Resin composition and molded article made thereof

Abstract

The present invention provides a resin composition and molded articles made therefrom that exhibit excellent impact resistance, fluidity, and resistance to humid heat. [Solution] A polycarbonate resin composition characterized by containing 0.001 to 1 part by weight of (C) an organic thiophosphate compound (component C) per 100 parts by weight of a resin component comprising (A) 40 to 90 parts by weight of polycarbonate resin (component A) and (B) 10 to 60 parts by weight of a copolymer obtained by polymerizing aromatic vinyl monomer and vinyl cyanide monomer (component B).

Description

Technical Field

[0001] The present invention relates to a resin composition excellent in impact resistance, fluidity, and heat and moisture resistance, and a molded product made therefrom.

Background Art

[0002] Polycarbonate resin has excellent mechanical properties and thermal properties, and is therefore used in various applications mainly in the fields of automobiles, OA equipment, and electronic and electrical equipment. In addition, alloy resins in which ABS resin or AS resin is blended with polycarbonate resin take advantage of their excellent fluidity and are used in applications such as automobile parts, printer parts, personal computer casings, and computer parts. In recent years, especially in the automotive field, the use of alloy resins in which ABS resin is blended with polycarbonate resin has been increasing. However, there is a problem that the impact resistance is impaired by blending ABS resin. Therefore, studies have been made to improve the impact resistance. Patent Document 1 discloses a method of blending an impact modifier such as an acrylic graft copolymer with an alloy resin in which ABS resin is blended with polycarbonate resin. Patent Document 2 discloses adding a phosphorus compound to an alloy resin in which ABS resin is blended with polycarbonate resin. However, although the impact resistance is improved by these methods, the heat and moisture resistance has not been improved.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] The object of the present invention is to provide a resin composition and a molded article made therefrom that exhibits excellent impact resistance, fluidity, and moisture and heat resistance. [Means for solving the problem]

[0005] As a result of diligent research aimed at achieving the above objective, the present inventors have discovered that by adding an organic thiophosphate compound to a resin component consisting of a copolymer obtained by polymerizing polycarbonate resin, aromatic vinyl monomer, and vinyl cyanide monomer, it is possible to provide a resin composition and molded articles made therefrom that have excellent impact resistance, fluidity, and moisture and heat resistance, thus arriving at the present invention.

[0006] In other words, the present invention is as follows. 1. A polycarbonate resin composition characterized by containing 0.001 to 1 part by weight of (C) an organic thiophosphate compound (component C) per 100 parts by weight of a resin component comprising (A) 40 to 90 parts by weight of polycarbonate resin (component A) and (B) 10 to 60 parts by weight of a copolymer obtained by polymerizing aromatic vinyl monomers and vinyl cyanide monomers (component B). 2. The polycarbonate resin composition according to item 1 above, characterized in that component C is zinc dialkyldithiophosphate. 3. The polycarbonate resin composition according to item 1 or 2 above, characterized in that component B is a copolymer produced by a bulk polymerization method that does not use dispersants and emulsifiers. 4. A polycarbonate resin composition according to any one of items 1 to 3 above, characterized in that it contains 0.5 to 10 parts by weight of an impact modifier other than component (D)B, per 100 parts by weight of the resin component. 5. The polycarbonate resin composition according to item 4 above, characterized in that component D is an acrylic block copolymer containing a polymer block containing acrylic acid ester monomer units and a polymer block containing methacrylic acid ester monomer units. 6. The polycarbonate resin composition according to item 5 above, characterized in that component D is an acrylic block copolymer in which the content of polymer blocks containing methacrylic acid ester monomer units is 25% by weight or more of the total blocks. 7. A molded article made from a polycarbonate resin composition as described in any of items 1 to 6 above.

[0007] (Component A: Polycarbonate resin) The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0008] 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.

[0009] In this invention, in addition to bisphenol A-based polycarbonate resins, which are general-purpose polycarbonate resins, it is also possible to use special polycarbonate resins manufactured using other divalent phenols as component A. For example, polycarbonate resins (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter sometimes abbreviated as "BCF") as some or all of the divalent phenol components are suitable for applications where dimensional changes due to water absorption and morphological stability are particularly demanding. It is preferable that these divalent phenols other than BPA be used in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate resin. In particular, when high rigidity and better heat and humidity 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%).

[0010] 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.

[0011] 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 moisture and heat 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 160-250°C, preferably 170-230°C, and a water absorption rate of 0.10-0.30%, preferably 0.13-0.30%, more preferably 0.14-0.27%.

[0012] 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.

