Polycarbonate resin composition and molded article comprising same

Abstract

The present invention provides a polycarbonate resin composition having excellent fluidity, heat resistance, rigidity, and thermal stability, and a molded article comprising the same.　The present invention is a polycarbonate resin composition comprising: 100 parts by weight of a component comprising (A) 35.0-95.0 parts by weight of a polycarbonate resin (component A) and (B) 65.0-5.0 parts by weight of a styrene resin (component B); (C) 0.5-10.0 parts by weight of a polyester resin (component C); (D) 0.001-1.0 parts by weight of a phosphonic acid compound (component D) excluding phosphonic acid esters; and (E) 5.0-110.0 parts by weight of an inorganic filler (component E).

Description

Polycarbonate resin composition and molded article made thereof

[0001] The present invention relates to a polycarbonate resin composition and a molded article made therefrom that has excellent fluidity, heat resistance, rigidity, and thermal stability.

[0002] Polycarbonate resin is widely used industrially due to its excellent mechanical and thermal properties. However, polycarbonate resin has the drawback of poor fluidity and moldability due to its high melt viscosity. To improve the fluidity 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. In the automotive field, there is a demand for resin materials with high rigidity as a substitute for metal for exterior components to reduce weight. In response to this demand, resin compositions have been developed by blending polycarbonate resin with inorganic fillers such as talc and mica. Furthermore, in recent years, there has been an increase in the integration of parts to reduce assembly man-hours, and the development of large parts has become active. Therefore, in order to obtain good strength and molded appearance even in thin-walled, large parts, there is a growing demand for resins with excellent fluidity, rigidity, and thermal stability. In response to the above demands, for example, a resin composition consisting of polycarbonate resin, ABS resin, talc, and a phosphate compound has been disclosed. (Patent Document 1) However, in recent years, the increasing size of parts due to the integration of parts has led to longer molding cycle times, requiring even greater thermal stability of the resin, and this is still not satisfactory.

[0003] Japanese Patent Publication No. 2022-115666

[0004] In view of the above, the object of the present invention is to provide a polycarbonate resin composition and a molded article made therefrom that is excellent in fluidity, heat resistance, rigidity, and thermal stability.

[0005] The present inventors, after diligent study to solve the above problems, have found that the above problems can be solved by the following configuration, and have arrived at the present invention. 1. A polycarbonate resin composition comprising 100 parts by weight of a component consisting of (A) 35.0 to 95.0 parts by weight of polycarbonate resin (component A) and (B) 65.0 to 5.0 parts by weight of styrene-based resin (component B), with (C) 0.5 to 10.0 parts by weight of polyester resin (component C), (D) 0.001 to 1.0 parts by weight of phosphonic acid compounds excluding phosphonic acid esters (component D) and (E) 5.0 to 110.0 parts by weight of inorganic filler (component E). 2. The polycarbonate resin composition according to item 1 above, wherein component B is at least one styrene-based resin selected from the group consisting of acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and acrylonitrile-styrene-acrylate copolymer. 3. 1. A polycarbonate resin composition according to item 1 or 2, wherein component C is at least one polyester resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin. 4. A polycarbonate resin composition according to any one of items 1 to 3, wherein component D is a phosphonic acid compound represented by the following general formula (1).

[0006]

[0007] [In the above general formula (1), R is a group other than a group containing an ester bond.] 5. A polycarbonate resin composition according to any one of paragraphs 1 to 4 above, wherein component E is at least one inorganic filler selected from the group consisting of wollastonite, mica, and talc. 6. A molded article made from the polycarbonate resin composition according to any one of paragraphs 1 to 5 above. 7. A molded article according to paragraph 6 above, which is an automobile exterior part.

[0008] The polycarbonate resin composition of the present invention is highly fluid, heat-resistant, rigid, and thermally stable, making it widely useful in electrical and electronic applications, mechanical applications, office automation applications, automotive exterior parts, medical applications, and various other applications. In particular, it provides molded products that are extremely useful as automotive exterior parts, and the industrial effects achieved by the present invention are extremely significant.

[0009] Further details of the present invention will be described below.

[0010] <Component A: Polycarbonate Resin> The polycarbonate resin used in this invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of reaction methods include interfacial polycondensation, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0011] Typical examples of divalent phenols used here include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)methane, bis{(4-hydroxy-3,5-dimethyl)phenyl}methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A), 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, and 2,2-bis{(4- 2,2-bis{(3-isopropyl-4-hydroxy)phenyl}propane, 2,2-bis{(4-hydroxy-3-phenyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-4-isopropylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis{(4-hydroxy-3-methyl)phenyl}fluorene, α,α'-bis(4-hydroxyphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxyphenyl)-m-di Examples include sopropylbenzene, α,α'-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, and 4,4'-dihydroxydiphenyl ester, which can be used individually or in combination of two or more.

[0012] Among these, homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)-3-methylbutane, 2,2-bis(4-hydroxyphenyl)-3,3-dimethylbutane, 2,2-bis(4-hydroxyphenyl)-4-methylpentane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferred. In particular, homopolymers of bisphenol A and copolymers of 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis{(4-hydroxy-3-methyl)phenyl}propane, or α,α'-bis(4-hydroxyphenyl)-m-diisopropylbenzene are preferred.

[0013] Carbonyl halides, carbonate esters, or haloformates can be used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0014] When producing polycarbonate resin by reacting the above-mentioned divalent phenol with a carbonate precursor by interfacial polycondensation or melt transesterification, catalysts, end-terminating agents, antioxidants for the divalent phenol, etc., may be used as needed. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, or a polyester carbonate resin copolymerized with an aromatic or aliphatic bifunctional carboxylic acid, or a mixture of two or more of the obtained polycarbonate resins.

[0015] The reaction methods such as the interfacial polymerization method, melt transesterification method, solid-phase transesterification method of carbonate prepolymer, and ring-opening polymerization method of cyclic carbonate compound, which are the methods for producing the polycarbonate resin of the present invention, are well-known methods in various literatures and patent gazettes. Although the viscosity-average molecular weight of the polycarbonate resin is not specified, if it is less than 1×10 ４ the high-temperature properties and the like will deteriorate, and if it exceeds 4×10 ４ the molding processability will deteriorate. Therefore, it is preferably 1×10 ４ to 4×10 ４ , more preferably 1.4×10 ４ to 3×10 ４ , and even more preferably 1.6×10 ４ to 2.5×10 ４ .

[0016] Two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix a polycarbonate resin whose viscosity-average molecular weight is outside the above range.

[0017] The viscosity-average molecular weight referred to in the present invention is obtained by inserting the specific viscosity (η ＳＰ ) of a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C into the following formula. η ＳＰ / c = [η] + 0.45×[η] ２ c (where [η] is the intrinsic viscosity) [η] = 1.23×10 －４ M ０.８３ c = 0.7

[0018] Branched polycarbonate resin can also be used as the polycarbonate resin of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1,1-bis(4 Examples include trisphenols such as hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0019] In branched polycarbonate resins, the structural units derived from polyfunctional aromatic compounds are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols and those derived from such polyfunctional aromatic compounds. Furthermore, especially in the case of melt transesterification, branched structural units may be produced as a side reaction, but the amount of such branched structural units is also preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of structural units derived from divalent phenols. １ It can be calculated by H-NMR measurement.

