Polycarbonate resin composition and molded article made thereof

Abstract

The present invention provides a polycarbonate resin composition which exhibits excellent fluidity and heat resistance and has a low coefficient of linear expansion.　The present invention is a polycarbonate resin composition which contains 5-45 parts by weight of a silicate mineral (C) (component C) relative to 100 parts by weight of a component constituted of 20-90 parts by weight of a polycarbonate resin (A) (component A) and 80-10 parts by weight of an ABS resin (B) (component B). The polycarbonate resin composition is characterized in that the content of SO4 2- in component B is at least 1 ppm and the content of PO4 3- is less than 1.5 ppm.

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article made thereof. More specifically, the present invention relates to a polycarbonate resin composition containing a specific ABS resin and a silicate mineral, which has excellent fluidity and heat resistance and a low coefficient of linear expansion, and to a molded article made thereof. [Background technology]

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

[0003] In the automotive field, exterior components such as garnishes and spoilers require materials with a low linear expansion coefficient in order to minimize gaps between components, and so resin compositions have been developed in which inorganic fillers such as talc and mica are blended with polycarbonate resin. However, the blending of inorganic fillers causes problems such as an increase in specific gravity, a decrease in impact resistance, and the occurrence of silver streaks due to a decrease in thermal stability, so there is a demand for improvements.

[0004] To meet these demands, a resin composition has been disclosed that exhibits a low coefficient of linear expansion and high impact resistance by blending a fluorine-containing resin and an olefin-maleic anhydride copolymer with a resin composition consisting of polycarbonate resin and talc (Patent Document 1). However, when an olefin-maleic anhydride copolymer is blended with a resin composition consisting of polycarbonate resin, ABS resin, and talc, the impact resistance is improved but the coefficient of linear expansion increases. Another resin composition has been disclosed that exhibits high impact resistance and excellent thermal stability by blending a specific alkoxysilane compound with a resin composition consisting of polycarbonate resin, styrene-based resin, and inorganic filler (Patent Document 2). However, because the coefficient of linear expansion depends solely on the amount of inorganic filler, further reductions in linear expansion have the problem of reduced impact resistance and increased specific gravity. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-158663 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-168822 Summary of the Invention [Problem to be solved by the invention]

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

[0007] As a result of extensive research conducted by the present inventors to solve the above problems, they discovered that by incorporating a predetermined amount of silicate mineral into a resin component consisting of a polycarbonate resin and a specific ABS resin, a resin composition having excellent fluidity and heat resistance and a low coefficient of linear expansion can be obtained, and thus completed the present invention.

[0008] That is, the present invention is as follows. 1. A polycarbonate resin composition comprising 20 to 90 parts by weight of a polycarbonate resin (component A) and 80 to 10 parts by weight of an ABS resin (component B) per 100 parts by weight of the components, and containing 5 to 45 parts by weight of a silicate mineral (component C). The content of SO4 in component B 2- is 1 ppm or more, and the content of PO4 3- is less than 1.5 ppm. A polycarbonate resin composition characterized by this. 2. The polycarbonate resin composition according to item 1 above, characterized by containing 0.001 to 1 part by weight of a phosphorus-based stabilizer (component D) per 100 parts by weight of the components composed of component A and component B. 3. The aromatic polycarbonate resin composition according to item 2 above, characterized in that component D is a phosphonic acid ester having an acid value of 0.01 to 0.30 mgKOH / g. 4. The thermoplastic resin composition according to item 3 above, characterized in that component D is triethyl phosphonoacetate. 5. A molded product made of the polycarbonate resin composition according to any one of items 1 to 4 above.

Effects of the Invention

[0009] The polycarbonate resin composition of the present invention is excellent in fluidity and heat resistance and has a low linear expansion coefficient. Therefore, it is widely useful in various fields such as housing equipment applications, building materials applications, daily necessities applications, infrastructure equipment applications, automotive applications, OA / EE applications, outdoor equipment applications, and other various fields. Therefore, the industrial effect of the present invention is extremely large.

Modes for Carrying Out the Invention

[0010] Hereinafter, the details of the present invention will be described. <Component A: Polycarbonate Resin> The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and examples of the reaction method include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0029] [ka]

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

[0031] [ka]

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

[0033] [ka]

[0034] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0035] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0036] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0037] [ka]

[0038] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0039] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0040] The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0041] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0042] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0043] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution.

[0044] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0045] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0046] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0047] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0048] As the solvent, various solvents inert to reactions, such as those used in the production of known polycarbonate resins, may be used alone or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0049] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0050] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0051] [ka]

[0052] (In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0053] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0054] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0055] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0056] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0057] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 Examples include trisphenols such as {1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, and among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0058] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0059] In some cases, the obtained polycarbonate-polydiorganosiloxane copolymer resin is subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of formula [ / c].

[0060] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification).

[0061] The average size of the polydiorganosiloxane domains in the polycarbonate-polydiorganosiloxane copolymer resin molded article is preferably in the range of 1 to 40 nm. This average size is more preferably 1 to 30 nm, and even more preferably 5 to 25 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be fully exhibited, while above the upper limit of this preferred range, impact resistance may not be stably exhibited. This provides a polycarbonate resin composition with excellent impact resistance and appearance.