[0013] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0014] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0015] Branched polycarbonate resins can impart properties such as drip prevention to the resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0016] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be generated as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. 1 It can be calculated by 1H-NMR measurement.

[0017] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0018] Reaction methods such as the interfacial polymerization method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of cyclic carbonate compound, which are the production methods of the polycarbonate resin of the present invention, are well-known methods in various literatures and patent gazettes.

[0019] In producing the resin composition of the present invention, the viscosity average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.5×10 4 ~4.0×10 4 and more preferably 1.7×10 4 ~3.5×10 4 and even more preferably 1.9×10 4 ~3.0×10 4 In the case of a polycarbonate resin having a viscosity average molecular weight of less than 1.5×10 4 , good mechanical properties may not be obtained. On the other hand, a resin composition obtained from a polycarbonate resin having a viscosity average molecular weight exceeding 4.0×10 4 is inferior in versatility in terms of poor fluidity during injection molding.

[0020] In addition, the polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, the above range (5×10 4Polycarbonate resins having a viscosity-average molecular weight exceeding 7 × 10 exhibit improved entropy elasticity. As a result, they exhibit good moldability in gas-assisted molding and foam molding, which are sometimes used when forming reinforced resin materials into structural members. This improvement in moldability is even better than that of the branched polycarbonate resin. In a more preferred embodiment, component A has a viscosity-average molecular weight of 7 × 10 4 ~3×10 5 Polycarbonate resin (component A-1-1) and viscosity-average molecular weight 1 × 10 4 ~3×10 4 It consists of aromatic polycarbonate resin (components A-1-2), and its viscosity-average molecular weight is 1.6 × 10⁻⁶. 4 ~3.5×10 4 Polycarbonate resin (component A-1) (hereinafter sometimes referred to as "high molecular weight component-containing polycarbonate resin") can also be used.

[0021] In such a polycarbonate resin containing high molecular weight components (component A-1), the molecular weight of component A-1-1 is 7 × 10⁻⁶. 4 ~2×10 5 Preferably, 8 × 10 4 ~2×10 5 More preferably 1 × 10 5 ~2×10 5 Particularly preferred is 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-2 is 1 × 10⁻⁶. 4 ~2.5×10 4 Preferably, and more preferably, 1.1 × 10 4 ~2.4×10 4 More preferably 1.2 × 10 4 ~2.4×10 4 Particularly preferred is 1.2 × 10 4 ~2.3×10 4 That is the case.

[0022] A polycarbonate resin containing high molecular weight components (component A-1) can be obtained by mixing component A-1-1 and component A-1-2 in various proportions and adjusting them to satisfy a predetermined molecular weight range. Preferably, component A-1-1 is 2 to 40% by weight of component A-1 out of 100% by weight of component A-1, more preferably 3 to 30% by weight of component A-1-1, even more preferably 4 to 20% by weight of component A-1-1, and particularly preferably 5 to 20% by weight of component A-1-1.

[0023] Furthermore, methods for preparing component A-1 include (1) a method of independently polymerizing component A-1-1 and component A-1-2 and mixing them; (2) a method of producing an aromatic polycarbonate resin that exhibits multiple polymer peaks in a molecular weight distribution chart by GPC method within the same system, as exemplified by the method shown in Japanese Patent Application Publication No. 5-306336, and producing such an aromatic polycarbonate resin to satisfy the conditions for component A-1 of the present invention; and (3) a method of mixing the aromatic polycarbonate resin obtained by such a production method (production method of (2)) with separately produced component A-1-1 and / or component A-1-2.

[0024] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (H 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 required specific viscosity (H) SP The viscosity-average molecular weight M is calculated from the following formula. H SP / c=[H]+0.45×[H] 2 c (where [H] is the intrinsic viscosity) [H] = 1.23 × 10 -4 M 0.83 c = 0.7 Furthermore, the viscosity-average molecular weight of the polycarbonate resin in the resin composition of the present invention is calculated in the following manner. Specifically, the composition is mixed with methylene chloride in an amount 20 to 30 times its weight to dissolve the soluble components in the composition. These soluble components are collected by Celite filtration. The solvent is then removed from the resulting solution. The solid after solvent removal is thoroughly dried to obtain a solid of the components that dissolve in methylene chloride. The specific viscosity at 20°C is determined from a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride in the same manner as above, and the viscosity-average molecular weight M is calculated from this specific viscosity in the same manner as above.

[0025] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. Preferably, the polycarbonate-polydiorganosiloxane copolymer resin is 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).

[0026] [ka]

[0027] [In the above general formula (1), R 1 and R 2 Each 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.

[0028] [ka]

[0029] [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.

[0030] [ka]

[0031] [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 10Each 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.

