnation molding and a decrease in mechanical strength. On the other hand, if it exceeds 60 parts by weight, mechanical properties, conductivity, and surface smoothness during stagnation molding decrease.

[0071] <Component D: Conductive Carbon Black> The conductive carbon black used in the present invention is a conductive carbon black having an average particle size preferably of 1 to 500 μm, more preferably 10 to 100 μm, and ketjen black, acetylene black or various furnace-based conductive carbon blacks can be used.

[0072] The content of Component D is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of Component A. When the content of Component D exceeds 30 parts by weight, the fluidity decreases, resulting in poor surface smoothness during retention molding. On the other hand, when it is less than 1 part by weight, sufficient conductivity cannot be imparted. Also, the dibutyl phthalate (DBP) absorption amount of Component D is preferably 200 cm 3 / 100 g or more, and more preferably 300 cm 3 / 100 g or more. When the dibutyl phthalate (DBP) absorption amount of Component D is within this range, the balance between conductivity and fluidity may be good. Also, the upper limit of the dibutyl phthalate (DBP) absorption amount is not particularly limited, but it is preferably 500 cm 3 / 100 g or less. The DBP absorption amount is measured in accordance with JIS K6217.

[0073] <Component E: Phosphate> The polycarbonate resin composition of the present invention contains at least one phosphate selected from the group consisting of phosphonic acid ester (Component E-1) having an acid value of 0.01 to 0.30 mgKOH / g, acidic phosphate (Component E-2) having an acid value of 10 to 200 mgKOH / g, and zinc stearyl phosphate (Component E-3). When a phosphate other than Component E is used, the surface smoothness during retention molding deteriorates due to gas generation.

[0074] The content of Component E is 0.001 to 1 part by weight, preferably 0.01 to 0.1 part by weight, more preferably 0.01 to 0.07 part by weight, based on 100 parts by weight of Component A. When the content of Component E is less than 0.001 part by weight or exceeds 1 part by weight, the surface smoothness during retention molding deteriorates.

[0075] <Component E-1: Phosphonic Acid Ester> As the phosphonic acid ester used in the present invention, phosphonic acid monoester, phosphonic acid diester, and phosphonic acid triester can be used, but phosphonic acid triester is preferred. Various combinations of esters with carbon numbers from 1 to 22 can be used, but triethyl phosphonoacetate is most preferred. The acid value of the phosphonic acid ester is 0.01 to 0.30 mgKOH / g, preferably 0.01 to 0.20 mgKOH / g, more preferably 0.05 to 0.15 mgKOH / g. Those with an acid value less than 0.01 mgKOH / g are not practical in production, and when the acid value is greater than 0.30 mgKOH / g, the surface smoothness during retention molding deteriorates. The acid value was measured using a potentiometric titration apparatus, and an alcohol solution of the phosphonic acid ester was titrated with a KOH alcohol solution.

[0076] <Component E-2: Acidic Phosphoric Ester> As the acidic phosphoric ester used in the present invention, phosphoric acid monoester, phosphoric acid diester, phosphoric acid triester, and mixtures can be used, but a mixture of monoester and diester is preferred. Various combinations of esters with carbon numbers from 1 to 22 can be used, but stearyl acid phosphate is most preferred. The acid value of the acidic phosphoric ester is 10 to 200 mgKOH / g, preferably 120 to 180 mgKOH / g, more preferably 150 to 170 mgKOH / g. When the acid value is less than 10 mgKOH / g, it is not practical in production as an acidic phosphoric ester, and when the acid value is greater than 200 mgKOH / g, the surface smoothness during retention molding deteriorates. The acid value was measured using a potentiometric titration apparatus, and an alcohol solution of the acidic phosphoric ester was titrated with a KOH alcohol solution.