[0062] The average domain size of the polydiorganosiloxane domain in the polycarbonate-polydiorganosiloxane copolymer resin molded product in the present invention was evaluated by the small angle X-ray scattering method (SAXS). The small angle X-ray scattering method is a method of measuring diffuse scattering and diffraction that occurs in a small angle region where the scattering angle (2θ) is less than 10°. In this small angle X-ray scattering method, when there are regions with different electron densities on the order of 1 to 100 nm in a substance, diffuse scattering of X-rays is measured due to the electron density difference. Based on this scattering angle and scattering intensity, the particle size of the measurement object is determined. In the case of a polycarbonate-polydiorganosiloxane copolymer resin having an aggregated structure in which polydiorganosiloxane domains are dispersed in the matrix of a polycarbonate polymer, diffuse scattering of X-rays occurs due to the electron density difference between the polycarbonate matrix and the polydiorganosiloxane domains. The scattering intensity I at each scattering angle (2θ) in the range where the scattering angle (2θ) is less than 10° is measured to measure the small angle X-ray scattering profile. Assuming that the polydiorganosiloxane domains are spherical domains and there is a variation in the particle size distribution, a simulation is performed using commercially available analysis software from a hypothetical particle size and a hypothetical particle size distribution model to obtain the average size of the polydiorganosiloxane domains. According to the small angle X-ray scattering method, the average size of the polydiorganosiloxane domains dispersed in the matrix of the polycarbonate polymer, which cannot be accurately measured by observation with a transmission electron microscope, can be measured accurately, simply, and with good reproducibility. The average domain size means the number average of the individual domain sizes.

[0063] The term "average domain size" used in connection with the present invention indicates a measured value obtained by measuring the 1.0 mm thick portion of the three-stage plate produced by the method described in the examples by such small angle X-ray scattering method. Also, analysis was performed using an isolated particle model that does not consider inter-particle interaction (inter-particle interference). <Component B: ABS resin> The resin composition of the present invention contains an ABS resin as component B. ABS resin is a copolymer obtained by graft polymerizing acrylonitrile and styrene onto polybutadiene. Styrene and α-methylstyrene are particularly preferred as styrenes. The proportion of the components grafted onto the polybutadiene is preferably 95 to 20% by weight, and particularly preferably 90 to 50% by weight, based on 100% by weight of the ABS resin component. Furthermore, the proportion of acrylonitrile is preferably 5 to 50% by weight and the proportion of styrene is preferably 95 to 50% by weight, based on 100% by weight of the total amount of acrylonitrile and styrene. Furthermore, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc., can be used as a part of the components graft polymerized onto the polybutadiene, and the content of these is preferably 15% by weight or less in the ABS resin component. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., can be used as needed in the reaction. In the ABS resin of the present invention, the polybutadiene particle size is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The polybutadiene particle size distribution may be either a single distribution or a distribution with two or more peaks. Furthermore, the morphology may be either a single-phase distribution or a salami structure formed by the inclusion of an occluded phase around the particles. It is well known that ABS resins contain copolymers of acrylonitrile and styrene that are not grafted to a diene rubber component. The ABS resin of the present invention may also contain free polymer components generated during the polymerization. The reduced viscosity (30°C) of such a copolymer of free acrylonitrile and styrene is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g. The proportion of grafted acrylonitrile and styrene relative to polybutadiene is preferably 20 to 200%, more preferably 20 to 70%, in terms of graft rate (% by weight).Such ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization methods, but emulsion polymerization is particularly preferred. Also, the copolymerization method may be single-stage copolymerization or multi-stage copolymerization. Further, a blend of a vinyl compound polymer obtained by separately copolymerizing acrylonitrile and styrene with the ABS resin obtained by such a production method can also be preferably used.

[0064] The content of component B is 10 to 80 parts by weight, preferably 15 to 70 parts by weight, more preferably 20 to 60 parts by weight, in 100 parts by weight in total of components A and B. When the content of component B is less than 10 parts by weight, the fluidity deteriorates, and when it exceeds 80 parts by weight, the heat resistance decreases.

[0065] The content of SO4 in component B 2- is 1 ppm or more, and the content of PO4 3- is less than 1.5 ppm. The content of SO4 2- is preferably 1.5 ppm or more, more preferably 2 ppm or more. On the other hand, the content of PO4 3- is preferably less than 1.0 ppm, more preferably less than 0.5 ppm. When the contents of SO4 2- and PO4 3- are out of the range, the linear expansion coefficient increases. Note that the upper limit of the content of SO4 2- is not particularly limited, but it is preferably 10 ppm or less, and the lower limit of the content of PO4 3- is also not particularly limited, but it is preferably 0.005 ppm or more. The contents of SO4 2- and PO4 3- are measured by the following procedure using an ion chromatograph device. After dissolving 1 g of an ABS resin sample in 100 ml of methylene chloride, 20 ml of water is added and shaken. Then, it is allowed to stand for a while, the aqueous layer is collected, and ion chromatographic measurement is carried out. For ion chromatographic measurement, DIONEX ion chromatograph: Integrion HPIC RF-IC manufactured by Dionex Corporation, Japan can be used. <Component C: Silicate mineral> The resin composition of the present invention contains a silicate mineral as component C. Commonly known silicate minerals such as wollastonite, kaolin, mica, and talc can be used as the silicate mineral. The silicate mineral used as component C of the present invention is a mineral composed of at least a metal oxide component and an SiO2 component, and orthosilicate, disilicate, cyclic silicate, and chain silicate are preferred. Silicate minerals are in a crystalline state, and the crystals can take various shapes, such as fibers and plates.