[0020] Examples of aromatic difunctional carboxylic acids include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbendicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfisoisophthalic acid, and ethylene-bis-p-benzoic acid. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as adipic acid, sebacic acid (decandioic acid), azelaic acid, dodecandioic acid, tetradecandioic acid, octadecandioic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. Alicyclic diols are more preferred as bifunctional alcohols, and examples include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

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

[0022] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin of the present invention. The polycarbonate-polydiorganosiloxane copolymer resin is preferably a copolymer resin prepared by copolymerizing a divalent phenol represented by the following general formula (2) and a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (4).

[0023]

[0024] [In the above general formula (2), R １ and R ２Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups of each, they may be the same or different. e and f are integers from 1 to 4, and W is at least one group selected from the group consisting of a single bond or a group represented by the general formula (3) below.

[0025]

[0026] [In the above general formula (3), R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R １９ and R ２０ Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.

[0027]

[0028] [In the above general formula (4), R ３ , R ４, R ５ , R ６ , R ７ and R ８ Each is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R ９ and R １０ Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0029] Examples of divalent phenols (I) represented by general formula (2) 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, and 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-H hydroxyphenyl)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.

[0030] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, 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, which has excellent strength and good durability, is the most suitable. These may be used individually or in combination of two or more.

[0031] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (4), the following compounds are preferably used, for example.

[0032]

[0033] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosiliculation reaction of olefinic unsaturated carbon-carbon bonded phenols, preferably vinylphenol, 2-allylphenol, isopropenylphenol, and 2-methoxy-4-allylphenol, to the ends of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, and (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes are particularly preferred. Hydroxyaryl-terminated polydiorganosiloxanes (II) preferably have a molecular weight distribution (Mw / Mn) of 3 or less. Furthermore, in order to exhibit excellent low outgassing and low-temperature impact resistance during high-temperature molding, such molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this suitable range is exceeded, the amount of outgassing during high-temperature molding increases, and the low-temperature impact resistance may be poor.

[0034] Furthermore, in order to achieve high impact resistance, the degree of diorganosiloxane polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is appropriately set to 10 to 300. This degree of diorganosiloxane 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 characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, and above the upper limit of this preferred range, appearance defects appear.

[0035] The polydiorganosiloxane content in the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. More preferably, the polydiorganosiloxane content is 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. Above the lower limit of this preferred range, excellent impact resistance and flame retardancy are obtained, and below the upper limit of this preferred range, a stable appearance less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and polydiorganosiloxane content are: １ It can be calculated by H-NMR measurement.

[0036] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more may be used.

[0037] Furthermore, to the extent that it does not interfere with the present invention, other comonomers other than the above-mentioned divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in a range of 10% by weight or less relative to the total weight of the copolymer.

[0038] In the present invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by the reaction of divalent phenol(I) and a carbonate ester-forming compound in a mixture of a water-insoluble organic solvent and an alkaline aqueous solution. When generating the divalent phenol(I) oligomer, the entire amount of divalent phenol(I) used in the method of the present invention may be converted into an oligomer at once, or a portion of it may be added as a reaction raw material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and it is not necessary to add it if it is not needed.

[0039] The method of this oligomer formation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0040] The proportion of ester-forming compounds used can be adjusted as appropriate, taking into account the stoichiometric ratio (equivalent) of the reaction. Furthermore, when using gaseous ester-forming compounds such as phosgene, a suitable method is to bubble them into the reaction system.

[0041] Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. The proportion of acid binder used should be determined appropriately, taking into account the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slightly excess amount of acid binder relative to the number of moles of divalent phenol(I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0042] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0043] There are no particular restrictions on the reaction pressure for oligomer formation; it can be atmospheric pressure, pressurized pressure, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization is often exothermic, it is desirable to cool the reaction with water or ice. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out in 0.2 to 10 hours. The pH range for the oligomer formation reaction is the same as that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0044] In this invention, a mixed solution containing an oligomer of divalent phenol (I) having terminal chloroformate groups is obtained, and while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (4), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, is added to the divalent phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0045]

[0046] [In the above general formula (4), R ３ , R ４ , R ５ , R ６ , R ７ and R ８ Each is independently a hydrogen atom, a C1-C12 alkyl group, or a C6-C12 substituted or unsubstituted aryl group, R ９ and R １０ Each of the following is independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0047] When carrying out an interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into consideration the stoichiometric ratio (equivalent) of the reaction. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, or mixtures thereof. Specifically, when adding a portion of the hydroxyaryl-terminated polydiorganosiloxane (II) or the divalent phenol (I) as described above as a post-added monomer to this reaction step, it is preferable to use 2 equivalents or an excess amount of alkali relative to the total number of moles of the post-added divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0048] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0049] In such polymerization reactions, end-terminating agents or molecular weight modifiers are commonly used. Examples of end-terminating agents include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenols, p-tert-butylphenol, p-cumylphenol, and tribromophenol, as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, alkyl hydroxybenzoates, hydroxyphenylalkylates, and alkyl etherphenols. The amount used is preferably in the range of 100 to 0.5 moles, more preferably 50 to 2 moles, per 100 moles of all divalent phenolic compounds used, and it is naturally possible to use two or more compounds in combination.

[0050] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added.

[0051] The reaction time for such polymerization is preferably 30 minutes or more, and more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0052] Branching agents can be used in combination with the above-mentioned divalent phenolic compounds to form branched polycarbonate-polydiorganosiloxanes. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, and 4-{4-[1 Examples include trisphenols such as 1-bis(4-hydroxyphenyl)ethyl]benzene-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred. The proportion of polyfunctional compounds in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, even more preferably 0.01 to 0.8 mol%, and particularly preferably 0.05 to 0.4 mol%, of the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. １ It can be calculated by H-NMR measurement.

[0053] <Component B: Styrene Resin> The polycarbonate resin composition of the present invention contains a styrene resin as component B. This styrene resin has good moldability and moderate heat resistance, making it a preferred thermoplastic resin for maintaining a balance of these properties.

[0054] The styrene-based resin is preferably a polymer obtained by copolymerizing a polymer or copolymer of an aromatic vinyl compound, or, if necessary, one or more vinyl monomers and rubbery polymers that can copolymerize with these.

[0055] Styrene is particularly preferred as the aromatic vinyl compound. Other vinyl monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds and (meth)acrylic acid ester compounds. Acrylonitrile is a particularly preferred vinyl cyanide compound, and methyl methacrylate is a particularly preferred (meth)acrylic acid ester compound.

[0056] Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth)acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and α,β-unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid.

[0057] Examples of rubbery polymers copolymerizable with the above aromatic vinyl compounds include polybutadiene, polyisoprene, diene copolymers (e.g., random and block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, and copolymers of alkyl (meth)acrylates and butadiene), copolymers of ethylene and α-olefins (e.g., random and block copolymers of ethylene-propylene, random and block copolymers of ethylene-butene), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers), and copolymers of ethylene and aliphatic vinyls (e.g., Examples include ethylene-vinyl acetate copolymers, ethylene-propylene-nonconjugated diener polymers (e.g., ethylene-propylene-hexadiene copolymers), acrylic rubbers (e.g., polybutyl acrylate, poly(2-ethylhexyl acrylate), copolymers of butyl acrylate and 2-ethylhexyl acrylate, etc.), and silicone rubbers (e.g., polyorganosiloxane rubber, IPN-type rubber consisting of a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component; that is, rubber having a structure in which the two rubber components are intertwined so that they cannot be separated, and IPN-type rubber consisting of a polyorganosiloxane rubber component and a polyisobutylene rubber component).