[0077] <E-component: Zinc salt of stearyl acid phosphate> Examples of the zinc salt of stearyl acid phosphate used in the present invention include zinc distearyl acid phosphate, zinc monostearyl acid phosphate, and mixtures thereof. When using such a mixture, the mixing ratio (molar ratio) of zinc distearyl acid phosphate and zinc monostearyl acid phosphate is preferably 1:2.

[0078] <F-component: Phosphite> The polycarbonate resin composition of the present invention can contain a phosphite in addition to the E-component.

[0079] Examples of phosphite esters 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, and Examples include ris(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.

[0080] The content of component F is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 parts by weight, and even more preferably 0.01 to 0.07 parts by weight, per 100 parts by weight of component A. If the content of component F is less than 0.001 parts by weight or more than 1 part by weight, the surface smoothness during retention molding may deteriorate.

[0081] (Other additives) The polycarbonate resin composition of the present invention is advantageously utilized by using additives used for improvements in its thermal stability and aesthetic properties. These additives will be described in detail below.

[0082] (I) Heat stabilizers The polycarbonate resin composition of the present invention may contain various stabilizers other than the known components E and F. Examples of stabilizers include hindered phenol-based antioxidants.

[0083] (i) Hindered phenol antioxidant The polycarbonate resin composition of the present invention may contain a hindered phenol-based antioxidant. Such a formulation has the effect of suppressing, for example, deterioration of color during molding and deterioration of color during long-term use. Examples of hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylphenol)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5 -Di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methylbenzyl-p-cresol)2,2'-ethyl Den-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-te rt-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-Thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, N,N'-Hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1 Examples include 3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, and tetrakis[methylene-3-(3',5'-di-tert-butyl-4-hydroxyphenyl)propionate]methane. All of these are readily available. The above-mentioned hindered phenol antioxidants can be used alone or in combination of two or more. The content of the hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 parts by weight, and even more preferably 0.005 to 0.3 parts by weight, per 100 parts by weight of component A.

[0084] (ii) Heat stabilizers other than hindered phenol antioxidants The polycarbonate resin composition of the present invention may also contain other heat stabilizers besides hindered phenol antioxidants. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as those represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene. Details of such stabilizers are described in Japanese Patent Publication No. 7-233160. Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and these compounds can be used. Furthermore, stabilizers obtained by mixing these compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the aforementioned company is a suitable example. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of component A. Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. The content of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A. The polycarbonate resin composition of the present invention may optionally contain epoxy compounds. Such epoxy compounds are added for the purpose of suppressing mold corrosion, and basically all epoxy functional groups can be used. Specific examples of preferred epoxy compounds include 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 1,2-epoxy-4-(2-oxyranyl)cyclosexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, copolymers of methyl methacrylate and glycidyl methacrylate, copolymers of styrene and glycidyl methacrylate, and the like. The content of such epoxy compounds is preferably 0.003 to 0.2 parts by weight, more preferably 0.004 to 0.15 parts by weight, and even more preferably 0.005 to 0.1 parts by weight, per 100 parts by weight of component A.

[0085] (II) Flame retardants The polycarbonate resin composition of the present invention may contain various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins, but more preferably (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt-based flame retardants (e.g., alkali (earth) metal salts of organic sulfonic acid, metal salt-based flame retardants of borate, and metal salt-based flame retardants of stannate), and (iv) silicone-based flame retardants consisting of silicone compounds. Furthermore, the blending of compounds used as flame retardants may not only improve flame retardancy but also, depending on the properties of each compound, bring about improvements such as antistatic properties, fluidity, rigidity, and thermal stability.

[0086] The flame retardant content is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, per 100 parts by weight of component A. If the flame retardant content is less than 0.01 parts by weight, sufficient flame retardancy may not be obtained, and if it exceeds 30 parts by weight, the mechanical properties may deteriorate significantly.