[0032] 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.

[0033] 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.

[0034] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), the following compounds are preferably used, for example.

[0035] [ka]

[0036] 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.

[0037] 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.

[0038] The polydiorganosiloxane content in the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. More preferably, the polydiorganosiloxane content is 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of this preferred range, a stable appearance less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and polydiorganosiloxane content are: 1 It can be calculated by 1H-NMR measurement.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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).

[0044] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0045] 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.

[0046] 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.

[0047] [ka]

[0048] [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.

[0049] 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).

[0050] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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 [H SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0056] 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.

[0057] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 60 nm. More preferably, this average size is 3 to 55 nm, and even more preferably 5 to 50 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.

[0058] (Component B: Copolymer obtained by polymerizing aromatic vinyl monomers and vinyl cyanide monomers) Component B of the present invention is a copolymer obtained by polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, and is preferably a copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and a diene-based rubber polymer. Component B preferably consists of 40-90% by weight of aromatic vinyl monomer, 10-50% by weight of vinyl cyanide monomer, and 0-50% by weight of other polymers or monomers.

[0059] Examples of aromatic vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, and tribromstyrene, with styrene being particularly preferred. The proportion of aromatic vinyl monomer in component B is, out of 100% by weight of component B, more preferably 45% by weight at the lower limit, even more preferably 50% by weight, and particularly preferably 55% by weight at the upper limit, more preferably 75% by weight, even more preferably 70% by weight, and particularly preferably 65% ​​by weight.

[0060] Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. The proportion of vinyl cyanide monomer in component B is, out of 100% by weight of component B, more preferably 12% by weight at the lower limit, even more preferably 14% by weight, and particularly preferably 15% by weight at the upper limit, more preferably 28% by weight, even more preferably 26% by weight, and particularly preferably 25% by weight.

[0061] Furthermore, copolymers of other polymers or monomers copolymerized with these are also acceptable. In this case, examples of copolymerizable polymers include diene-based rubber polymers using rubber components such as polybutadiene, polyisoprene, and styrene-butadiene copolymers. Examples of other copolymerizable monomers include monomers other than (meth)acrylic acid ester compounds, such as maleimide monomers like maleimide, N-methylmaleimide, N-cyclohexylmaleimide, and N-phenylmaleimide; acrylamide monomers like acrylamide and N-methylacrylamide; unsaturated anhydrides like maleic anhydride and itaconic anhydride; and unsaturated acids like acrylic acid and methacrylic acid. The proportion of other monomers in component B is preferably 40% by weight and even more preferably 30% by weight, out of 100% by weight of component B.

[0062] Specific examples of component B include acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, and acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer, with acrylonitrile-butadiene-styrene copolymer being the most preferred. These copolymers may be used individually or as a mixture of two or more.

[0063] Component B is preferably produced by bulk polymerization without the use of dispersants and emulsifiers, and the copolymerization method may be single-stage grafting or multi-stage grafting. It may also be a mixture with a copolymer consisting only of graft components produced as by-products during manufacturing.

[0064] The content of component B is 10 to 60 parts by weight, preferably 15 to 50 parts by weight, and more preferably 20 to 45 parts by weight, per 100 parts by weight of the resin component. If the content of component B is less than 10 parts by weight, sufficient fluidity cannot be obtained, and if it exceeds 60 parts by weight, the moisture and heat resistance and impact resistance deteriorate.

[0065] (Component C: Organic thiophosphate compound) The polycarbonate resin composition of the present invention contains an organic thiophosphate compound. If a phosphorus-based compound other than the organic thiophosphate compound is used, the moisture and heat resistance deteriorates. Examples of organic thiophosphate compounds include thiophosphate, thiophosphate esters, and metal salts thereof, with metal thiophosphate salts being preferred. Furthermore, among metal thiophosphate salts, zinc dialkyldithiophosphate (ZnDTP), represented by the following formula (4), is particularly preferred.

[0066] [ka]

[0067] [In the above general formula (4), R 1 ~R 4This is a hydrocarbon group, and it may be the same or different.

[0068] R 1 ~R 4 Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, isobutyl group, pentyl group, 4-methylpentyl group, hexyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, isodecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group, docosyl group, tetracosyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group, dimethylcyclohexyl group, cycloheptyl group, phenyl group, tolyl group, xylyl group, ethylphenyl group, propylphenyl group, butylphenyl group, pentylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl Examples include, but are not limited to, the tetradecylphenyl group, hexadecylphenyl group, octadecylphenyl group, and benzyl group.

