Polycarbonate resin composition and molded article formed from same

Abstract

The present invention provides a polycarbonate resin composition which is excellent in flow stability and thermal stability and which provides a molded article with excellent appearance.　The present invention is a polycarbonate resin composition containing (C) 0.001-1.0 part by weight of a phosphonic acid compound (component C) excluding phosphonic acid esters with respect to 100 parts by weight of a resin component composed of: (A) 50.0-95.0 parts by weight of a polycarbonate resin (component A); and (B) 50.0-5.0 parts by weight of a polyester resin (component B).

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 flow stability, thermal stability, and molded article appearance.

[0002] Polycarbonate / polyester alloys, which are alloys of polycarbonate resin and polyester resin, are widely used in the automotive sector due to their excellent mechanical properties and chemical resistance. In recent years, there has been a trend towards integrating parts in automotive exterior components to reduce assembly man-hours, and the development of large components has become active. Therefore, in order to obtain a good molded appearance even for large components, there is a growing demand for resins with higher thermal stability than conventional resins, and thus flow stability during continuous injection molding is required. On the other hand, polymer alloys consisting of polycarbonate resin and polyester resin have a problem in that the fluidity of the resin composition is unstable due to excessive heating during melt mixing in an extruder or during retention in an injection molding machine, which causes excessive transesterification reactions. In the past, methods to improve thermal stability have been disclosed, such as using phosphate compounds and phosphite compounds or phosphonite compounds in combination as thermal stabilizers (see, for example, Patent Document 1) and adding organophosphate ester compounds (see, for example, Patent Document 2). However, these do not disclose polycarbonate resin compositions that are superior in flow stability, thermal stability, and molded product appearance, and they have the problem of poor flow stability during continuous injection molding.

[0003] Patent No. 5640734 Patent No. 4983427

[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, particularly an automotive exterior part, that has excellent flow stability, thermal stability, and molded article appearance.

[0005] As a result of diligent research to solve the aforementioned problems, the inventors of the present invention discovered that the above problems can be solved by the following configuration, and thus arrived at the present invention.

[0006] 1. A polycarbonate resin composition comprising 100 parts by weight of a resin component consisting of 50.0 to 95.0 parts by weight of (A) polycarbonate resin (component A) and 50.0 to 5.0 parts by weight of polyester resin (component B), and containing 0.001 to 1.0 parts by weight of (C) a phosphonic acid compound excluding phosphonic acid esters (component C). 2. The polycarbonate resin composition according to item 1, wherein comprising 5.0 to 110.0 parts by weight of (D) an inorganic filler (component D) per 100 parts by weight of the resin component consisting of components A and B. 3. The polycarbonate resin composition according to item 1 or 2, wherein component B 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 any one of items 1 to 3, wherein component C is a phosphonic acid compound represented by formula (1). [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 item 4 above, wherein component C is at least one phosphonic acid compound selected from the group consisting of phenylphosphonic acid, nitrilotris (methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid. 6. A molded article made from the polycarbonate resin composition according to any one of items 1 to 5 above. 7. A molded article according to item 6 above, which is an automobile exterior part.

[0007] The polycarbonate resin composition of the present invention is highly useful in a wide range of applications, including electrical and electronic applications, mechanical applications, office automation applications, automotive exterior parts, medical applications, and various other applications, due to its excellent flow stability, thermal stability, and molded product appearance. 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.

[0008] Further details of the present invention will be described below.

[0009] <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.

[0010] 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.

[0011] 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.

[0012] Carbonyl halides, carbonate esters, or haloformates can be used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0013] 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.

[0014] 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 .

[0015] Two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix a polycarbonate resin having a viscosity-average molecular weight outside the above range.

[0016] 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

[0017] 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.

[0018] 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.

[0019] Among aliphatic difunctional carboxylic acids, α,ω-dicarboxylic acids are preferred. Examples of aliphatic difunctional carboxylic acids include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanediic acid), dodecanediic acid, tetradecanediic acid, octadecanediic acid, and eicosanedioic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. As for difunctional alcohols, alicyclic diols are more preferred, with examples including cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0020] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0021] 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).

[0022]

[0023] [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.

[0024]

[0025] [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.

[0026]

[0027] [In the above general formula (4), R ３ , R ４ , R５ , 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.

[0028] 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.

[0029] 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.

[0030] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (4), the following compounds are preferably used, for example.

[0031]

[0032] 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.

[0033] 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.

[0034] 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.

[0035] In the present invention, only one hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more may be used. Furthermore, other comonomers other than the above-mentioned divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of 10% by weight or less relative to the total weight of the copolymer, as long as it does not interfere with the present invention.