[0058] Specific examples of the styrene-based resins mentioned above include polystyrene resin, HIPS resin, MS resin, ABS resin (acrylonitrile-styrene-butadiene copolymer), AS resin (acrylonitrile-styrene copolymer), AES resin, ASA resin (acrylonitrile-styrene-acrylate copolymer), MBS resin, MABS resin, MAS resin, SMA resin, (hydrogenated) styrene-butadiene-styrene copolymer resin, and (hydrogenated) styrene-isoprene-styrene copolymer resin. The notation "(hydrogenated)" means that both unhydrogenated and hydrogenated resins are included. Here, MS resin refers to a copolymer resin mainly composed of methyl methcrete and styrene, AES resin refers to a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber and styrene, MABS resin refers to a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene and styrene, MAS resin refers to a copolymer resin mainly composed of methyl methacrylate, acrylic rubber and styrene, and SMA resin refers to a copolymer resin mainly composed of styrene and maleic anhydride (MA).

[0059] Furthermore, such styrene-based resins may have high stereoregularity, such as syndiotactic polystyrene, due to the use of catalysts such as metallocene catalysts during their manufacture. In addition, depending on the circumstances, polymers and copolymers with a narrow molecular weight distribution, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and radical living polymerization may also be used.

[0060] Among these, AS resin, ABS resin, and ASA resin are preferred. It is also possible to use a mixture of two or more styrene-based resins.

[0061] The AS resin used in this invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Acrylonitrile is particularly preferred as the vinyl cyanide compound. Styrene and α-methylstyrene are preferred as the aromatic vinyl compound. In the AS resin, when the total is 100% by weight, the vinyl cyanide compound is preferably 5 to 50% by weight, more preferably 15 to 35% by weight, and the aromatic vinyl compound is preferably 95 to 50% by weight, more preferably 85 to 65% by weight. Furthermore, other copolymerizable vinyl compounds described above can be mixed with these vinyl compounds, and it is preferable that their content is 15% by weight or less of the AS resin components. In addition, various conventionally known initiators, chain transfer agents, etc., can be used in the reaction as needed.

[0062] The AS resin may be manufactured by bulk polymerization, suspension polymerization, or emulsion polymerization, but bulk polymerization is preferred. The copolymerization method may also be one-stage copolymerization or multi-stage copolymerization. The reduced viscosity of the AS resin is preferably 0.2 to 1.0 dl / g, and more preferably 0.3 to 0.5 dl / g. The reduced viscosity was measured using an Ubbelohde viscometer at 30°C after accurately weighing 0.25 g of the AS resin and dissolving it in 50 ml of dimethylformamide over 2 hours. The viscometer used has a solvent flow time of 20 to 100 seconds. Reduced viscosity is measured using the solvent flow time (t ０ The reduced viscosity (η) is calculated from the η and the time (t) the solution flows down using the following formula: ｓｐ / C) = {(t / t ０ ) - 1} / 0.5

[0063] If the reduced viscosity is less than 0.2 dl / g, the impact may decrease, and if it exceeds 1.0 dl / g, the fluidity may deteriorate.

[0064] The ABS resin used in this invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerizing a diene-based rubber component with a vinyl cyanide compound and an aromatic vinyl compound, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. As the diene-based rubber component that forms this ABS resin, for example, rubber with a glass transition temperature of -30°C or lower, such as polybutadiene, polyisoprene, and styrene-butadiene copolymer, is used, and its proportion is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and particularly preferably 10 to 30% by weight, of 100% by weight of the ABS resin component. Acrylonitrile is particularly preferred as the vinyl cyanide compound grafted onto the diene-based rubber component. Styrene and α-methylstyrene are particularly preferred as the aromatic vinyl compound grafted onto the diene-based rubber component. The proportion of the component grafted onto the diene-based rubber component is preferably 95 to 20% by weight, and more preferably 50 to 90% by weight, of 100% by weight of the ABS resin component. Furthermore, it is preferable that the vinyl cyanide compound accounts for 5 to 50% by weight and the aromatic vinyl compound for 95 to 50% by weight, based on 100% by weight of the total amount of the vinyl cyanide compound and aromatic vinyl compound. In addition, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc., can be mixed and used as part of the components grafted onto the above diene-based rubber component, and it is preferable that the content of these is 15% by weight or less of the ABS resin component. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., can be used in the reaction as needed.

[0065] In the ABS resin of the present invention, the rubber particle diameter is preferably 0.1 to 5.0 μm, more preferably 0.15 to 1.5 μm, and even more preferably 0.2 to 0.8 μm. The distribution of such rubber particle diameters can be either a single distribution or one with two or more peaks. Furthermore, in terms of morphology, the rubber particles may form a single phase, or they may have a salami structure due to the inclusion of an occluded phase around the rubber particles.

[0066] Furthermore, it is well known that ABS resin contains vinyl cyanide compounds and aromatic vinyl compounds that are not grafted onto the diene rubber component, and the ABS resin of the present invention may also contain free polymer components generated during such polymerization. The reduced viscosity of the copolymer consisting of such free vinyl cyanide compounds and aromatic vinyl compounds is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g, as determined by the method described above at 30°C.

[0067] Furthermore, the proportion of grafted vinyl cyanide compounds and aromatic vinyl compounds is preferably 20 to 200%, and more preferably 20 to 70%, in terms of graft rate (weight%) relative to the diene rubber component.

[0068] The ABS resin may be manufactured by any of the following methods: bulk polymerization, suspension polymerization, or emulsion polymerization, but bulk polymerization is particularly preferred. Representative examples of such bulk polymerization methods include the continuous bulk polymerization method (the so-called Toray method) described in Chemical Engineering, Vol. 48, No. 6, p. 415 (1984), and the continuous bulk polymerization method (the so-called Mitsui Toatsu method) described in Chemical Engineering, Vol. 53, No. 6, p. 423 (1989). Any of these ABS resins can be suitably used as the ABS resin of the present invention. The copolymerization method may also be a single-step or multi-step copolymerization. Furthermore, a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with the ABS resin obtained by such a manufacturing method can also be suitably used. ABS resins that do not contain lubricants (such as ethylenebisstearamide (EBS)) exhibit superior flame retardancy.

[0069] The ASA resin used in this invention is a mixture of a thermoplastic graft copolymer, obtained by graft polymerizing an acrylic rubber component with a vinyl cyanide compound and an aromatic vinyl compound, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. The acrylic rubber component that forms this acrylonitrile-styrene-acrylate copolymer is mainly composed of alkyl acrylate, and examples include rubbers such as 2-ethylhexyl acrylate and n-butyl acrylate. It is preferable that such alkyl acrylate is present in an amount of 50% by weight or more of 100% by weight of the acrylic rubber component.

[0070] The proportion of such acrylic rubber component is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, and even more preferably 10 to 30% by weight, of 100% by weight of the acrylonitrile styrene acrylate copolymer.