[0069] The content of component C is 0.001 to 1 part by weight, preferably 0.02 to 0.15 parts by weight, and more preferably 0.04 to 0.1 parts by weight, per 100 parts by weight of the resin component consisting of components A and B. If the content of component C is less than 0.001 parts by weight, the moisture and heat resistance deteriorates, and if it exceeds 1 part by weight, both the moisture and heat resistance and the fluidity deteriorate.

[0070] (Component D: Impact modifier other than component B) The polycarbonate resin composition of the present invention may contain impact modifiers other than component B. The impact modifier other than component B is preferably at least one selected from the group consisting of a graft polymer obtained by graft polymerizing at least one compound containing a (meth)acrylic acid ester compound onto one rubber selected from the group consisting of butadiene rubber, acrylic rubber, and silicone-acrylic composite rubber, and a glycidyl group-containing polyethylene copolymer, and a graft polymer having a core-shell structure is more preferred. Alternatively, the core-shell type graft polymer is a graft copolymer obtained by copolymerizing a rubber component with a glass transition temperature of 10°C or less as the core, with one or more monomers selected from vinyl compounds copolymerizable with these, including (meth)acrylic acid ester compounds and aromatic alkenyl compounds, as the shell.

[0071] Examples of rubber components for component D include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, silicone-acrylic composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those in which hydrogen is added to the unsaturated bond portion. However, from the standpoint of environmental impact, rubber components that do not contain halogen atoms are preferred due to concerns about the generation of harmful substances during combustion. Furthermore, the glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower. For these reasons, butadiene rubber and acrylic-silicone-acrylic composite rubber are particularly preferred as rubber components. A composite rubber refers to rubber obtained by copolymerizing two types of rubber components or rubber polymerized to take an IPN structure in which the components are intertwined in an inseparable manner. In core-shell type graft polymers, the weight-average particle diameter of the core is preferably 240-300 nm, more preferably 250-290 nm, and even more preferably 260-280 nm. Better impact resistance may be achieved within the range of 240-300 nm. Furthermore, a bidispersion type particle size distribution with two peaks is desirable, and a bidispersion type with two peaks around 100 nm and 300 nm is particularly preferred, which may achieve better impact resistance than a monodispersion type with a single peak.

[0072] Aromatic vinyl compounds copolymerized with rubber components as the shell of a core-shell type graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate, while examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is especially preferable to include methacrylic acid esters such as methyl methacrylate as essential components, and it is even more preferable to omit aromatic vinyl components from the viewpoint of mechanical properties and flame retardancy. This is because the core-shell type graft polymer has excellent affinity with polycarbonate resin, resulting in a greater presence of rubber components in the resin, which more effectively exhibits the good impact resistance of the polycarbonate resin, and as a result, the impact resistance of the resin composition is improved. More specifically, it is preferable that the methacrylic acid ester is contained in an amount of 10% by weight or more, more preferably 15% by weight or more, in 100% by weight of the graft component (or 100% by weight of the shell in the case of a core-shell type polymer). The elastic polymer containing a rubber component with a glass transition temperature of 10°C or lower may be produced by any of the polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and the copolymerization method may be single-stage grafting or multi-stage grafting. It may also be a mixture with a copolymer consisting only of the graft component produced as a by-product during production. Furthermore, in addition to the general emulsion polymerization method, examples of polymerization methods include soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. In suspension polymerization, methods such as separately holding the aqueous phase and the monomer phase and accurately supplying both to a continuous disperser to control the particle size by the rotation speed of the disperser, and in a continuous production method, supplying the monomer phase to an aqueous liquid with dispersibility by passing it through a small-diameter orifice or porous filter with a diameter of several to tens of mm to control the particle size may be used.In the case of core-shell type graft polymers, the reaction may be a single step or a multi-step process for both the core and the shell.

[0073] Such polymers are commercially available and easily obtainable. For example, among those with butadiene rubber as the main component, there is the Metabren E series from Mitsubishi Chemical Corporation (for example, E-875A, whose shell component is mainly methyl methacrylate, and E-870A, whose shell component is mainly methyl methacrylate-styrene). Among those with acrylic rubber as the main component, there is the W series from Mitsubishi Chemical Corporation (for example, W-600A, whose shell component is mainly methyl methacrylate). Among those with silicone-acrylic composite rubber as the main component, there is the Metabren S series from Mitsubishi Chemical Corporation (for example, S-2001 and S-2030, whose shell component is mainly methyl methacrylate).