[0036] In this invention, a mixed solution containing an oligomer having terminal chloroformate groups is prepared in advance by reacting divalent phenol(I) with 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 this invention may be converted into an oligomer at once, or a portion of it may be added as a reaction material to the subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to expedite the subsequent polycondensation reaction, and does not need to be added if unnecessary. The method of this oligomer generation reaction is not particularly limited, but it is generally preferable to carry it out in a solvent in the presence of an acid binder.

[0037] 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.

[0038] 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).

[0039] 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.

[0040] 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.

[0041] 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.

[0042]

[0043] [In the above general formula (4), R３ , 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 with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, where p is a natural number, q is 0 or a natural number, and p+q is a natural number from 10 to 300. X is a divalent aliphatic group with 2 to 8 carbon atoms.

[0044] 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).

[0045] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture. In such polymerization reactions, end-stoppers or molecular weight modifiers are usually used. Examples of end-stoppers 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 phenol compounds used, and it is naturally possible to use two or more compounds in combination.

[0046] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine like triethylamine or a quaternary ammonium salt may be added. The reaction time for such polymerization is preferably 30 minutes or more, more preferably 50 minutes or more. Optionally, a small amount of antioxidant such as sodium sulfite or hydrosulfide may be added.

[0047] 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.

[0048] <Component B: Polyester Resin> The polycarbonate resin composition of the present invention contains a polyester resin as component B. 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.

[0049] 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.

[0050] 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 that is a known precursor to polycondensation, and it is also possible to deactivate such catalysts with a phosphoric acid or phosphorous acid compound, etc. after the completion of the transesterification reaction 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.

[0051] 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.

[0052] 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.

[0053] 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 yield a satisfactory polymer may be used in the preparation of the aromatic polyarylate resin, and one or more types may be used in combination. Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. Mixtures thereof may also be used.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] The content of component B is 50.0 to 5.0 parts by weight, preferably 45.0 to 7.5 parts by weight, and more preferably 40.0 to 10.0 parts by weight, per 100 parts by weight of the resin component. If the content of component B exceeds 50 parts by weight, the flow stability deteriorates, and if it is less than 5.0 parts by weight, the thermal stability and the appearance of the molded product deteriorate.

[0059] <Component C: 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 C. If compounds other than these are used as component C, the flow stability may deteriorate, and the thermal stability and appearance of the molded product may deteriorate. Component C is preferably a phosphonic acid compound represented by the following formula (1).

[0060]

[0061] [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.

[0062] The content of component C is 0.001 to 1.0 parts by weight per 100 parts by weight of the resin component, preferably 0.002 to 0.8 parts by weight, more preferably 0.005 to 0.5 parts by weight, even more preferably 0.01 to 0.5 parts by weight, particularly preferably 0.05 to 0.5 parts by weight, and most preferably 0.08 to 0.4 parts by weight. When the content of component C is less than 0.001 parts by weight or more than 1 part by weight, the flow stability, thermal stability, and appearance of the molded product deteriorate.

[0063] <Component D: Inorganic Filler> The polycarbonate resin composition of the present invention preferably contains an inorganic filler as component D. 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 D of the present invention contains at least a metal oxide component and SiO ２ The minerals consist 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.

[0064] 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 two or more single oxides and 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 ２ It can be in any form as an oxygen molecule.

[0065] 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.

[0066] 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.

[0067] 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).

[0068] Na ２Those containing O in their components include 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 ２ O·Al ２ O ３ ·4SiO ２ (Jadeite), 2Na ２ O·3CaO·5SiO ２ , 3Na ２ O·2CaO·5SiO ２ , and Na ２ O·Al ２ O ３ ·6SiO ２ (Anorthite), etc. can be mentioned.

[0069] Those containing Li ２ O in their components include 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<​​​​​​​​​​​​​​​​​​​​​Substances containing BaO as a component include BaO·SiO ２ , 2BaO・SiO ２ BaO・Al ２ O ３ ・2SiO ２ (Celsian), and BaO・TiO ２ 3SiO ２ Examples include (bentite).

[0071] Examples of substances containing CaO include 3CaO·SiO ２ (Alite, a 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 ・H２ 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 ２ Examples include (pleochroite), as well as clinozoisite, rhodochroite, charnet, vesuvianite, onoite, scoutite, and augite.

[0072] 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 cements. Additionally, various blended cements, such as blast furnace cement, silica cement, and fly ash cement, can also be used as component D. Other silicate minerals containing CaO include blast furnace slag and ferrite.

[0073] Substances containing ZnO include ZnO·SiO ２ , 2ZnO・SiO ２ (Trostite), and 4ZnO・2SiO ２ ・H ２ Examples include O (hemipolar ore).