[0071] Acrylonitrile is particularly preferred as the vinyl cyanide compound. Styrene and α-methylstyrene are preferred as the aromatic vinyl compound. In the acrylonitrile-styrene copolymer, when the total is 100% by weight, the vinyl cyanide compound is preferably 5 to 50% by weight, more preferably 15 to 35% by weight, and the aromatic vinyl compound is preferably 95 to 50% by weight, more preferably 85 to 65% by weight. Furthermore, other copolymerizable vinyl compounds described above can be mixed with these vinyl compounds, and it is preferable that their content is 15% by weight or less of the acrylonitrile-styrene copolymer component. In addition, various conventionally known initiators, chain transfer agents, etc., can be used in the reaction as needed.

[0072] Such acrylonitrile-styrene-acrylate copolymers may be produced by bulk polymerization, suspension polymerization, or emulsion polymerization, but bulk polymerization is preferred. The copolymerization method may also be either single-step copolymerization or multi-step copolymerization.

[0073] Styrene resins with reduced alkali (earth) metal content are more preferable in terms of good thermal stability and hydrolysis resistance. The alkali (earth) metal content in styrene resins is preferably less than 100 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, and particularly preferably less than 10 ppm. From this point of view, AS resins and ABS resins produced by bulk polymerization are suitably used. Furthermore, in relation to such good thermal stability and hydrolysis resistance, when emulsifiers are used in AS resins and ABS resins, the emulsifiers are preferably sulfonates, and more preferably alkyl sulfonates. When a coagulant is used, sulfuric acid or an alkaline earth metal salt of sulfuric acid is preferred.

[0074] The content of component B is 5.0 to 65.0 parts by weight, preferably 10.0 to 60.0 parts by weight, and more preferably 15.0 to 55.0 parts by weight, per 100 parts by weight of the component consisting of components A and B. If the content is less than 5.0 parts by weight, sufficient fluidity cannot be obtained, and if it exceeds 65.0 parts by weight, the heat resistance deteriorates.

[0075] <Component C: Polyester Resin> The polycarbonate resin composition of the present invention contains a polyester resin as component C. Examples of polyester resins include polyethylene terephthalate resin, polybutylene terephthalate resin, and aromatic polyarylate resin, with polyethylene terephthalate resin and polybutylene terephthalate resin being preferred.

[0076] The polyethylene terephthalate resin and polybutylene terephthalate resins suitably used in the present invention are those in which, of the dicarboxylic acid and diol components forming the polyester, 70 mol% or more of the 100 mol% dicarboxylic acid component is an aromatic dicarboxylic acid, more preferably 90 mol% or more, and most preferably 99 mol% or more is an aromatic dicarboxylic acid. Examples of these dicarboxylic acids include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenidicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfisoisophthalic acid, ethylene-bis-p-benzoic acid, and the like. These dicarboxylic acids can be used individually or in combination of two or more. In addition to the above-mentioned aromatic dicarboxylic acids, the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin of the present invention can be copolymerized with aliphatic dicarboxylic acid components in an amount of less than 30 mol%. Specific examples include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, and tetrabromobisphenol A-bis(2-hydroxyethyl ether). These can be used individually or in combination of two or more. Preferably, the divalent phenol content in the diol component is 30 mol% or less.

[0077] The polyethylene terephthalate resin and polybutylene terephthalate resin used in the present invention are produced by conventional methods, in which the dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc., and the by-product water or lower alcohol is discharged from the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, etc., and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. In addition, the present invention can also use compounds such as manganese, zinc, calcium, and magnesium, which are used in the transesterification reaction, a known pre-step of polycondensation, and it is also possible to deactivate such catalysts with a phosphoric acid or phosphorous acid compound, etc., after the transesterification reaction is completed and then perform polycondensation. Furthermore, the polyethylene terephthalate resin and polybutylene terephthalate resin can be produced using either a batch method or a continuous polymerization method.

[0078] The molecular weight of the polyethylene terephthalate resin and polybutylene terephthalate resin of the present invention is not particularly limited, but it is preferably 0.4 to 1.5, and more preferably 0.5 to 1.2, intrinsic viscosity measured at 25°C with o-chlorophenol as the solvent.

[0079] Furthermore, the amount of terminal carboxyl groups in the polyethylene terephthalate resin and polybutylene terephthalate resin used in the present invention is preferably 5 to 75 eq / ton, more preferably 5 to 70 eq / ton, and even more preferably 7 to 65 eq / ton.

[0080] The aromatic polyarylate resins suitably used in the present invention are obtained from aromatic dicarboxylic acids or their derivatives and divalent phenols or their derivatives. Any aromatic dicarboxylic acid that reacts with divalent phenols to give a satisfactory polymer can be used in the preparation of the aromatic polyarylate resin, and one or more types may be used in combination.

[0081] Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. Mixtures thereof may also be used.

[0082] Specific examples of divalent phenol components include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl, and hydroquinone. These divalent phenol components are para-substituted compounds, but other isomers may also be used, and ethylene glycol, propylene glycol, neopentyl glycol, etc. may be used in combination with the divalent phenol components.

[0083] Among the above, preferred aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component consists of terephthalic acid and isophthalic acid, and the divalent phenol component consists of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9 / 1 to 1 / 9 (molar ratio), and particularly desirable is 7 / 3 to 3 / 7 in terms of melt processability and performance balance.

[0084] Other representative aromatic polyarylate resins include those in which the aromatic dicarboxylic acid component is terephthalic acid and the divalent phenol component is bisphenol A and hydroquinone. The ratio of bisphenol A to hydroquinone is preferably bisphenol A / hydroquinone = 50 / 50 to 70 / 30 (molar ratio), more preferably 55 / 45 to 70 / 30, and even more preferably 60 / 40 to 70 / 30.

[0085] In the present invention, the viscosity-average molecular weight of the aromatic polyarylate resin is preferably in the range of 7,000 to 100,000 from the perspective of physical properties and extrusion processability. Furthermore, the aromatic polyarylate resin can be polymerized using either the interfacial polycondensation method or the transesterification reaction method.

[0086] The content of component C is 0.5 to 10.0 parts by weight, preferably 0.75 to 8.0 parts by weight, and more preferably 1.0 to 6.0 parts by weight, per 100 parts by weight of the component consisting of components A and B. If the content of component B exceeds 10.0 parts by weight, the heat resistance deteriorates, and if it is less than 0.5 parts by weight, the thermal stability deteriorates.

[0087] <Component D: Phosphonic acid compounds excluding phosphonic acid esters> The polycarbonate resin composition of the present invention contains phosphonic acid compounds excluding phosphonic acid esters as component D. If a compound other than these compounds is used as component D, the thermal stability deteriorates. Component D is preferably a phosphonic acid compound represented by the following formula (1).

[0088]

[0089] [In the above general formula (1), R is a group other than a group containing an ester bond.] Examples of phosphonic acid compounds include phenylphosphonic acid, methylphosphonic acid, ethylphosphonic acid, vinylphosphonic acid, decylphosphonic acid, benzylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and nitrilotris (methylenephosphonic acid), among which phenylphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, and nitrilotris (methylenephosphonic acid) are preferred.