[0087] (III) Drip inhibitor As a drip-preventing agent, fibril-forming fluorine-containing polymers are preferably used, and polytetrafluoroethylene (fibrillated PTFE) is particularly preferred. The fibrillated PTFE may be fibrillated PTFE alone, or a mixed form of fibrillated PTFE, i.e., a polytetrafluoroethylene mixture consisting of fibrillated PTFE particles and an organic polymer. Fibrillated PTFE has an extremely high molecular weight and tends to bond with other PTFE particles to form fibers under external forces such as shear force. Its number-average molecular weight is in the range of 1.5 million to tens of millions. The lower limit is more preferably 3 million. This number-average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380°C, as disclosed, for example, in Japanese Patent Application Publication No. 6-145520. That is, fibrillated PTFE has a melt viscosity at 380°C of 10, as measured by the method described in that publication. 7 ~10 13 The range of poise, preferably 10 8 ~10 12 This falls within the scope of poise. Such fibrillated PTFE can be used in solid form as well as in aqueous dispersion form. Furthermore, to improve the dispersibility of such fibrillated PTFE in resins and to obtain even better flame retardancy and mechanical properties, it is also possible to use PTFE mixtures in mixed form with other resins.

[0088] Furthermore, as disclosed in Japanese Patent Publication No. 6-145520, a structure having such fibrillated PTFE as a core and low molecular weight polytetrafluoroethylene as a shell is also preferably used.

[0089] Examples of commercially available fibrillated PTFE include Teflon® 6J from Mitsui DuPont Fluorochemicals Ltd., and Polyflon MPA FA500 and F-201L from Daikin Chemical Industries, Ltd.

[0090] As for the mixed form of fibrillated PTFE, (1) a method of mixing an aqueous dispersion of fibrillated 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 fibrillated 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 fibrillated PTFE with an organic polymer particle solution and obtaining a co-aggregated mixture from such mixture (1) A mixture obtained by methods of simultaneously removing each medium (methods described in Japanese Patent Publication No. 06-220210, Japanese Patent Publication No. 08-188653, etc.), (2) polymerizing monomers that form an organic polymer in an aqueous dispersion of fibrillated PTFE (method described in Japanese Patent Publication No. 9-95583), and (3) uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, then further polymerizing vinyl monomers in the mixed dispersion, and then obtaining a mixture (method described in Japanese Patent Publication No. 11-29679, etc.) can be used.

[0091] Examples of commercially available fibrillated PTFE in these mixed forms include the Metabren A series, represented by Mitsubishi Rayon Co., Ltd.'s "Metabren A3000" (product name), "Metabren A3700" (product name), and "Metabren A3800" (product name), Shine Polymer's SN3300B7 (product name), and GE Specialty Chemicals' "BLENDEX B449" (product name).

[0092] The proportion of fibrillated PTFE in the mixed form is preferably 1% to 95% by weight, more preferably 10% to 90% by weight, and most preferably 20% to 80% by weight, of 100% by weight of the mixture.

[0093] When the proportion of fibrillated PTFE in the mixed form is within this range, good dispersibility of fibrillated PTFE can be achieved. The content of fibrillated PTFE is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 0.5 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. If the content is less than 0.005 parts by weight, the flame retardant effect is difficult to obtain, and if it exceeds 20 parts by weight, the thermal shock resistance (electromagnetic shielding properties) may decrease.

[0094] (IV) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting diverse design properties. Examples of dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can also be blended with metallic pigments to obtain better metallic colors. Aluminum powder is a suitable metallic pigment. In addition, by blending with fluorescent whitening agents or other fluorescent dyes that emit light, even better design effects utilizing the luminescent color can be provided.

[0095] (V) Fluorescent whitening agent In the polycarbonate resin composition of the present invention, the fluorescent whitening agent is not particularly limited as long as it is used to improve the color tone of the resin, etc., to white or bluish-white. Examples include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specifically, examples include CI Fluorescent Brightener 219:1, EASTOBRITE OB-1 manufactured by Eastman Chemical Corporation, and "Hakkoll PSR" manufactured by Showa Chemical Co., Ltd. The fluorescent whitening agent absorbs the ultraviolet energy of light rays and radiates this energy to the visible region. The content of the fluorescent whitening agent is preferably 0.001 to 0.1 parts by weight, and more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of component A. Even if the amount exceeds 0.1 parts by weight, the effect of improving the color tone of the composition may be small.