[0066] Silicate minerals may be any of the compounds of complex oxides, oxyacid salts (composed of ionic lattices), and solid solutions. Furthermore, complex oxides may be any of a combination of two or more single oxides, or a combination of two or more single oxides and oxyacid salts. Furthermore, solid solutions may be any of a solid solution of two or more metal oxides, or a solid solution of two or more oxyacid salts. Silicate minerals may also be hydrates. The form of water of crystallization in hydrates is Si-OH, which is hydrogen silicate ion, or hydroxide ion (OH) in relation to metal cations. - ) or enters the gaps in the structure as H2O molecules.

[0067] The silicate mineral may be an artificially synthesized product corresponding to a natural product, such as a silicate mineral obtained by various conventionally known synthesis methods, such as solid-state reaction, hydrothermal reaction, and ultra-high pressure reaction.

[0068] Specific examples of silicate minerals in each metal oxide component (MO) include the following: The notation in parentheses indicates the name of a mineral containing such a silicate mineral as a main component, and means that the compound in parentheses can be used as the exemplified metal salt.

[0069] Examples of rocks containing K2O include K2O·SiO2, K2O·4SiO2·H2O, K2O·Al2O3·2SiO2 (kalsilite), K2O·Al2O3·4SiO2 (leucite), and K2O·Al2O3·6SiO2 (orthoclase).

[0070] Minerals containing Na2O include Na2O·SiO2 and its hydrates, Na2O·2SiO2, 2Na2O·SiO2, Na2O·4SiO2, Na2O·3SiO2·3H2O, Na2O·Al2O3·2SiO2, Na2O·Al2O3·4SiO2 (jadeite), 2Na2O·3CaO·5SiO2, 3Na2O·2CaO·5SiO2, and Na2O·Al2O3·6SiO2 (albite).

[0071] Examples of compounds containing Li2O include Li2O·SiO2, 2Li2O·SiO2, Li2O·SiO2·H2O, 3Li2O·2SiO2, Li2O·Al2O3·4SiO2 (petalite), Li2O·Al2O3·2SiO2 (eucryptite), and Li2O·Al2O3·4SiO2 (spodumene).

[0072] Examples of compounds containing BaO include BaO·SiO2, 2BaO·SiO2, BaO·Al2O3·2SiO2 (celsian), and BaO·TiO2·3SiO2 (bentite).

[0073] Examples of materials containing CaO include 3CaO·SiO2 (alite, a cement clinker mineral), 2CaO·SiO2 (belite, a cement clinker mineral), 2CaO·MgO·2SiO2 (akermanite), 2CaO·Al2O3·SiO2 (gehlenite), a solid solution of akermanite and gehlenite (melilite), CaO·SiO2 (wollastonite (including both α- and β-types)), CaO·MgO·2SiO2 (diopside), CaO·MgO·SiO2 (magnesium olivine), 3CaO·MgO·2SiO2 (merwinite), CaO·Al2O3·2SiO2 (anorthite), 5CaO·6SiO2·5H2O (tobermorite, and others such as 5CaO·6SiO2·9H2O), and other tobermorite groups. These include loop hydrates, wollastonite group hydrates such as 2CaO·SiO2·H2O (hillebrandite), xonotlite group hydrates such as 6CaO·6SiO2·H2O (xonotlite), gyrolite group hydrates such as 2CaO·SiO2·2H2O (gyrolite), CaO·Al2O3·2SiO2·H2O (lawsonite), CaO·FeO·2SiO2 (hedengite), 3CaO·2SiO2 (chilcoanite), 3CaO·Al2O3·3SiO2 (grossula), 3CaO·Fe2O3·3SiO2 (andradite), 6CaO·4Al2O3·FeO·SiO2 (pleochroite), as well as clinozoisite, pimerite, allanite, vesuvianite, onoite, scotite, and augite.

[0074] Portland cement is another example of a silicate mineral containing CaO. There are no particular limitations on the type of Portland cement, and any type can be used, including normal, early-strength, ultra-early-strength, medium-heat, sulfate-resistant, and white. Furthermore, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component C.

[0075] Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0076] Examples of compounds containing ZnO include ZnO·SiO2, 2ZnO·SiO2 (troostite), and 4ZnO·2SiO2·H2O (hemimorphite).

[0077] Examples of materials containing MnO include MnO·SiO2, 2MnO·SiO2, CaO·4MnO·5SiO2 (rhodonite), and cosrite.

[0078] Examples of FeO-containing minerals include FeO·SiO2 (ferrosilite), 2FeO·SiO2 (ferroolivine), 3FeO·Al2O3·3SiO2 (almandine), and 2CaO·5FeO·8SiO2·H2O (tetactinocene).