[0090] The content of component D is 0.001 to 1.0 parts by weight, preferably 0.01 to 0.7 parts by weight, more preferably 0.05 to 0.5 parts by weight, and even more preferably 0.08 to 0.4 parts by weight, per 100 parts by weight of the component consisting of components A and B. Thermal stability deteriorates when the content of component D is less than 0.001 parts by weight and when it exceeds 1 part by weight. <Component E: Inorganic filler> The polycarbonate resin composition of the present invention contains an inorganic filler as component E. The inorganic filler is preferably a silicate mineral. As the silicate mineral, commonly known silicate minerals such as wollastonite, kaolin, mica, and talc can be used. The silicate mineral used as component E of the present invention contains at least a metal oxide component and SiO ２ These are minerals composed of various components, with orthosilicates, disilicates, cyclic silicates, and chain silicates being preferred. Silicate minerals exist in a crystalline state, and their crystal shapes can also take various forms, such as fibrous or plate-like structures.

[0091] Silicate minerals may be complex oxides, oxyacids (consisting of an ionic lattice), or solid solutions. Furthermore, complex oxides may be combinations of two or more single oxides or combinations of a single oxide and two or more oxyacids. Similarly, solid solutions may be solid solutions of two or more metal oxides or solid solutions of two or more oxyacids. Silicate minerals may also be hydrates. In hydrates, the form of water of crystals may be Si-OH as a hydrogen silicate ion, or hydroxide ions (OH) relative to the metal cation. － ) which enters ionically and H in the gaps of the structure ２It can be in any form as an oxygen molecule.

[0092] Silicate minerals can also be synthesized from natural products. These synthetic compounds can be obtained using various conventionally known methods, such as solid-state reactions, hydrothermal reactions, and ultra-high-pressure reactions.

[0093] Specific examples of silicate minerals in each metal oxide component (MO) are listed below. The names in parentheses indicate minerals, etc., whose main component is such silicate mineral, and mean that the compounds in parentheses can be used as example metal salts.

[0094] K ２ As for substances that contain O as an ingredient, K ２ O.Sio ２ _K ２ O・4SiO ２ ・H ２ O, K ２ O. Al ２ O ３ ・2SiO ２ (Calcilight), K ２ O. Al ２ O ３ 4SiO ２ (White dragonite) and K ２ O. Al ２ O ３ 6SiO ２ Examples include (orthoclase).

[0095] Na ２ As for substances that contain O as one of their components, Na ２ O.Sio ２ and its hydrate, Na ２ O・2SiO ２ , 2Na ２ O.Sio ２ Na ２ O・4SiO ２ Na ２ O・3SiO ２ 3H ２ O, Na ２ O. Al ２ O ３ ・2SiO ２ Na ２O·Al ２ O ３ ·4SiO ２ (jadeite pyroxene), 2Na ２ O·3CaO·5SiO ２ 、3Na ２ O·2CaO·5SiO ２ 以及Na ２ O·Al ２ O ３ ·6SiO ２ (albite) and the like can be mentioned.

[0096] Li ２ O contained in its components includes Li ２ O·SiO ２ 、2Li ２ O·SiO ２ 、Li ２ O·SiO ２ ·H ２ O、3Li ２ O·2SiO ２ 、Li ２ O·Al ２ O ３ ·4SiO ２ (petalite), Li ２ O·Al ２ O ３ ·2SiO ２ (eucryptite) and Li ２ O·Al ２ O ３ ·4SiO ２ (spodumene) and the like can be mentioned.

[0097] BaO contained in its components includes BaO·SiO ２ 、2BaO·SiO ２ 、BaO·Al ２ O ３ ·2SiO ２ (celsian) and BaO·TiO ２ ·3SiO ２ (bentorite) and the like can be mentioned.

[0098] CaO contained in its components includes 3CaO·SiO ２ (alite of cement clinker mineral), 2CaO·SiO ２(Belite, a cement clinker mineral), 2CaO・MgO・2SiO ２ (Okermanite), 2CaO·Al ２ O ３ SiO ２ (Gehlenite), solid solution of okermaite and gehlenite (Mellilite), CaO・SiO ２ (Wollastonite (including both α- and β- forms)), CaO・MgO・2SiO ２ (Diopside), CaO・MgO・SiO ２ (Magnesium olivine), 3CaO・MgO・2SiO ２ (Melwinite), CaO・Al ２ O ３ ・2SiO ２ (Anorthite), 5CaO・6SiO ２ ・5H ２ O (tobermorite, other 5CaO・6SiO ２ 9H ２ Tobermorite group hydrates such as 0, 2CaO・SiO ２ ・H ２ Wollastonite group hydrates such as O (finbrandite), 6CaO・6SiO ２ ・H ２ Zonotlite group hydrates such as O (zonotlite), 2CaO・SiO ２ ・2H ２ Gyrolite group hydrates such as O (gyrolite), CaO・Al ２ O ３ ・2SiO ２ ・H ２ O (lawsonite), CaO・FeO・2SiO ２ (Hedenite), 3CaO・2SiO ２ (Chillcore Night), 3CaO・Al ２ O ３ 3SiO ２ (Grossula), 3CaO・Fe ２ O ３ 3SiO ２ (Andradite), 6CaO・4Al ２ O ３ FeO・SiO ２Examples include (pleochroite), as well as clinozoisite, rhodochroite, charnet, vesuvianite, onoite, scoutite, and augite.

[0099] Furthermore, Portland cement can be cited as a silicate mineral containing CaO as a component. The type of Portland cement is not particularly limited; any type can be used, including ordinary, rapid-hardening, ultra-rapid-hardening, medium-heat-resistant, sulfate-resistant, and white types. Additionally, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component E.

[0100] Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0101] Substances containing ZnO include ZnO·SiO ２ , 2ZnO・SiO ２ (Trowstite) and 4ZnO・2SiO ２ ・H ２ Examples include O (hemipolar ore).

[0102] Substances containing MnO include MnO·SiO ２ , 2MnO·SiO ２ , CaO・4MnO・5SiO ２ Examples include rhodonite and causerite.

[0103] Substances containing FeO include FeO·SiO ２ (ferrosilite), 2FeO・SiO ２ (Iron olivine), 3FeO・Al ２ O ３ 3SiO ２ (Almandine) and 2CaO・5FeO・8SiO ２ ・H ２ Examples include O (Tetsuaktinoseite).

[0104] Substances containing CoO as a component include CoO·SiO ２ and 2CoO·SiO ２ These are some examples.

[0105] Substances containing MgO include MgO·SiO ２ (Steatite, Enstatite), 2MgO・SiO ２ (Forsterite), 3MgO・Al ２ O ３ 3SiO ２ (Virope), 2MgO・2Al ２ O ３ 5SiO ２ (cordierite), 2MgO・3SiO ２ ・5H ２ O, 3MgO・4SiO ２ ・H ２ O (talc), 5MgO・8SiO ２ 9H ２ O (attapulgite), 4MgO・6SiO ２ 7H ２ O (sepiolite), 3MgO・2SiO ２ ・2H ２ O (chrysolite), 5MgO・2CaO・8SiO ２ ・H ２ O (Persicate), 5MgO・Al ２ O ３ 3SiO ２ 4H ２ O (chlorite), K ２ O・6MgO・Al ２ O ３ 6SiO ２ ・2H ２ O (phlogobite), Na ２ O・3MgO・3Al ２ O ３ 8SiO ２ ・H ２ Examples include O (lansene), as well as magnesium tourmaline, orthozoite, cumingtonite, vermiculite, and smectite.