[0096] (VI) Compounds having heat-absorbing properties The polycarbonate resin composition of the present invention may contain compounds having heat-absorbing properties. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, imonium oxide, and titanium oxide, various metal compounds with excellent near-infrared absorption properties such as metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers. For example, MIR-362, manufactured by Mitsui Chemicals, Inc., is a commercially available and readily obtainable phthalocyanine-based near-infrared absorber. Examples of carbon fillers include carbon black, graphite (including both natural and artificial), and fullerenes, with carbon black and graphite being preferred. These can be used individually or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight, per 100 parts by weight of component A. The content of the metal oxide-based near-infrared absorber, metal boride-based near-infrared absorber, and carbon filler in the polycarbonate resin composition of the present invention is preferably in the range of 0.1 to 200 ppm (by weight), and more preferably in the range of 0.5 to 100 ppm.

[0097] (VII) Light Diffuser The polycarbonate resin composition of the present invention can be given a light-diffusing effect by incorporating a light-diffusing agent. Examples of such light-diffusing agents include polymer microparticles, inorganic microparticles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer microparticles are already known as light-diffusing agents for polycarbonate resins. More preferably, examples include acrylic crosslinked particles with a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane. Examples of light-diffusing agent shapes include spherical, disc-shaped, columnar, and amorphous. Such spherical shapes do not need to be perfect spheres and include deformed ones, and such columnar shapes include cubes. Preferred light-diffusing agents are spherical, and the more uniform the particle size, the better. The content of the light-diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight, per 100 parts by weight of component A. Two or more types of light-diffusing agents can be used in combination.

[0098] (VIII) White pigment for high light reflectivity The polycarbonate resin composition of the present invention can be given a light-reflecting effect by incorporating a light-reflecting white pigment. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of such light-reflecting white pigment is preferably 3 to 30 parts by weight, and more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more light-reflecting white pigments can be used in combination.

[0099] (IX) UV absorber Weather resistance can be imparted to the polycarbonate resin composition of the present invention by incorporating an ultraviolet absorber. Specific examples of such ultraviolet absorbers include benzophenone-based agents such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Specifically, examples of UV absorbers include benzotriazole-based compounds such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, and 2-(2-hydroxy-5-tert-octylphenyl) Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer.Examples of UV absorbers include, specifically, hydroxyphenyltriazine compounds such as 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, examples include compounds in which the phenyl group of the above example compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol. Examples of UV absorbers include cyclic iminoesters such as 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazine-4-one). Examples of cyanoacrylate-based UV absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the above-mentioned ultraviolet absorber may also be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or photostable monomer with a monomer such as alkyl (meth)acrylate, by adopting the structure of a monomer compound that can undergo radical polymerization. Suitable examples of the ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.Among the above, benzotriazole and hydroxyphenyltriazine types are preferred in terms of ultraviolet absorption capacity, while cyclic iminoester and cyanoacrylate types are preferred in terms of heat resistance and hue. Specifically, examples include Chemipro Chemical Co., Ltd.'s "Chemisorb 79" and BASF Japan Ltd.'s "Chinubin 234". The ultraviolet absorbers may be used alone or as a mixture of two or more.

[0100] The amount of ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, even more preferably 0.05 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A.