[0079] Examples of materials that contain CoO include CoO·SiO2 and 2CoO·SiO2.

[0080] Materials containing MgO include MgO·SiO2 (steatite, enstatite), 2MgO·SiO2 (forsterite), 3MgO·Al2O3·3SiO2 (byrope), 2MgO·2Al2O3·5SiO2 (cordierite), 2MgO·3SiO2·5H2O, 3MgO·4SiO2·H2O (talc), 5MgO·8SiO2·9H2O (attapulgite), 4MgO·6SiO2·7H2O (sepiolite), and Examples include 3MgO·2SiO2·2H2O (chrysolite), 5MgO·2CaO·8SiO2·H2O (tremolite), 5MgO·Al2O3·3SiO2·4H2O (chlorite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), Na2O·3MgO·3Al2O3·8SiO2·H2O (lanthusite), as well as magnesium tourmaline, anthosphite, cummingtonite, vermiculite, and smectite.

[0081] Examples of materials that contain Fe2O3 include Fe2O3·SiO2.

[0082] Examples of materials that contain ZrO2 include ZrO2·SiO2 (zircon) and AZS refractories.

[0083] Examples of materials containing Al2O3 include Al2O3·SiO2 (sillimanite, andalusite, kyanite), 2Al2O3·SiO2, Al2O3·3SiO2, 3Al2O3·2SiO2 (mullite), Al2O3·2SiO2·2H2O (kaolinite), Al2O3·4SiO2·H2O (pyrophyllite), Al2O3·4SiO2·H2O (bentonite), K2O·3Na2O·4Al2O3·8SiO2 (nepheline), K2O·3Al2O3·6SiO2·2H2O (muscovite, sericite), K2O·6MgO·Al2O3·6SiO2·2H2O (phlogovite), as well as various zeolites, fluorphlogopite, and biotite.

[0084] Among the silicate minerals, mica, talc, and wollastonite are particularly suitable, and one or more silicate minerals containing talc are particularly preferred. (talc) Talc in the present invention is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO2·3MgO·2H2O. It is typically a scaly particle with a layered structure, and is composed of 56-65 wt% SiO2, 28-35 wt% MgO, and approximately 5 wt% H2O. Other minor components include 0.03-1.2 wt% Fe2O3, 0.05-1.5 wt% Al2O3, 0.05-1.2 wt% CaO, 0.2 wt% or less K2O, and 0.2 wt% or less Na2O. The particle size of the talc, as measured by the sedimentation method, is preferably in the range of 0.1-15 μm (more preferably 0.2-12 μm, even more preferably 0.3-10 μm, and particularly preferably 0.5-5 μm). Furthermore, the bulk density should be 0.5 (g / cm 3It is particularly preferable to use talc having a particle size of 0.05 mm or more as the raw material. The average particle size of talc refers to the D50 (median diameter of particle size distribution) measured by X-ray transmission, which is one of the liquid phase sedimentation methods. A specific example of an apparatus for performing such measurements is the Sedigraph 5100 manufactured by Micromeritics.

[0085] There are no particular limitations on the method for pulverizing talc from raw ore, and methods such as axial flow milling, annular milling, roll milling, ball milling, jet milling, and container rotation compression shear milling can be used. Furthermore, the talc after pulverization is preferably classified using various classifiers to achieve a uniform particle size distribution. There are no particular limitations on the classifier, and examples include impactor-type inertial force classifiers (such as variable impactors), Coanda effect-based inertial force classifiers (such as elbow jets), and centrifugal field classifiers (such as multi-stage cyclones, microplexes, dispersion separators, AccuCuts, turboclassifiers, turboplexes, micron separators, and super separators). Furthermore, talc is preferably in an agglomerated state for ease of handling, and methods for producing such talc include degassing and compression, and compression using a sizing agent. In particular, the method of degassing and compressing is preferred because it is simple and does not allow unnecessary sizing agent resin components to be mixed into the resin composition of the present invention. (mica) Mica with an average particle size of 10 to 100 μm as measured by microtrack laser diffraction is preferably used. More preferably, the average particle size is 20 to 50 μm. Mica with an average particle size of less than 10 μm may not provide sufficient rigidity improvement, while mica with an average particle size of more than 100 μm is not preferred because it may not provide sufficient rigidity improvement and may significantly reduce mechanical strength, such as impact resistance. Mica with a thickness of 0.01 to 1 μm as measured by electron microscope observation is preferred. A more preferred thickness is 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. Muscovite mica is preferred, and its Mohs hardness is approximately 3. Muscovite mica can achieve higher rigidity and strength than other micas, such as phlogopite, and thus achieves a more satisfactory solution to the problems of the present invention. The mica may be produced by either a dry or wet grinding method. Dry grinding is more common and less expensive, while wet grinding is effective for grinding mica into thinner, finer particles, which results in a greater effect of improving the rigidity of the resin composition. (Wollastonite) The fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1 to 3 μm. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. The fiber diameter is measured by observing the reinforcing filler with an electron microscope, determining the individual fiber diameters, and calculating the number-average fiber diameter from the measured values. An electron microscope is used because it is difficult to accurately measure the size of the target using an optical microscope. The fiber diameter is measured by randomly selecting fillers to be measured from the image obtained by electron microscope observation, measuring the fiber diameter near the center, and calculating the number-average fiber diameter from the obtained measured values. The magnification of the observation is approximately 1000x, and the number of measured fibers is 500 or more (600 or less is preferable for practical purposes). Meanwhile, the average fiber length is measured by observing the filler with an optical microscope, determining the individual lengths, and calculating the number-average fiber length from the measured values. Observation under an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap too much. Observation is carried out using a 20x objective lens, and the observed image is captured as image data on a CCD camera with approximately 250,000 pixels. The obtained image data is then analyzed using an image analyzer, and the fiber length is calculated using a program that determines the maximum distance between two points on the image data. Under these conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of fibers measured is 500 or more (600 or less is optimal for practical purposes).