[0106] Fe ２ O ３ As for those containing Fe as an ingredient, ２ O ３ SiO ２ These are some examples.

[0107] ZrO ２ As for substances that contain it as an ingredient, ZrO２ SiO ２ Examples include zircon and AZS refractories.

[0108] Al ２ O ３ As for those containing Al as an ingredient, ２ O ３ SiO ２ (Sillimanite, Andalusite, Kyanite), 2Al ２ O ３ SiO ２ Al ２ O ３ 3SiO ２ , 3Al ２ O ３ ・2SiO ２ (Mullite), Al ２ O ３ ・2SiO ２ ・2H ２ O (kaolinite), Al ２ O ３ 4SiO ２ ・H ２ O (pyrophyllite), Al ２ O ３ 4SiO ２ ・H ２ O (bentonite), K ２ O-3Na ２ O・4Al ２ O ３ 8SiO ２ (Kasumi stone), K ２ O・3Al ２ O ３ 6SiO ２ ・2H ２ O (mascobite, sericite), K ２ O・6MgO・Al ２ O ３ 6SiO ２ ・2H ２ Examples include phlogobite (O), various zeolites, fluorinated phlogopite, and biotite.

[0109] Among the silicate minerals mentioned above, mica, talc, and wollastonite are particularly preferred, and it is even more preferable that one or more silicate minerals containing talc are used.

[0110] <Talc> In this invention, talc is chemically composed of hydrated magnesium silicate, and is generally known by the chemical formula 4SiO ２ 3MgO・2H ２ It is represented by O, and is usually a flaky particle with a layered structure, and its composition is SiO ２ 56-65% by weight of H, 28-35% by weight of MgO, H ２ It consists of approximately 5% by weight of oxygen. Other small amounts of Fe are also included. ２ O ３ 0.03 to 1.2% by weight, Al ２ O ３ 0.05 to 1.5% by weight of , CaO 0.05 to 1.2% by weight, K ２ O is 0.2% by weight or less, Na ２ It contains 0.2% by weight or less of oxygen. The particle size of the talc is preferably in the range of 0.1 to 15 μm (more preferably 0.2 to 12 μm, even more preferably 0.3 to 10 μm, and particularly preferably 0.5 to 5 μm) as measured by the sedimentation method. Furthermore, the bulk density is 0.5 g / cm³. ３ It is particularly preferable to use talc of a certain size or larger as the raw material. The average particle size of the talc is defined as D50 (median diameter of the particle size distribution) measured by X-ray transmission, which is one of the liquid-phase sedimentation methods. A specific example of a device for performing such a measurement is the Sedigraph 5100 manufactured by Micromeristics.

[0111] Furthermore, there are no particular restrictions on the method used to crush talc from its raw material, and methods such as axial flow milling, annular milling, roll milling, ball milling, jet milling, and container-rotating compression shear milling can be used. In addition, the crushed talc is preferably classified using various classifiers to ensure a uniform particle size distribution. There are no particular restrictions on the classifiers, 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, AccuCut, turboclassifiers, turboplexes, micron separators, and super separators). Furthermore, the talc is preferably in an aggregated state for ease of handling, and methods for achieving this include degassing and compression, and compression using a sizing agent. The degassing and compression method is particularly preferable because it is simple and does not involve mixing unnecessary sizing agent resin components into the polycarbonate resin composition of the present invention.

[0112] <Mica> Mica with an average particle size of 10 to 100 μm, as measured by microtrac laser diffraction, is preferably used. More preferably, the average particle size is 20 to 50 μm. If the average particle size of the mica is less than 10 μm, the improvement effect on rigidity may not be sufficient, and even if it exceeds 100 μm, the improvement in rigidity may not be sufficient, and the decrease in mechanical strength such as impact properties may be significant. Mica with a thickness of 0.01 to 1 μm, as measured by observation with an electron microscope, is preferably used. More preferably, the thickness is 0.03 to 0.3 μm. The aspect ratio can preferably be 5 to 200, more preferably 10 to 100. Furthermore, muscovite mica is preferred for use, and its Mohs hardness is approximately 3. Compared to other mica such as phlovite, muscovite mica can achieve higher rigidity and strength, and solves the problems of the present invention at a better level. Furthermore, the mica may be manufactured by either a dry grinding method or a wet grinding method. While dry grinding is less expensive and more common, wet grinding is effective in grinding mica into thinner and finer particles, resulting in a greater improvement in the rigidity of the polycarbonate resin composition.

[0113] <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 higher. The upper limit of the aspect ratio is 30 or less. Here, the fiber diameter is determined by observing the reinforcing filler with an electron microscope, determining the diameter of each individual fiber, and calculating the number-average fiber diameter from these measurements. An electron microscope is used because it is difficult to accurately measure the size of the target level with an optical microscope. To determine the fiber diameter, randomly select fillers to be measured from the image obtained by observing with an electron microscope, measure the fiber diameter near the center, and calculate the number-average fiber diameter from the obtained measurements. The observation magnification is approximately 1000x, and the number of measurements is 500 or more (600 or less is preferable for practical purposes). On the other hand, the average fiber length is measured by observing the filler with an optical microscope, determining the length of each individual fiber, and calculating the number-average fiber length from these measurements. Observation using an optical microscope begins with preparing a sample in which the fillers are dispersed so that they do not overlap too much. The observation is performed under conditions of a 20x objective lens, and the observed image is captured as image data in a CCD camera with approximately 250,000 pixels. The obtained image data is then analyzed using an image analysis device, and the fiber length is calculated using a program that determines the maximum distance between two points in the image data. Under these conditions, the size of one pixel corresponds to a length of 1.25 μm, and the measurement is performed on 500 or more fibers (600 or fewer is preferable for practical purposes).

[0114] In order to fully reflect the inherent whiteness of the wollastonite of the present invention in the polycarbonate resin composition, it is preferable to remove as much iron as possible from the raw ore and from the iron mixed in due to wear of the equipment when crushing the raw ore using a magnetic separator. Through such magnetic separator treatment, the iron content in the wollastonite is reduced to Fe ２ O ３ It is preferable that the amount is 0.5% by weight or less when converted to this ratio.

[0115] Silicate minerals (more preferably mica, talc, or wollastonite) are preferably untreated, but may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes. Furthermore, they may be granulated with various resins, higher fatty acid esters, and waxes to form granules.

[0116] The content of component E is 5.0 to 110.0 parts by weight, preferably 7.0 to 80.0 parts by weight, more preferably 12.5 to 50.0 parts by weight, and particularly preferably 15.0 to 35.0 parts by weight, based on 100 parts by weight of the component consisting of components A and B. If the content of component E is less than 5.0 parts by weight, the rigidity deteriorates, and if it exceeds 110.0 parts by weight, the thermal stability and fluidity deteriorate.

[0117] <Other Components> <Impact Modifier> The polycarbonate resin composition of the present invention may contain impact modifiers other than the styrene resin which is component B, to the extent that the effects of the present invention are exhibited. Examples of impact modifiers include core-shell type composite rubbers made of acrylic polymers and polyorganosiloxanes in which vinyl monomers are graft polymerized, butadiene rubber-containing methyl methacrylate graft copolymer rubbers, and acrylic rubbers, which are commercially available as "Metablen S2001" and "Metablen S2030" from Mitsubishi Chemical Corporation, "KaneAce M711" and "KaneAce M724" from Kaneka Corporation, and "Clarity LA2250" and "Clarity LA4285" from Kuraray Corporation.