[0101] (X) Antistatic agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) phosphonium aryl sulfonates, such as phosphonium dodecylbenzenesulfonates, and phosphonium alkyl sulfonates, as well as phosphonium borates, such as phosphonium tetrafluoroborate. The content of the phosphonium salt is appropriately 5 parts by weight or less per 100 parts by weight of component A, preferably in the range of 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight. Examples of antistatic agents include (2) alkali (earth) metal salts of organic sulfonates, such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. As mentioned above, such metal salts are also used as flame retardants. Examples of such metal salts include, more specifically, metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of alkali (earth) metal salts of organic sulfonic acid is appropriately 0.5 parts by weight or less per 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight. Alkali metal salts such as potassium, cesium, and rubidium are particularly preferred.

[0102] Examples of antistatic agents include (3) ammonium alkyl sulfonates and ammonium aryl sulfonates, which are organic ammonium sulfonates. The amount of the ammonium salt is appropriate to be 0.05 parts by weight or less per 100 parts by weight of the components consisting of components A and B. Examples of antistatic agents include (4) polymers containing poly(oxyalkylene) glycol components, such as polyether ester amides, as constituent components. The amount of the polymer is appropriate to be 5 parts by weight or less per 100 parts by weight of component A.

[0103] (XI) Filler The polycarbonate resin composition of the present invention may be blended with various known fillers other than component B as reinforcing fillers. Such fillers can include various fibrous fillers, plate-like fillers other than component B, and granular fillers. Here, plate-like fillers are fillers whose shape is plate-like (including those with uneven surfaces or curved plates). Granular fillers are fillers of other shapes, including irregular shapes.

[0104] Examples of fibrous fillers include glass fibers, metal-coated glass fibers, and glass-milled fibers. The glass fibers that form the base of such fibrous glass fillers are obtained by rapidly cooling molten glass while stretching it in various ways to form a predetermined fibrous shape. The rapid cooling and stretching in this case are not particularly limited. In addition to a circular cross-section, the shape of the cross-section may be other than a perfect circle, such as an ellipse, cocoon shape, flattened shape, and trefoil shape. Furthermore, a mixture of circular and non-circular shapes is also acceptable. A flattened shape is defined as a shape in which the average major axis of the fiber cross-section is 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and the average ratio of major axis to minor axis (major axis / minor axis) is 1.5 to 8, preferably 2 to 6, and even more preferably 2.5 to 5.

[0105] Furthermore, the average fiber diameter of fibrous glass fillers having a high aspect ratio, such as glass fibers, is preferably 1 to 25 μm, and more preferably 3 to 17 μm. When a filler with an average fiber diameter in this range is used, it may be possible to achieve good mechanical strength without impairing the appearance of the molded product. In addition, the fiber length of the high aspect ratio fibrous glass filler is preferably 60 to 500 μm, more preferably 100 to 400 μm, and particularly preferably 120 to 350 μm, as the number average fiber length in the polycarbonate resin composition. This number average fiber length is calculated by an image analysis device from images obtained by observing the residue of the filler collected after processing such as high-temperature ashing, dissolution with solvents, and decomposition with chemicals using an optical microscope. Furthermore, in calculating this value, the fiber diameter is used as a guideline, and fibers with a length less than that are not counted. The aspect ratio of the high aspect ratio fibrous glass filler is preferably 10 to 200, more preferably 15 to 100, and even more preferably 20 to 50. The aspect ratio of the filler is the value obtained by dividing the average fiber length by the average fiber diameter.

[0106] Glass milled fibers are typically produced by shortening glass fibers using a pulverizer such as a ball mill. The aspect ratio of fibrous glass fillers having a low aspect ratio, such as glass milled fibers, is preferably 2 to 10, more preferably 3 to 8. The fiber length of the low aspect ratio fibrous glass filler is preferably 5 to 150 μm, more preferably 9 to 80 μm, as the number average fiber length in the polycarbonate resin composition. The average fiber diameter is preferably 1 to 15 μm, more preferably 3 to 13 μm.