[0074] Furthermore, acrylic block copolymers can be cited as impact modifiers. The acrylic block copolymer used in the present invention is not particularly limited as long as it mainly consists of a copolymer having one or more polymer blocks obtained by polymerizing monomer components containing methacrylic acid and their derivatives. However, acrylic block copolymers containing polymer blocks containing acrylic acid ester monomer units and polymer blocks containing methacrylic acid ester monomer units are preferred, and it is more preferred that the content of polymer blocks containing methacrylic acid ester monomer units in the acrylic block copolymer is 25% by weight or more of the total blocks. If the content is less than 25% by weight, the impact resistance may decrease. The content is even more preferably 30% by weight or more, and particularly preferably 35% by weight or more. There is no particular upper limit to the content, but it is preferably 60% by weight or less.

[0075] Examples of acrylic acid ester monomers include methyl acrylate, ethyl acrylate, propyl acrylate, N-butyl acrylate, isobutyl acrylate, N-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, phenyl acrylate, and dimethylaminoethyl acrylate.

[0076] Examples of methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, N-butyl methacrylate, T-butyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, nonyl methacrylate, octadecyl methacrylate, dodecyl methacrylate, and 2-ethylhexyl methacrylate.

[0077] The content of component D is preferably 0.5 to 10 parts by weight, more preferably 0.8 to 8 parts by weight, and even more preferably 1 to 6 parts by weight, per 100 parts by weight of the resin component. If the content of component D is less than 0.5 parts by weight, the impact resistance may not be sufficiently improved, and if it exceeds 10 parts by weight, the fluidity or impact resistance may deteriorate.

[0078] (Other additives) (I) Phosphorus-based antioxidants other than component C The resin composition of the present invention may contain phosphorus-based antioxidants other than component C in addition to component C, to the extent that they do not impair the effects of the present invention.

[0079] Phosphorus-based antioxidants are not particularly limited, but examples include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and their esters, and tertiary phosphines, excluding component C. Such phosphorus-based antioxidants can be used not only individually but also in mixtures of two or more. Examples of phosphite compounds include trialkyl phosphites such as tridecyl phosphite, dialkyl monoaryl phosphites such as didecyl monophenyl phosphite, monoalkyldiaryl phosphites such as monobutyldiphenyl phosphite, triaryl phosphites such as triphenyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, and bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite. Examples of pentaerythritol phosphites include tol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, as well as cyclic phosphites such as 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite and 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl) phosphite. Examples of phosphate compounds include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenylmonoorthoxenyl phosphate, tributoxyethyl phosphate and diisopropyl phosphate, with triphenyl phosphate and trimethyl phosphate being preferred. Preferred examples of phosphonite compounds include tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite, with tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred.Such phosphonate compounds are preferably used in combination with phosphite compounds having aryl groups substituted with two or more alkyl groups. Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. Examples of tertiary phosphines include triphenylphosphine.

[0080] The content of phosphorus-based antioxidants other than component C is preferably 0.01 to 3.0 parts by weight, more preferably 0.05 to 2.0 parts by weight, and even more preferably 0.1 to 1.0 parts by weight, per 100 parts by weight of the resin component.

[0081] (II) Hindered phenol antioxidants The hindered phenol antioxidant used in the present invention is not particularly limited, and various compounds commonly used in resins can be used. Examples of such hindered phenol antioxidants include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxyphenyl Cybenzylphosphonate 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'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butyl Lyden-bis(4-methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terene Phthalates, 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) (d), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)iso Cyanurate, 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-Tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, Tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, Triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate Pionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane. Particularly preferred is 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0082] 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 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of the resin component. If the content is less than 0.05 parts by weight, the effect of suppressing thermal decomposition during processing may not be observed, and a decrease in mechanical properties may occur. If the content exceeds 1.0 part by weight, a decrease in mechanical properties may also occur.

[0083] It is preferable that either a phosphorus-based antioxidant other than component C or a hindered phenol-based antioxidant be included, and their combined use is even more preferable. In the case of combined use, it is preferable that 0.01 to 0.5 parts by weight of a phosphorus-based antioxidant other than component C and 0.01 to 0.5 parts by weight of a hindered phenol-based antioxidant be included per 100 parts by weight of the resin component.

[0084] (III) Heat stabilizers other than phosphorus-based and hindered phenol-based antioxidants The resin composition of the present invention may contain other heat stabilizers besides the phosphorus-based and hindered phenol-based antioxidants described above. Such heat stabilizers are preferably used in combination with these antioxidants, and particularly preferably in combination with both. 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 mixed with such compounds and various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. Such pre-mixed stabilizers can also be used in the present invention. 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 the resin component.

[0085] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is applied to rotational molding. 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 the resin component.