[0086] In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the resin composition, it is preferable to use a magnetic separator to remove as much iron as possible from the raw ore and from the equipment worn during the grinding of the raw ore. After such magnetic separator treatment, the iron content in the wollastonite is preferably 0.5% by weight or less, calculated as Fe2O3.

[0087] The silicate minerals (more preferably mica, talc, wollastonite) are preferably not surface-treated, but may be surface-treated with various surface-treating agents such as silane coupling agents, higher fatty acid esters, and waxes. Further, it may be granulated into granules with a sizing agent such as various resins, higher fatty acid esters, and waxes.

[0088] The content of component C is 5 to 45 parts by weight, preferably 8 to 40 parts by weight, more preferably 10 to 35 parts by weight, based on 100 parts by weight of the component composed of component A and component B. When the content of component C is less than 5 parts by weight, a sufficient linear expansion coefficient cannot be obtained, and when it exceeds 45 parts by weight, extrusion becomes difficult. <Component D: Phosphorus-based stabilizer> The resin composition of the present invention preferably contains a phosphorus-based stabilizer as component D. As the phosphorus-based stabilizer, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters, and tertiary phosphine can be used, but phosphonic acid esters are preferred. As the phosphonic acid ester, 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 preferably 0.01 to 0.30 mgKOH / g, more preferably 0.01 to 0.20 mgKOH / g, and even 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 it is greater than 0.30 mgKOH / g, appearance defects such as silver may occur. The acid value was measured using a potentiometric titrator, and an alcohol solution of the phosphonic acid ester was titrated with a KOH alcohol solution.

[0089] The content of component D 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 the components A and B. If the content of component B is less than 0.001 part by weight, poor appearance such as silver may occur. On the other hand, since a sufficient effect is exhibited with 1 part by weight or less, if the content exceeds 1 part by weight, costs will increase. <Other ingredients> The resin composition of the present invention may also contain phenolic stabilizers, release agents, ultraviolet absorbers, core-shell type graft polymers, dyes and pigments (carbon black, titanium oxide, etc.), and the like. (i) Phenol-based stabilizers and other heat stabilizers The resin composition of the present invention can be blended with various heat stabilizers, excluding phosphorus-based stabilizers, including phenolic stabilizers such as hindered phenol compounds. Various compounds typically blended into resins can be used as the hindered phenol compounds. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di- tert-Butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene N-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-methyl 6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-trithiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5 -Triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate , tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris2[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-hydroxyphenyl)propionate hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferably used in the present invention. Particularly preferred is 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane. The above hindered phenol compounds can be used alone or in combination of two or more.

[0090] The content of the phenolic stabilizer is preferably 0.001 to 3.0 parts by weight, more preferably 0.01 to 2.0 parts by weight, and even more preferably 0.05 to 1.0 part by weight, relative to 100 parts by weight of the components A and B.

[0091] The polycarbonate resin composition of the present invention can also contain heat stabilizers other than the phosphorus-based stabilizers and phenol-based stabilizers described above. Such other heat stabilizers are preferably used in combination with either one of these stabilizers or antioxidants, and particularly preferably in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound mixed with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the same company is a suitable example. Such premixed 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, and more preferably 0.001 to 0.03 parts by weight, relative to 100 parts by weight of the components A and B.

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

[0093] The content of the release agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, and even more preferably 0.1 to 2.5 parts by weight, relative to 100 parts by weight of the components A and B. (iii) UV absorber The polycarbonate resin composition of the present invention may contain an ultraviolet absorber. Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridobenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Benzotriazoles include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as azole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer.Examples of hydroxyphenyltriazines include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol.Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazin-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazin-4-one).

[0094] Examples of cyanoacrylates include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0095] Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0096] The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and even more preferably 0.03 to 1.0 part by weight, relative to 100 parts by weight of the components A and B. (iv) Core-shell type graft polymer The polycarbonate resin composition of the present invention may contain a core-shell graft polymer. The core-shell graft polymer is a graft copolymer in which a rubber component having a glass transition temperature of 10°C or less is used as a core and one or more monomers selected from aromatic vinyl, vinyl cyanide, acrylic acid ester, methacrylic acid ester, and vinyl compounds copolymerizable therewith are copolymerized as a shell.