[0074] Substances containing MnO include MnO·SiO ２ , 2MnO·SiO ２ , CaO・4MnO・5SiO ２ Examples include rhodonite and causerite.

[0075] Substances containing FeO include FeO·SiO ２ (ferrosilite), 2FeO・SiO ２ (Iron olivine), 3FeO・Al ２ O３ 3SiO ２ (Almandine), and 2CaO・5FeO・8SiO ２ ・H ２ Examples include O (Tetsuaktinoseite).

[0076] Substances containing CoO as a component include CoO·SiO ２ and 2CoO·SiO ２ These are some examples.

[0077] 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 ２Examples include O (lansene), as well as magnesium tourmaline, orthozoite, cumingtonite, vermiculite, and smectite.

[0078] Fe ２ O ３ As for those containing Fe as an ingredient, ２ O ３ SiO ２ These are some examples.

[0079] ZrO ２ As for substances that contain it as an ingredient, ZrO ２ SiO ２ Examples include zircon and AZS refractories.

[0080] 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 ２O (mascobite, sericite), K ２ O・6MgO・Al ２ O ３ 6SiO ２ ・2H ２ Examples include phlovite (O), various zeolites, fluorinated phlophthomikte, and biotite.

[0081] 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.

[0082] (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.

[0083] Furthermore, there are no particular restrictions on the method of crushing 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.

[0084] (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 also 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. Muscovite mica is preferred for use, and its Mohs hardness is approximately 3. Muscovite mica can achieve higher rigidity and strength compared to other mica such as phlovite, 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.

[0085] (Wollastonite) The fiber diameter of the 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. For the fiber diameter, the filler to be measured is randomly selected from the image obtained by observation with an electron microscope, the fiber diameter is measured near the center, and the number-average fiber diameter is calculated 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).

[0086] 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.

[0087] 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.

[0088] The content of component D is preferably 5.0 to 110.0 parts by weight, more preferably 7.0 to 80.0 parts by weight, even more preferably 12.5 to 50.0 parts by weight, and particularly preferably 15.0 to 35.0 parts by weight, per 100 parts by weight of the resin component. If the content of component D is less than 5.0 parts by weight, the rigidity may deteriorate, and if it exceeds 110.0 parts by weight, the thermal stability may deteriorate.

[0089] <Other Components> <Impact Modifier> The polycarbonate resin composition of the present invention may contain an impact modifier to the extent that it exhibits the effects of the present invention. 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 rubber, methyl methacrylate-butadiene-styrene copolymer rubber, and acrylic rubber, 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.

[0090] <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.

[0091] 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.

[0092] 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 in terms of standard polystyrene 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.

[0093] <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)benzotri Examples of polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton include 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-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).

[0094] Examples of cyanoacrylate-based 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.

[0095] 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 undergo radical polymerization. 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 a (meth)acrylic acid ester.

[0096] <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.

[0097] 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.

[0098] <Other Resins> In the polycarbonate resin composition of the present invention, resins other than components A and B may be used in small proportions, to the extent that the effects of the present invention are exhibited. Examples of such other resins include AES resin, ASA resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polymethacrylate resin, phenol resin, and fluororesin.

[0099] <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 the molded article or improve its properties. These additives are added in normal amounts as long as they do not impair the purpose 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.

[0100] <Regarding the method for producing the polycarbonate resin composition> The polycarbonate resin composition of the present invention can be produced by any method. For example, it can be produced by kneading in a single-screw or multi-screw extruder. The polycarbonate resin, polyester resin, phosphonic acid compounds excluding phosphonic acid esters, and other components can be mixed together, or some of the components may be mixed first, and then mixed and kneaded with the remainder. The polycarbonate resin composition thus obtained can be molded into automobile parts, electrical and electronic components, etc., by various known methods, such as injection molding and extrusion molding.

[0101] The polycarbonate resin composition of the present invention will be described in detail below based on examples. In the measurement conditions and examples below, "parts" refers to "parts by weight". <Materials Used> <Component A: Polycarbonate Resin> A-1: ​​L-1250WQ (product name) (manufactured by Teijin Limited, viscosity-average molecular weight 25100, linear polycarbonate resin) A-2: L-1225WX (product name) (manufactured by Teijin Limited, viscosity-average molecular weight 19700, 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)

[0102] <Component B: Polyester Resin> B-1: TRN-8550FF (product name) (manufactured by Teijin Limited, IV = 0.77, polyethylene terephthalate resin) B-2: TRN-MTJ (product name) (manufactured by Teijin Limited, IV = 0.55, polyethylene terephthalate resin) B-3: DuraNex 700FP EF201X (product name) (manufactured by Polyplastics, polybutylene terephthalate resin) B-4: RNNA68 (product name) (manufactured by Nanya, IV = 0.54, recycled polyethylene terephthalate resin)