[0118] <Phenol-based stabilizers and other heat stabilizers> The polycarbonate resin composition of the present invention can be blended with various heat stabilizers, including phenol-based stabilizers such as hindered phenol compounds. Various compounds that are normally blended into resins can be used as hindered phenol compounds. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, cinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 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'-dimethylenebis(6-α-methylbenzyl-p-cresol), 2,2'-ethylide 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-methyl6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5 - Triazine, N,N'-Hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-Tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-Trimethyl-2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, Tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxyphenyl) Droxy-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-2,4Examples 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.

[0119] 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 parts by weight, per 100 parts by weight of the component consisting of component A and component B.

[0120] The polycarbonate resin composition of the present invention may also contain other heat stabilizers other than the phosphonic acid compounds and phenolic stabilizers mentioned above, excluding the phosphonic acid esters. Such other heat stabilizers are preferably used in combination with either of these stabilizers or antioxidants, and are particularly preferably used 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 Japanese Patent Application Publication No. 7-233160). Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and these compounds can be used. Furthermore, stabilizers obtained by mixing these compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. In the present invention, such pre-mixed stabilizers can also be used. The content of the lactone-based stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the component consisting of component A and component B.

[0121] 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 polycarbonate resin composition is applied to rotational molding. The content of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of the component consisting of components A and B.

[0122] <Release Agents> The polycarbonate resin composition of the present invention may further contain known release agents such as fatty acid esters, polyolefin waxes, silicone compounds, fluorine compounds (fluorine oils such as polyfluoroalkyl ethers), paraffin waxes, and beeswax, for the purpose of improving productivity during molding and improving the dimensional accuracy of molded products.

[0123] Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol with two or more carbon atoms. The number of carbon atoms in the alcohol is preferably 3 to 32, more preferably 5 to 30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Among these, saturated aliphatic carboxylic acids are preferred. Fatty acid esters are preferred in that the full ester (full ester) exhibits excellent thermal stability at high temperatures. The acid value of the fatty acid ester is preferably 20 or less (may take substantially 0). The hydroxyl value of the fatty acid ester is preferably in the range of 0.1 to 30. Furthermore, the iodine value of the fatty acid ester is preferably 10 or less (may take substantially 0). These properties can be determined by the method specified in JIS K0070.

[0124] Examples of polyolefin waxes include ethylene homopolymers, homopolymers or copolymers of α-olefins having 3 to 60 carbon atoms, or copolymers of ethylene and α-olefins having 3 to 60 carbon atoms, with molecular weights of 1,000 to 10,000. Such molecular weights are number-average molecular weights measured on a standard polystyrene basis by GPC (gel permeation chromatography). The upper limit of such number-average molecular weights is more preferably 6,000, and even more preferably 3,000. The number of carbon atoms in the α-olefin component of the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Preferred polyolefin waxes are ethylene homopolymers or copolymers of ethylene and α-olefins having 3 to 60 carbon atoms. The proportion of α-olefins having 3 to 60 carbon atoms is preferably 20 mol% or less, more preferably 10 mol% or less. A commercially available product known as polyethylene wax is preferably used.

[0125] <UV absorber> The polycarbonate resin composition of the present invention may contain a small amount of UV absorber within the range that exhibits the effects of the present invention. Examples of benzophenone compounds 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-sulfoxytrihydridebenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Examples of benzotriazole derivatives include 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, and 2-(2-hydroxy-5-tert-octylphenyl)benzo Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as riazoles, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazine-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with a vinyl monomer copolymerizable with the monomer.Examples of hydroxyphenyltriazine compounds include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-butyloxyphenol. Furthermore, examples include compounds in which the phenyl group of the above example compounds has been replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol. Examples of cyclic iminoesters include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-(4,4'-diphenylene)bis(3,1-benzoxazine-4-one), and 2,2'-(2,6-naphthalene)bis(3,1-benzoxazine-4-one).

[0126] Examples of cyanoacrylate compounds include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0127] Furthermore, the above-mentioned ultraviolet absorber may also be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or a photostable monomer having a hindered amine structure with a monomer such as an alkyl (meth)acrylate, by adopting the structure of a monomer compound that can be radically polymerized. Suitable examples of the above-mentioned ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of the (meth)acrylic acid ester.

[0128] <Colorants> The polycarbonate resin composition of the present invention can further contain various colorants within the range that exhibits the effects of the present invention, and can provide molded articles that exhibit diverse design properties. Examples of dyes and pigments used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, phthalocyanine dyes, carbon black, and the like.

[0129] The polycarbonate resin composition of the present invention can also be enriched with metallic pigments to obtain better metallic colors. Aluminum powder is a suitable metallic pigment. Furthermore, by incorporating fluorescent whitening agents or other fluorescent dyes that emit light, an even better design effect can be achieved by utilizing the luminescent color. Examples of fluorescent dyes (including fluorescent whitening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiaidine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because they have good heat resistance and do not degrade during the molding process of the polycarbonate resin.

[0130] <Other Resins> In the polycarbonate resin composition of the present invention, resins other than components A, B, and C may be used in small proportions, as long as the effects of the present invention are exhibited. Examples of such other resins include polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, and fluororesins.

[0131] <Other Additives> In addition, the polycarbonate resin composition of the present invention may contain small amounts of well-known additives to impart various functions to molded articles or improve their properties. These additives are added in normal amounts as long as they do not impair the objectives of the present invention. Examples of such additives include lubricants (e.g., PTFE particles), flame retardants (e.g., phosphorus-based flame retardants, metal salt flame retardants), light diffusing agents (e.g., acrylic crosslinked particles, silicon crosslinked particles, ultrathin glass flakes, calcium carbonate particles), inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), antistatic agents, nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (e.g., fine-particle titanium dioxide, fine-particle zinc oxide), radical generators, infrared absorbers (heat absorbers), and photochromic agents. <Method for Manufacturing the Polycarbonate Resin Composition> The polycarbonate resin composition of the present invention can be manufactured by any method. For example, it can be manufactured by kneading in a single-screw or multi-screw extruder. Polycarbonate resin, styrene resin, polyester resin, phosphonic acid compounds (excluding phosphonic acid esters), inorganic fillers, and other components may be mixed together, or some of the components may be mixed first, and then mixed and kneaded with the remainder. The polycarbonate resin composition obtained in this way can be molded into automotive parts, electrical and electronic components, etc., by various known methods, such as injection molding and extrusion molding.

[0132] The present inventor's current best-in-class embodiment of the invention is a combination of the preferred ranges of the above requirements, and a representative example is described in the following examples. Of course, the present invention is not limited to these embodiments.

[0133] The polycarbonate resin composition of the present invention will be described in detail below based on examples.