[0097] Examples of rubber components for core-shell graft polymers include butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, acrylic-silicone composite rubber, isobutylene-silicone composite rubber, isoprene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, nitrile rubber, ethylene-acrylic rubber, silicone rubber, epichlorohydrin rubber, fluororubber, and those with hydrogen added to the unsaturated bonds. However, due to concerns about the release of harmful substances during combustion, halogen-free rubber components are preferred in terms of environmental impact. The glass transition temperature of the rubber component is preferably -10°C or lower, more preferably -30°C or lower. Butadiene rubber, butadiene-acrylic composite rubber, acrylic rubber, and acrylic-silicone composite rubber are particularly preferred. Composite rubber refers to rubber obtained by copolymerizing two types of rubber components or rubber obtained by polymerizing them to form an IPN structure in which the components are inseparably intertwined. In the core-shell type graft polymer, the particle size of the core is preferably 0.05 to 0.8 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.15 to 0.5 μm, in terms of weight average particle size. If it is in the range of 0.05 to 0.8 μm, better impact resistance can be achieved.

[0098] Examples of aromatic vinyl compounds in the vinyl compounds copolymerized with the rubber component as the shell of the core-shell graft polymer include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene. Examples of acrylic esters include methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, and octyl acrylate. Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, and octyl methacrylate, with methyl methacrylate being particularly preferred. Among these, it is preferable to include a methacrylic ester such as methyl methacrylate as an essential component. This is because the core-shell graft polymer has excellent affinity with the aromatic polycarbonate resin, resulting in a larger amount of rubber component present in the resin, which more effectively utilizes the excellent impact resistance of the aromatic polycarbonate resin, resulting in improved impact resistance of the resin composition. More specifically, the methacrylic acid ester content is preferably 10% by weight or more, more preferably 15% by weight or more, based on 100% by weight of the graft component (100% by weight of the shell in the case of a core-shell polymer). Elastic polymers containing a rubber component with a glass transition temperature of 10°C or less may be produced by any of the following polymerization methods: bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. The copolymerization method may be either single-stage or multi-stage grafting. They may also be a mixture with a copolymer of only the graft component, which is a by-product of production. Polymerization methods include, in addition to standard emulsion polymerization, soap-free polymerization using an initiator such as potassium persulfate, seed polymerization, and two-stage swelling polymerization. In addition, suspension polymerization may involve separately maintaining the aqueous phase and the monomer phase and accurately feeding them into a continuous disperser, controlling the particle size by adjusting the rotation speed of the disperser. Alternatively, continuous production methods may involve feeding the monomer phase into an aqueous liquid with dispersibility through a small orifice or porous filter with a diameter of several to several tens of micrometers, thereby controlling the particle size. In the case of a core-shell type graft polymer, the reaction may be one-stage or multi-stage for both the core and the shell.

[0099] Such polymers are commercially available and easily available. For example, those containing butadiene rubber as the main component of the rubber component include Kane Ace M series manufactured by Kaneka Corporation (e.g., M-711 whose shell component is mainly composed of methyl methacrylate, M-701 whose shell component is mainly composed of methyl methacrylate and styrene), Metablen C series manufactured by Mitsubishi Rayon Co., Ltd. (e.g., C-223A whose shell component is mainly composed of methyl methacrylate and styrene), E series (e.g., E-870A whose shell component is mainly composed of methyl methacrylate and styrene), and Paraloid EXL series manufactured by Dow Chemical Co., Ltd. (e.g., EXL-2690 whose shell component is mainly composed of methyl methacrylate). Examples of products whose main component is acrylic rubber or butadiene-acrylic composite rubber include the W series (such as W-600A, whose shell component is primarily methyl methacrylate) and Dow Chemical's Paraloid EXL series (such as EXL-2390, whose shell component is primarily methyl methacrylate). Products whose main component is acrylic-silicone composite rubber include Mitsubishi Rayon's Metablen S-2501, whose shell component is primarily methyl methacrylate, and SX-200R, whose shell component is primarily acrylonitrile-styrene. (v) Other resins The polycarbonate resin composition of the present invention may contain other resins in small proportions as long as the effects of the present invention are achieved. Examples of such other resins include AES resin, ASA resin, polyester 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. (vi) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments, allowing for the provision of molded articles with diverse design possibilities. By blending in a fluorescent brightening agent or other fluorescent dye that emits light, it is possible to impart even better design effects by taking advantage of the emitted color. It is also possible to provide polycarbonate resin compositions that are colored with extremely small amounts of dyes and pigments and have vivid color development.

[0100] 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, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and are less susceptible to deterioration during molding and processing of polycarbonate resins.

[0101] Examples of dyes other than the bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Suitable metallic pigments include those having a metal coating or a metal oxide coating on various plate-like fillers.