[0107] Examples of plate-shaped fillers other than component B include glass flakes other than component B, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-shaped fillers in which dissimilar materials such as metals or metal oxides are surface-coated to these fillers. The particle size is preferably in the range of 0.1 to 300 μm. In the region up to about 10 μm, this particle size is the value obtained by the median diameter (D50) of the particle size distribution measured by X-ray transmission, a liquid-phase sedimentation method; in the region from 10 to 50 μm, it is the value obtained by the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering; and in the region from 50 to 300 μm, it is the value obtained by the vibrating sieving method. This particle size is the particle size in the resin composition. The plate-shaped filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based materials, or it may be a granulated product that has been bundled or compressed with various resins such as olefin-based resins, styrene-based resins, acrylic-based resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

[0108] (XII) Other resins and elastomers In the polycarbonate resin composition of the present invention, other resins or elastomers other than component C may be used in small proportions in place of a portion of the polycarbonate resin, as long as the effects of the present invention are not impaired. The amount of other resins or elastomers blended is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, even more preferably 5 parts by weight or less, and most preferably 3 parts by weight or less, per 100 parts by weight of component A. Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, epoxy resins, and the like. Examples of elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and core-shell type elastomers such as MBS (methyl methacrylate / sterene / butadiene) rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

[0109] (XIII) Other additives The polycarbonate resin composition of the present invention may contain other fluid modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, and photochromic agents.

[0110] <Regarding the manufacture of resin compositions> The polycarbonate resin composition of the present invention can be pelletized by melt-kneading using an extruder such as a single-screw extruder or a twin-screw extruder. Various reinforcing fillers and additives can also be incorporated into the preparation of these pellets.

[0111] <Regarding the manufacturing of molded products> The polycarbonate resin composition of the present invention can be used to produce various molded products by injection molding pellets manufactured as described above. Furthermore, it is also possible to directly form sheets, films, irregularly shaped extruded products, direct blow molded products, and injection molded products from a resin composition melted and kneaded in an extruder without going through pellets. In such injection molding, molded products can be obtained using injection molding methods such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. In addition, molding can be selected from either the cold runner method or the hot runner method. Furthermore, the resin composition of the present invention can also be used in the form of various irregularly shaped extruded products, sheets, and films by extrusion molding. Inflation, calendering, and casting methods can also be used for molding sheets and films. Furthermore, it is possible to mold it as a heat-shrinkable tube by applying a specific stretching operation. Furthermore, the resin composition of the present invention can be molded into a product by methods such as rotational molding or blow molding. [Effects of the Invention]

[0112] The polycarbonate resin composition of the present invention is a conductive polycarbonate resin composition that is excellent in surface smoothness, rigidity, and dimensional stability during molding. Therefore, it is useful in applications where conductivity is required and further high appearance and thin-walled, lightweight construction are desired, as well as in applications where conductivity and high rigidity are required, and the industrial effects it provides are extremely significant. [Modes for carrying out the invention]

[0113] 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. [Examples]

[0114] The present invention will be further explained with reference to the following examples, but is not limited thereto. The following items were evaluated: (i) Surface smoothness (appearance) during stagnation molding The pellets obtained from each composition of the examples were dried in a hot air dryer at 100°C for 5 hours. Ten consecutive shots of a 100mm x 50mm x 1~3mmt three-tiered plate were then molded using an injection molding machine [Sumitomo Heavy Industries, Ltd. SG150U·SM IV] at a cylinder temperature of 300°C. The operation of the molding machine was then stopped to allow the resin to remain in the cylinder. After 10 minutes, five more shots were molded, and the surface of the molded product was observed and evaluated according to the following criteria. ○: Glass flakes or silver are not noticeable. △: Some glass flakes or silver are slightly noticeable. ×: The glass flakes or silver are noticeably prominent.