[0134] <Materials Used> <Component A: Polycarbonate Resin> A-1: ​​L-1225WX (product name) (manufactured by Teijin Limited, viscosity-average molecular weight 19700, linear polycarbonate resin) A-2: L-1225WP (product name) (manufactured by Teijin Limited, viscosity-average molecular weight 22400, linear polycarbonate resin) A-3: W-0052 (product name) (manufactured by Teijin Limited, viscosity-average molecular weight 19700, polycarbonate-polydiorganosiloxane copolymer resin) A-4: PC-WB101A (product name) (manufactured by NINGBO TOP CENTRAL NEW MATERIAL, viscosity-average molecular weight 23500, recycled branched polycarbonate resin) A-5: PC116A (product name) (manufactured by Ningbo Asahi Hongyu Technology Co., Ltd., viscosity average molecular weight 20500, recycled linear polycarbonate resin) A-6: PC-50S (product name) (manufactured by Ningbo Asahi Hongyu Technology Co., Ltd., viscosity average molecular weight 15200, recycled linear polycarbonate resin)

[0135] <Component B: Polystyrene resin> B-1: MAGNUM A156 (product name) (manufactured by TRINSEO S.A., ABS resin produced by bulk polymerization) B-2: GA-704 (product name) (manufactured by Nippon A&L Co., Ltd., ABS resin produced by emulsion polymerization) B-3: 777K (product name) (manufactured by INEOS, ASA resin) B-4: BS-207 (product name) (manufactured by Nippon A&L Co., Ltd., AS resin)

[0136] <Component C: Polyester Resin> C-1: TRN-8550FF (product name) (manufactured by Teijin Limited, IV = 0.77, polyethylene terephthalate resin) C-2: TRN-MTJ (product name) (manufactured by Teijin Limited, IV = 0.55, polyethylene terephthalate resin) C-3: 1100-211MD (product name) (manufactured by Changchun Artificial Resin Co., Ltd., polybutylene terephthalate resin) C-4: RNNA68 (product name) (manufactured by Nanya Co., Ltd., IV = 0.54, recycled polyethylene terephthalate resin)

[0137] <Component D: Phosphonic acid compounds excluding phosphonic acid esters> D-1: PPA (trade name) (manufactured by Nissan Chemical Corporation, phenylphosphonic acid) D-2: Kirest PH-210 (trade name) (manufactured by Kirest Corporation, 1-hydroxyethane-1,1-diphosphonic acid) D-3: JPCN-300 (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., nitrilotris (methylenephosphonic acid)) D-4 (comparative example): JC-224 (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., triethylphosphonoacetate)

[0138] <Component E: Inorganic Filler> E-1: TK-RC (product name) (manufactured by Katsumitsuyama Mining Co., Ltd., talc) E-2: KGP-H40 (product name) (manufactured by Kansai Matec Co., Ltd., wollastonite) E-3: GM-6 (product name) (manufactured by Kinsei Matec Co., Ltd., mica)

[0139] <Other Ingredients> (Phenol-based stabilizer) F-1: Irganox 1076 (product name) (manufactured by BASF Japan, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) (Release agent) F-2: Unistar H476S (product name) (manufactured by NOF Corporation, special fatty acid ester) (Carbon masterbatch) F-3: ROYAL BLACK90003S (product name) (manufactured by Koshigaya Chemical Industries, masterbatch consisting of carbon black and polystyrene resin)

[0140] <Production of Polycarbonate Resin Compositions> (Examples 1-22, Comparative Examples 1-9) The components shown in Tables 1 and 2 were premixed in the proportions shown in Tables 1 and 2, and melt-kneaded using a twin-screw extruder [TEX30α-31, manufactured by Japan Steel Works] at a screw rotation speed of 200 rpm, a discharge rate of 25 kg / h, and a vent vacuum of -1.0 kPa to obtain pellets. The extrusion temperature was 260°C from the first feed port to the die portion.

[0141] <Evaluation Method> The obtained pellets were dried in a hot air circulation dryer at 110°C for 5 hours or more, and then evaluated using the following evaluation method. The results are shown in Tables 1 and 2. 1. Thermal Stability Evaluation Using an injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], the resin was left in the cylinder for 10 minutes under conditions of cylinder temperature 260°C and mold temperature 60°C. Then, plates (50 mm wide x 90 mm long x 2 mm thick) were molded, and the appearance of the 2nd to 5th plates was observed with the naked eye according to the following criteria. ◎: 0 plates with silver. ○: 1 to 2 plates with silver. △: 3 plates with silver. ×: 4 plates with silver. 2. Using a rigidity evaluation injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], test specimens (80 mm x 10 mm x 4 mm thick) for evaluating the flexural modulus were molded under conditions of cylinder temperature 260°C and mold temperature 60°C. Measurements were performed according to ISO 178 standards, and the results were judged according to the following criteria: ◎: Flexural modulus is 4500 MPa or higher. ○: Flexural modulus is 2500 MPa or higher and less than 4500 MPa. ×: Flexural modulus is less than 2500 MPa. 3. Using a fluidity evaluation injection molding machine [SE130EV-A, manufactured by Sumitomo Heavy Industries], the spiral flow length (cm) was measured for 15 consecutive shots using an Archimedes spiral flow mold with a channel thickness of 2 mmt and a channel width of 8 mm, under the conditions of cylinder temperature 260°C, mold temperature 70°C, and injection pressure 98 MPa. The spiral flow length (cm) of the last 5 shots was then averaged and calculated. The evaluation was conducted according to the following criteria: ○: Spiral flow length is 20 cm or more. △: Spiral flow length is 15 cm or more and less than 20 cm. ×: Spiral flow length is less than 15 cm. 4. Using a heat-resistant injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], test specimens (80 mm x 10 mm x 4 mm thick) for evaluating load deflection temperature were molded under conditions of cylinder temperature 260°C and mold temperature 60°C. Measurements were performed according to ISO 178 standards, and the results were judged according to the following criteria. The measurement load was 1.80 MPa. ◎: Load deflection temperature is 100°C or higher.○: The temperature of deflection under load is 95°C or higher and less than 100°C. ×: The temperature of deflection under load is less than 95°C.

[0142]

[0143]

[0144] As shown in Tables 1 and 2, the present invention provides polycarbonate resin compositions and molded articles made therefrom, particularly automotive exterior parts, that are excellent in fluidity, heat resistance, rigidity, and thermal stability.

[0145] The polycarbonate resin composition and molded articles of the present invention can be used in automotive exterior parts such as housings for electrical, electronic, and office automation equipment, interior panels, roof spoilers, window garnishes, and roof panels.

Claims

1. A polycarbonate resin composition comprising 100 parts by weight of a component consisting of (A) 35.0 to 95.0 parts by weight of polycarbonate resin (component A) and (B) 65.0 to 5.0 parts by weight of styrene resin (component B), with (C) 0.5 to 10.0 parts by weight of polyester resin (component C), (D) 0.001 to 1.0 parts by weight of phosphonic acid compounds excluding phosphonic acid esters (component D), and (E) 5.0 to 110.0 parts by weight of inorganic filler (component E).

2. The polycarbonate resin composition according to claim 1, wherein component B is at least one styrene-based resin selected from the group consisting of acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene copolymer, and acrylonitrile-styrene-acrylate copolymer.

3. The polycarbonate resin composition according to claim 1 or 2, wherein component C is at least one polyester resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin.

4. The polycarbonate resin composition according to claim 1 or 2, wherein component D is a phosphonic acid compound represented by the following general formula (1). [In the above general formula (1), R is a group other than the group containing the ester bond.] 5. The polycarbonate resin composition according to claim 1 or 2, wherein component E is at least one inorganic filler selected from the group consisting of wollastonite, mica, and talc.

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

7. The molded article according to claim 6, which is an automotive exterior part.

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