[0102] The content of the dye or pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of the components A and B. (vii) Flame retardants The polycarbonate resin composition of the present invention can contain various compounds conventionally known as flame retardants for thermoplastic resins, particularly polycarbonate resins. Among these, preferred are (i) halogen-based flame retardants (e.g., brominated polycarbonate compounds), (ii) phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and phosphazene compounds), (iii) metal salt-based flame retardants (e.g., alkali (earth) metal organic sulfonates, borate metal salt-based flame retardants, and stannate metal salt-based flame retardants), and (iv) silicone-based flame retardants consisting of silicone compounds. The incorporation of the compounds used as flame retardants not only improves flame retardancy, but also, depending on the properties of each compound, improves antistatic properties, fluidity, rigidity, and thermal stability, among other things.

[0103] The content of the flame retardant is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 28 parts by weight, and even more preferably 0.08 to 25 parts by weight, relative to 100 parts by weight of the components consisting of Components A and B. If the content of the flame retardant is less than 0.01 part by weight, sufficient flame retardancy may not be obtained, whereas if it exceeds 30 parts by weight, mechanical properties may be significantly reduced. (viii) Highly reflective white pigment The polycarbonate resin composition of the present invention can be blended with a highly light-reflecting white pigment to impart a light-reflecting effect. Examples of such white pigments include zinc sulfide, zinc oxide, barium sulfate, calcium carbonate, and calcined kaolin. The content of such highly light-reflecting white pigment is preferably 1 to 30 parts by weight, more preferably 3 to 25 parts by weight, per 100 parts by weight of the components A and B. Two or more types of highly light-reflecting white pigments can be used in combination. (ix) Other additives In addition, the resin composition of the present invention can contain small amounts of known additives to impart various functions to molded articles or improve their properties. These additives can be added in conventional amounts as long as they do not impair the objectives of the present invention. Examples of such additives include sliding agents (e.g., PTFE particles), colorants (e.g., pigments such as carbon black, dyes), light diffusing agents (e.g., acrylic cross-linked particles, silicon cross-linked particles, ultrathin glass flakes, calcium carbonate particles), fluorescent dyes, inorganic phosphors (e.g., phosphors with aluminate as their host crystal), antistatic agents, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., titanium dioxide microparticles, zinc oxide microparticles), radical generators, infrared absorbers (heat ray absorbers), and photochromic agents. <Method for preparing polycarbonate resin composition> The polycarbonate resin composition of the present invention is prepared by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, or extruder. Melt-kneading using a twin-screw extruder is preferred as the mixer. If necessary, any component may be fed into the other melt-mixed components through a second feed port using a side feeder or the like. The extruded resin as described above is either directly cut and pelletized, or formed into strands, which are then cut and pelletized using a pelletizer. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The resulting pellets may have common shapes such as cylinders, prisms, and spheres, but cylinders are preferred. The diameter of the cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. The length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm. <Regarding molded articles made from the polycarbonate resin composition of the present invention> The polycarbonate resin composition of the present invention can be used to produce various products by injection molding the pellets obtained by the above-mentioned method. In such injection molding, molded articles can be obtained using not only conventional molding methods but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including injection of supercritical fluids), insert molding, in-mold coating molding, insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, either a cold runner system or a hot runner system can be used for molding.

[0104] The present inventors currently consider the best mode of the invention to be a combination of the preferred ranges of each of the above-mentioned requirements, and representative examples thereof are described in the following examples, although the present invention is not limited to these modes. [Example]

[0105] The present invention will be further explained below with reference to examples, which were evaluated by the following methods. (i) Linear expansion coefficient ISO tensile test specimens obtained by the method described below were annealed (dried at 110°C for 1 hour) and then cut into 5 mm square test specimens. The linear expansion coefficient of the test specimens was measured at a temperature rise rate of 2°C / min from -30°C to 80°C using a linear expansion coefficient measuring device "TMA4000SE" manufactured by NETZSCH, with the direction of measurement being the direction of resin flow during injection molding. The polycarbonate resin composition of the present invention exhibited a linear expansion coefficient reduction of 0.15 x 10 per part by weight of component C, calculated by the following formula: ―5 / ℃ or higher.

[0106] Reduction in linear expansion coefficient per part by weight of component C = (linear expansion coefficient of components consisting of components A and B - linear expansion coefficient of polycarbonate resin composition of the present invention) / content of component C (ii) Appearance of molded product After obtaining an ISO tensile test specimen using the method described below, the molding machine was stopped for 10 minutes under the same conditions as described below, and the molten resin was allowed to stagnate within the molding machine cylinder. 10 minutes after stopping the molding machine, molding was restarted and an ISO tensile test specimen was obtained from the second shot after remolding. The product before the molding machine was stopped was considered a continuous molded product, and the second shot after remolding was considered a retention molded product, and the appearance of each was evaluated visually. The evaluation was performed according to the following criteria. ◯: No defects in appearance were observed in either the continuous molded product or the retention molded product. △: No defects in appearance were observed in the continuous molded product, but defects in appearance such as silver spots were observed in the retention molded product. ×: Appearance defects such as silver spots were observed in both the continuous molded product and the retention molded product. (iii) Deflection temperature under load Using ISO flexural test specimens obtained by the following method, the deflection temperature under load (load 1.80 MPa) was measured in accordance with ISO 75-1 and ISO 75-2. The polycarbonate resin composition of the present invention must have a deflection temperature under load of 90°C or higher. (iv) Liquidity Using pellets obtained by the method described below, the Archimedes spiral flow length with a channel thickness of 2 mm and a channel width of 8 mm was measured using an injection molding machine [SE130EV-A manufactured by Sumitomo Heavy Industries, Ltd.]. The measurement was carried out at a cylinder temperature of 260°C, a mold temperature of 70°C, and an injection pressure of 98 MPa. The spiral flow length of the polycarbonate resin composition of the present invention must be 20 cm or more.