[0115] (ii) Conductivity (surface resistivity) Pellets obtained from each composition of the examples were dried in a hot air dryer at 120°C for 5 hours. Three-tiered plates measuring 100 mm × 50 mm × 1~3 mmt were then molded in 10 shots using an injection molding machine (Sumitomo Heavy Industries, Ltd.; SE130EV-A), and the surface resistivity was measured. Surface resistivity was measured in accordance with JIS K7194. After conditioning the samples in an atmosphere of 23°C and 50% relative humidity for 24 hours, the surface resistivity was measured under ambient conditions of 23°C and 50% relative humidity and evaluated according to the following criteria. ○: Surface resistivity is 1.0 × 10 10 Ω / □ or less △: Surface resistivity is 1.0 × 10 10 Ω / □ or more 1.0×10 11 Ω / □ or less ×: Surface resistivity is 1.0 × 10 11 Ω / □ or more

[0116] (iii) Stiffness (flexural modulus) The pellets obtained from each composition of the examples were dried in a hot air dryer at 120°C for 5 hours. Test specimens measuring 10 mm × 80 mm × 4 mmt were formed using an injection molding machine (Sumitomo Heavy Industries, Ltd.; SE130EV-A), and the flexural modulus was measured in accordance with ISO 179 and evaluated according to the following criteria. ○: Flexural modulus of elasticity of 7000 MPa or higher △: Flexural modulus of elasticity is between 6500 MPa and less than 7000 MPa ×: Flexural modulus less than 6500 MPa

[0117] (iv) Dimensional stability (molding shrinkage rate) The pellets obtained from each composition of the examples were dried in a hot air dryer at 120°C for 5 hours. Using an injection molding machine (Sumitomo Heavy Industries, Ltd.; SE130EV-A), a flat plate with a short side of 50 mm, a long side of 100 mm, and a thickness of 2 mm was formed, with a 1.5 mm thick film gate on one of the short sides. After conditioning at 23°C, 50% RH for 24 hours, the dimensions of the flat plate in the flow direction (MD) and perpendicular direction (TD) were measured using a three-dimensional measuring machine (Tokyo Seimitsu Co., Ltd. XYZAX AXCEL 7 / 7 / 5 RDS), and the molding shrinkage rates in the flow direction and perpendicular direction were determined. ○: The molding shrinkage rate is less than 0.2% in both the flow direction and the perpendicular direction. △: Molding shrinkage rate is 0.2% or more and less than 0.25% in both the flow direction and the perpendicular direction. ×: The molding shrinkage rate is 0.25% or higher in both the flow direction and the perpendicular direction.

[0118] [Examples 1-18, Comparative Examples 1-15] Resin compositions consisting of the blending ratios shown in Tables 1 to 3 were prepared as follows. The explanation will follow the symbols in the tables below. Each component in the proportions shown in the tables 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-30XSST, 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, a vent vacuum of 3 kPa, and an extrusion temperature of 280°C. 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 Tables 1 to 3. The symbols in Tables 1 to 3 indicate the following components.

[0119] (Component A: Polycarbonate resin) A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 20,700, manufactured by conventional methods from bisphenol A and phosgene; manufactured by Teijin Limited, product name: Panlite L-1225WX)

[0120] (Component B: Glass flakes) B-1: Glass flakes (average thickness 0.7 μm, number average particle size 160 μm, manufactured by Nippon Sheet Glass Co., Ltd., product name MEG160FY-M02) B-2: Glass flakes (average thickness 0.35 μm, number average particle size 15 μm, manufactured by Nippon Sheet Glass Co., Ltd., MEC015FYX(3421) (product name)) B-3: Glass flakes (average thickness 1.3 μm, number average particle size 130 μm, manufactured by Glassflak, GFE-00101E (product name)) B-4: Glass flakes (average thickness 0.7 μm, number average particle size 5 μm, manufactured by Nippon Sheet Glass Co., Ltd., MEG005FYX(1150) (product name)) B-5 (Comparative Example): Glass flakes (average thickness 0.35 μm, number average particle size 140 μm, manufactured by Nippon Sheet Glass Co., Ltd., product name MEG140D02) B-6 (Comparative Example): Glass flakes (average thickness 0.05 μm, number average particle size 15 μm, manufactured by Glassflak, GFL500 nm (product name)) B-7 (Comparative Example): Glass flakes (average thickness 5 μm, number average particle size 140 μm, manufactured by Nippon Sheet Glass Co., Ltd., REFG-301 (product name)) B-8 (Comparative Example): Glass flakes (average thickness 0.5 μm, number average particle size 3 μm, manufactured by Glassflak, GF250 nm (product name)) B-9 (Comparative Example): Glass flakes (average thickness 1.3 μm, number average particle size 400 μm, manufactured by Glassflak, GF100 (product name))