[0086] (IV) Release agent The resin composition of the present invention may contain a mold release agent, to the extent that it does not impede the effects of the present invention, for the purpose of improving productivity during molding and reducing distortion of molded products. Known mold release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, silicone compounds, fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax. Among these, fatty acid esters are preferred as mold release agents. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols of two or more hydric values. The number of carbon atoms in the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid esters of the present invention. On the other hand, aliphatic carboxylic acids are preferably having 3 to 32 carbon atoms, and particularly preferably aliphatic carboxylic acids having 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, eicosanic acid, and docosanic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids with 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are particularly preferred. Stearic acid and palmitic acid are especially preferred.The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural oils and fats, such as animal fats and fats represented by beef tallow and lard, and vegetable oils represented by palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Accordingly, in the production of fatty acid esters of the present invention, aliphatic carboxylic acids produced from such natural oils and fats, in the form of mixtures containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used. The fatty acid ester may be either a partial ester or a full ester. However, since partial esters usually have a high hydroxyl value and tend to induce decomposition of resins at high temperatures, full esters are more preferable. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These characteristics can be determined by the method specified in JIS K 0070.

[0087] The release agent content is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, per 100 parts by weight of the resin component.

[0088] (V) UV absorber The resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone-based absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridebenzophenone, 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.Benzotriazole derivatives include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-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)benzo Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as riazoles, 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 hydroxyphenyltriazine compounds include 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 cyclic iminoesters include 2,2'-P-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).

[0089] Examples of cyanoacrylate compounds 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.

[0090] Furthermore, the above-mentioned ultraviolet absorber may be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, by adopting the structure of a monomer compound that can be radically polymerized. Suitable examples of the above-mentioned 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 the (meth)acrylic acid ester.

[0091] The amount of ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 part by weight, per 100 parts by weight of the resin component.

[0092] (VI) Other resins The resin composition of the present invention may also contain other resins in small proportions, as long as the effects of the present invention are still achieved. Examples of such other resins include polypropylene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenolic resin, and fluororesin.

[0093] (VII) Dyes and Pigments The resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting diverse design properties. By incorporating fluorescent whitening agents or other fluorescent dyes that emit light, even better design effects can be imparted by utilizing the luminescent color. Furthermore, a resin composition that can be colored with a minute amount of dye and pigment and exhibits vivid color development can also be provided.

[0094] Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and do not degrade much during the molding process of polycarbonate resin.

[0095] Other dyes besides the bluing agents and fluorescent dyes mentioned above include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be further enhanced by incorporating metallic pigments to obtain better metallic colors. Suitable metallic pigments include those having a metal coating or metal oxide coating on various plate-shaped fillers.

[0096] The content of the dye / pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the resin component.

[0097] (VIII) Flame retardants The resin composition of the present invention can be made of various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins. More preferably, it is a silicone-based flame retardant consisting of (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 borate-based flame retardants, and metal stainate-based flame retardants), and (IV) silicone compounds. The compound blend used as a flame retardant not only improves flame retardancy but also brings about improvements in properties such as antistatic properties, fluidity, rigidity, and thermal stability, depending on the properties of each compound.

[0098] 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 the resin component. 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.

[0099] (IX) White pigment for high light reflectivity The resin composition of the present invention can be given a light-reflecting effect by incorporating a light-reflecting white pigment. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such light-reflecting white pigment is preferably 1 to 30 parts by weight, and more preferably 3 to 25 parts by weight, per 100 parts by weight of the resin component. Two or more light-reflecting white pigments can be used in combination.

[0100] (X) Carbon Black The resin composition of the present invention can be colored by incorporating carbon black. The raw material type and manufacturing method of the carbon black are not limited, and any conventionally known type can be used. For example, acetylene black, Ketjen black, channel black, and oil furnace black can be used. Furthermore, there are no restrictions on the average particle size, structure, and surface properties, and commercially available products can be appropriately selected and used.

[0101] The resin composition of the present invention preferably includes carbon black as a masterbatch with a styrene-based resin, and the styrene-based resin is preferably polystyrene resin or acrylonitrile-styrene resin. The masterbatch may also contain components other than carbon black and styrene-based resin. The method for producing the masterbatch is not particularly limited, but it is preferably a method of kneading the components containing carbon black and styrene-based resin using an extruder. The carbon black content in the masterbatch is preferably 20 to 60 parts by weight, more preferably 30 to 55 parts by weight, per 100 parts by weight of the masterbatch. The carbon black content is preferably 0.01 to 3 parts by weight, more preferably 0.05 to 2.5 parts by weight, and even more preferably 0.1 to 2 parts by weight, per 100 parts by weight of the resin component.