[0107] [Examples 1 to 19, Comparative Examples 1 to 8] A mixture consisting of the components listed in Tables 1 and 2, excluding the ABS resin (component B) and the silicate mineral (component C), was fed into the first feed port of an extruder. This mixture was obtained by blending in a V-type blender. The ABS resin (component B) and the silicate mineral (component C) were fed into the second feed port using a side feeder. The extrusion was performed using a 30 mm diameter vented twin-screw extruder (TEX30α-38.5BW-3V, manufactured by The Japan Steel Works, Ltd.) at a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa to obtain melt-mixed pellets. The extrusion temperature from the first feed port to the die was 260°C. The resulting pellets were dried in a hot air circulating dryer at 110°C for 6 hours and then molded into ISO flexural and tensile test specimens using an injection molding machine (cylinder temperature: 260°C, mold temperature: 60°C). The results are shown in Tables 1 and 2.

[0108] The following raw materials were used: (Component A) A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 19,800, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WX) A-2: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 22,400, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WP) A-3: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 16,000, made by a conventional method from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite CM-1000) (B component) B-1: ABS resin (SO4 2- Content 3.4ppm, PO4 3- Content 0.01 ppm, GA-704 (product name) manufactured by Nippon A&L Co., Ltd. B-2: ABS resin (SO4 2- Content 4.0ppm, PO4 3-Content 0.01 ppm, SXH-330 (product name) manufactured by Nippon A&L Co., Ltd. B-3: ABS resin (SO4 2- Content 3.2ppm, PO4 3- Content 0.01 ppm, Formosa Chemical & Fiber Corp. AF-3510 (product name) B-4: ABS resin (SO4 2- Content 0.02ppm, PO4 3- Content: 0.01 ppm, AT-05 (product name) manufactured by Nippon A&L Co., Ltd. B-5: ABS resin (SO4 2- Content 5.1ppm, PO4 3- Content 5.2ppm, manufactured by INEOS ABS CO LTD ABS250 (product name)) B-6: ABS resin (mixture of B-1 and B-4 (weight ratio 1:1) SO4 2- Content 1.7ppm, PO4 3- Content 0.01ppm) B-7: ABS resin (mixture of B-1 and B-5 (weight ratio 4:1) SO4 2- Content 3.7ppm, PO4 3- Content 1.1ppm) B-8: ABS resin (mixture of B-1 and B-4 (weight ratio 1:5) SO4 2- Content 0.6ppm, PO4 3- Content 0.01ppm) B-9: ABS resin (mixture of B-1 and B-5 (weight ratio 2:1) SO4 2- Content 4.0ppm, PO4 3- Content 1.8ppm) (C component) C-1: Talc (product name: Victorilite TK-RC, manufactured by Shokozan Mining Co., Ltd.) C-2: Mica (Kinseimatec Co., Ltd. GM-6 (product name)) C-3: Wollastonite (SH-1800 (product name) manufactured by Kinseimatec Co., Ltd.) (D component) D-1: Triethyl phosphonoacetate (JC-224 (product name) manufactured by Johoku Chemical Industry Co., Ltd., acid value 0.08 mg KOH / g) D-1: Triethyl phosphonoacetate (Solvay, acid value 0.39 mg KOH / g) (Other ingredients) E-1: Phenolic heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, Irganox 1076 (product name) manufactured by BASF Japan Ltd.) E-2: Butadiene-based core-shell graft polymer (a graft copolymer having a core-shell structure in which the core is 60 wt% butadiene rubber as the main component and the shell is 40 wt% methyl methacrylate as the main component, manufactured by Kaneka Corporation, Kane Ace M-711 (product name)) E-3: Polyethylene terephthalate resin (Teijin Limited, product name: TRN-MTJ) E-4: Carbon black (Koshigaya Chemical Co., Ltd.: ROYAL BLACK RB90003S (product name))

[0109] [Table 1]

[0110] [Table 2]

[0111] From the above table, it can be seen that by adding a specific ABS resin and a silicate mineral in predetermined amounts to a polycarbonate resin, a polycarbonate resin composition having excellent fluidity and heat resistance and a low coefficient of linear expansion can be obtained.

Claims

1. A polycarbonate resin composition comprising 100 parts by weight of a component consisting of 20 to 90 parts by weight of (A) a polycarbonate resin (component A) and 80 to 10 parts by weight of (B) an ABS resin (component B), and containing 5 to 45 parts by weight of (C) a silicate mineral (component C) and 0.001 to 1 part by weight of (D) triethylphosphonoacetate (component D) having an acid value of 0.01 to 0.30 mgKOH / g, wherein the SO ４ ２－ The content of PO is 1 ppm or more, and ４ ３－ A polycarbonate resin composition characterized in that the content of

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

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