[0121] (Component C: Polyester resin) C-1: Polyethylene terephthalate resin (intrinsic viscosity 0.77, manufactured by Teijin Limited, product name TRN-8550FF)

[0122] (Component D: Conductive carbon black) D-1: Conductive Furnace Black (DBP oil absorption capacity 327ml / 100g, manufactured by CABOT Co., Ltd., product name VXCMAX22)

[0123] (E component) (Component E-1: Phosphonic acid ester) E-1-1: Triethylphosphonoacetate (manufactured by Johoku Chemical Industry Co., Ltd., product name JC-224, acid value 0.08 mg KOH / g) E-1-2: Triethyl phosphonoacetate (mixture of E-1-1 and E-1-3 (weight ratio 1:1), acid value 0.23 mg KOH / g) E-1-3 (Comparative Example): Triethylphosphonoacetate (Solvay, Inc., Acid Value 0.39 mg KOH / g) (Component E-2: Acidic phosphate ester) E-2-1: Stearyl acid phosphate (Manufactured by ADEKA Corporation, AX-71 (product name), acid value 158 mg KOH / g) E-2-2: Stearyl acid phosphate (mixture of E-2-1 and E-2-3 (weight ratio 1:1), acid value 187 mg KOH / g) E-2-3 (Comparative Example): Stearyl acid phosphate (A-18F (product name), manufactured by SC Organic Chemicals Co., Ltd., acid value 215 mg KOH / g) (Component E-3: Stearyl acid phosphate zinc salt) E-3: Stearyl acid phosphate zinc salt (a mixture of distearyl acid phosphate zinc salt and monostearyl acid phosphate zinc salt, manufactured by Johoku Chemical Industry Co., Ltd., product name JP-518Zn) E-4 (Comparative Example): Phenylephosphonic acid (PPA (product name) manufactured by Nissan Chemical Corporation)

[0124] (Component F: Phosphite ester) F-1: 3,9-Bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (Manufactured by ADEKA Corporation, PEP-36 (product name))

[0125] [Table 1]

[0126] [Table 2]

[0127] [Table 3]

Claims

1. A polycarbonate resin composition comprising: (A) 100 parts by weight of polycarbonate resin (component A); (B) 20 to 120 parts by weight of glass flakes (component B) having a number average particle size of 5 to 160 μm and an average thickness of 0.1 to 1.5 μm; (C) 20 to 60 parts by weight of polyester resin (component C); (D) 1 to 30 parts by weight of conductive carbon black (component D); and (E) 0.001 to 1 part by weight of at least one phosphate ester (component E) selected from the group consisting of phosphonic acid ester (component E-1) having an acid value of 0.01 to 0.30 mg KOH / g, acidic phosphate ester (component E-2) having an acid value of 10 to 200 mg KOH / g, and stearyl acid phosphate zinc salt (component E-3).

2. The polycarbonate resin composition according to claim 1, characterized in that component C is polyethylene terephthalate resin.

3. Component D is dibutyl phthalate (DBP), absorption amount is 200 cm ３ The polycarbonate resin composition according to claim 1 or 2, characterized in that it is conductive carbon black in an amount of 100 g or more.

4. The polycarbonate resin composition according to claim 1 or 2, characterized in that it contains 0.001 to 1 part by weight of (F) phosphite ester (component F) per 100 parts by weight of component A.

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

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