[0102] (XI) Other additives In addition, the resin composition of the present invention may contain small amounts of well-known additives to impart various functions to molded articles or improve their properties. These additives are added in normal amounts as long as they do not impair the objectives of the present invention. Examples of such additives include lubricants (e.g., PTFE particles), light diffusing agents (e.g., acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles), inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), antistatic agents, nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., fine particle titanium dioxide, fine particle zinc oxide), radical generators, infrared absorbers (heat absorbers), and photochromic agents.

[0103] (Method for preparing resin composition) The resin composition of the present invention is preferably prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, and extruder. As for the mixer, melt kneading using a twin-screw extruder is preferred, and if necessary, it is preferable to supply any component to the other molten components from a second supply port using a side feeder or the like. The resin extruded as described above is either directly cut to form pellets, or strands are formed and then these strands are cut with a pelletizer to form pellets. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellets can be general shapes such as cylinders, prismatics, and spheres, but more preferably cylinders. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0104] (Regarding molded articles made from the resin composition of the present invention) The resin composition of the present invention can be used to manufacture various products by injection molding pellets obtained by the method described above. 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 injection molding with 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. Furthermore, molding can be performed using either a cold runner system or a hot runner system. [Effects of the Invention]

[0105] The resin composition of the present invention has excellent impact resistance, fluidity, and moisture and heat resistance, making it suitable for use as a component in the automotive, office automation equipment, home appliance, and electrical / electronic fields, and is particularly suitable for automotive components, providing exceptional industrial benefits. [Modes for carrying out the invention]

[0106] The embodiments implemented by the present inventors represent a combination of preferred ranges of the above requirements, and representative examples are described in the following embodiments. Of course, the present invention is not limited to these embodiments. [Examples]

[0107] The present invention will be described in more detail below with reference to examples. Furthermore, unless otherwise specified, "parts" refers to "parts by weight," and "%" refers to "weight %." (1) Preparation of resin composition (1-1) Raw materials used (Component A) A-1: Polycarbonate resin powder with a molecular weight of 23,900 obtained by the following manufacturing method. A baffled reaction vessel was fitted with a three-stage, six-blade stirrer and a reflux condenser. 45.6 parts bisphenol A, 2.78 mol% p-tert-butylphenol relative to bisphenol A, 265 parts dichloromethane, and 200 parts water were added to the vessel, and nitrogen purging was performed to remove oxygen from the vessel. At this stage, the contents of the vessel were slightly less than 80% of its capacity. Next, approximately 80 parts of an aqueous solution containing 0.09 parts sodium hydrosulfite and 21.8 parts sodium hydroxide were added to the suspension, and bisphenol A was dissolved at 15°C. Under stirring, 23.35 parts phosgene were added to this mixture over 30 minutes. Then, 0.016 parts triethylamine (0.08 mol% relative to bisphenol A) was added, and the mixture was stirred for 60 minutes to terminate the reaction. The reaction mixture was then allowed to stand, and the organic phase was separated. To the obtained polycarbonate resin dichloromethane solution, methylene chloride was added to make a 14% by weight solution. Then, using a perforated centrifuge (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.), a 0.5% sodium hydroxide aqueous solution was supplied at a flow rate of 1,000 ml / min, and the organic phase at a flow rate of 1,000 ml / min, and the process was carried out at 3,500 rpm. After that, the organic phase was acidified with hydrochloric acid, and then washed repeatedly with water. When the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated to obtain polycarbonate resin powder.

[0108] (B component) B-1: ABS resin (TRINSEO SA MAGNUM A371 (product name); manufactured by bulk polymerization without the use of dispersants or emulsifiers) B-2: ABS resin (TRINSEO SA MAGNUM A156 (product name); manufactured by bulk polymerization without the use of dispersants or emulsifiers)

[0109] (C component) C-1: Zinc dialkyldithiophosphate (in chemical formula (4), R 1 ~R 4 Compounds containing an octyl group: O,O'-Dioctyldithiophosphate zinc (manufactured by Coraplus Pte. Ltd., product name LUBIMAX AW1188N) C-2 (Comparative Example): Phosphorus-based stabilizer (tris(2,4-di-tert-butylphenyl) phosphate, manufactured by Adeka Corporation, Adeka Stab 2112 (product name)) C-3 (Comparative Example): Phosphorus-based stabilizer (2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3,2]dioxaphosfepine, manufactured by Sumitomo Chemical Co., Ltd., Sumirizer GP (product name))

[0110] (D component) D-1: Acrylic block copolymer containing polymer blocks containing acrylic acid ester monomer units and polymer blocks containing methacrylic acid ester monomer units (Content of polymer blocks containing methacrylic acid ester monomer units in the total blocks: 50% by weight; manufactured by Kuraray Co., Ltd., Clarity LA4285) D-2: Acrylic block copolymer containing polymer blocks containing acrylic acid ester monomer units and polymer blocks containing methacrylic acid ester monomer units (Content of polymer blocks containing methacrylic acid ester monomer units in the total blocks: 30% by weight; manufactured by Kuraray Co., Ltd., Clarity LA2250) D-3: Butadiene-based core-shell graft polymer (a graft copolymer having a core-shell structure in which the core is mainly composed of butadiene rubber and the shell is mainly composed of methyl methacrylate (manufactured by Kaneka Corporation, product name: Kaneace M-724)) D-4: Butadiene-based core-shell type graft polymer (a graft copolymer having a core-shell structure in which the core is mainly composed of butadiene rubber and the shell is mainly composed of methyl methacrylate (manufactured by Kaneka Corporation, product name: Kaneace M-711))

[0111] (Other ingredients) E-1: Hindered phenol-based antioxidant (Adeka Stab AO-50 (product name), manufactured by Adeka Co., Ltd.) F-1: Release agent (fatty acid ester, manufactured by NOF Corporation, Unistar H-476-S (product name)) H-1: Carbon black masterbatch (Base resin: Acrylonitrile styrene resin, Carbon black ratio: 40% by weight, Manufactured by Resino Color Industries Co., Ltd., Product name: ABF-T-8961-MG) I-1: UV absorber (BASF's Chinuvin 234 (product name))

[0112] (2) Production of resin composition Each component listed in Tables 1 and 2 was mixed in the proportions indicated, and the mixture was supplied from the first feed port of the extruder. This mixture was then mixed in a V-type blender. Extrusion was performed using a 30 mmΦ vented twin-screw extruder (TEX30A-38.5BW-3V, manufactured by Japan Steel Works Ltd.), with a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa, to obtain pellets by melt-kneading. The extrusion temperature from the first feed port to the die section was 260°C.

[0113] (3) Evaluation items The following items were evaluated. The results are shown in Tables 1 and 2. (3-1) Liquidity The obtained pellets were dried at 110°C for 6 hours in a hot air circulating dryer, and then the melt volume rate (MVR) was measured using a semi-automatic melt indexer [(Toyo Seiki Seisakusho Co., Ltd. Semi-automatic melt indexer 2A)] at a temperature of 250°C and a load of 5000g. (3-2) Moisture and heat resistance The obtained pellets were subjected to moist heat treatment for 48 hours at 120°C and 100% RH using a pressure cooker tester TPC-412 (manufactured by ESPEC Corporation). After moist heat treatment, the pellets were dried in a hot air circulation dryer at 110°C for 6 hours, and the MVR was measured using the same method as in "(3-1) Fluidity," and the MVR increase rate was calculated using the following formula. A smaller MVR increase rate indicates superior resistance to moist heat. MVR increase rate (%) = [MVR of pellets after moist heat treatment / MVR of pellets before moist heat treatment] × 100 (3-3) Impact resistance The obtained pellets were dried in a hot air circulation dryer at 110°C for 6 hours, and then ISO bending test specimens were formed using an injection molding machine [EC130XII-4Y, manufactured by Toshiba Machine Co., Ltd.] under conditions of cylinder temperature 270°C and mold temperature 70°C. Using the obtained ISO bending test specimens, the low-temperature Charpy impact strength with a notch was measured in accordance with ISO 179 at -30°C.

[0114] [Table 1]

[0115] [Table 2]

Claims

1. A polycarbonate resin composition characterized by containing 0.001 to 1 part by weight of (C) an organic thiophosphate compound (component C) per 100 parts by weight of a resin component comprising (A) 40 to 90 parts by weight of polycarbonate resin (component A) and (B) 10 to 60 parts by weight of a copolymer obtained by polymerizing aromatic vinyl monomers and vinyl cyanide monomers (component B).

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

3. The polycarbonate resin composition according to claim 1 or 2, characterized in that component B is a copolymer produced by a bulk polymerization method that does not use dispersants and emulsifiers.

4. The polycarbonate resin composition according to claim 1 or 2, characterized in that it contains 0.5 to 10 parts by weight of an impact modifier other than component (component D)B, per 100 parts by weight of the resin component.

5. The polycarbonate resin composition according to claim 4, characterized in that component D is an acrylic block copolymer containing a polymer block containing acrylic acid ester monomer units and a polymer block containing methacrylic acid ester monomer units.

6. The polycarbonate resin composition according to claim 5, characterized in that component D is an acrylic block copolymer in which the content of polymer blocks containing methacrylic acid ester monomer units is 25% by weight or more of the total blocks.

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

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