[0103] <Component C: Phosphonic acid compounds excluding phosphonic acid esters> C-1: PPA (trade name) (manufactured by Nissan Chemical Corporation, phenylphosphonic acid) C-2: JPCN-300 (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., nitrilotris (methylenephosphonic acid)) C-3: Kirest PH-210 (trade name) (manufactured by Kirest, 1-hydroxyethane-1,1-diphosphonic acid) C-4 (comparative example): JC-224 (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., triethylphosphonoacetate) C-5 (comparative example): AX-71 (trade name) (manufactured by ADEKA Corporation, stearyl acid phosphate) C-6 (comparative example): JP-518Zn (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., stearyl acid phosphate zinc salt) C-7 (comparative example): Irganox 1076 (Trade name) (Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Japan)

[0104] <Component D: Inorganic Filler> D-1: TK-RC (product name) (manufactured by Katsumitsuyama Mining Co., Ltd., talc) D-2: KGP-H40 (product name) (manufactured by Kansai Matec Co., Ltd., wollastonite) D-3: GM-6 (product name) (manufactured by Kinsei Matec Co., Ltd., mica)

[0105] <Other Ingredients> (Impact Modifier) ​​E-1: S2030 (product name) (manufactured by Mitsubishi Chemical Corporation, silicone-acrylic impact modifier) ​​E-2: M724 (product name) (manufactured by Kaneka Corporation, methyl methacrylate-butadiene-styrene copolymer impact modifier) ​​E-3: LA-4285 (product name) (manufactured by Kuraray Co., Ltd., acrylic impact modifier) ​​(Release Agent) E-4: EW-400 (product name) (manufactured by Riken Vitamin Co., Ltd., special fatty acid ester) (UV Absorber) E-5: SEESORB701 (product name) (manufactured by Cipro Chemical Co., Ltd.) (Carbon Masterbatch) E-6: ROYAL BLACK90003S (product name) (manufactured by Koshigaya Chemical Industry Co., Ltd., masterbatch consisting of carbon black and polystyrene resin)

[0106] <Production of Polycarbonate Resin Composition> (Examples 1-41, Comparative Examples 1-8) The components shown in Tables 1-4 were premixed in the proportions shown in Tables 1-4, and melt-kneaded using a twin-screw extruder [TEX30α-31 manufactured by Japan Steel Works] at a screw rotation speed of 250 rpm, a discharge rate of 30 kg / h, and a vent vacuum of -1.0 kPa to obtain pellets. The extrusion temperature was 280°C from the first feed port to the die portion.

[0107] <Evaluation Method> The obtained pellets were dried in a hot air circulation dryer at 120°C for 5 hours or more, and then evaluated using the following evaluation method. The results are shown in Tables 1 to 4. 1. Flow Stability Evaluation Using an injection molding machine [SE130EV-A manufactured by Sumitomo Heavy Industries], the spiral flow length (cm) was measured for 20 consecutive shots using an Archimedes spiral flow mold with a flow channel thickness of 2 mmt and a flow channel width of 8 mm, under the conditions of cylinder temperature 280°C, mold temperature 70°C, and injection pressure 98 MPa, and the flow change rate was calculated using the following formula. The evaluation was carried out according to the following criteria. Flow change rate (%) = [(Maximum value of spiral flow length - Minimum value of spiral flow length) / Maximum value of spiral flow length] × 100 ○: Flow change rate is less than 8% △: Flow change rate is 8% or more and less than 10% ×: Flow change rate is 10% or more 2. Using a thermal stability evaluation injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], resin was left in the cylinder for 10 minutes under conditions of cylinder temperature 280°C and mold temperature 80°C. After molding, a plate (50 mm wide x 90 mm long x 2 mm thick) was formed, and the appearance of the third plate was observed visually and judged according to the following criteria. ◎: Area where silver was generated was 1 cm². ２ Less than 1 cm. ○: Area where silver was generated is 1 cm ２ More than 5cm ２ It is less than 5 cm. △: The area where silver was generated is 5 cm. ２ Above, 10cm ２ It is less than 10 cm². ×: The area where silver was generated is 10 cm². ２That concludes the report. 3. Evaluation of Molded Product Appearance Using an injection molding machine [EC130SX2-4Y, manufactured by Toshiba Machine Engineering], a rectangular plate (150 mm long x 150 mm wide x 2.5 mm thick) was molded without holding pressure under the conditions of cylinder temperature 280°C, mold temperature 60°C, and injection speed 70 mm / Sec. Its appearance was observed visually and judged according to the following criteria. ○: No surface unevenness or irregularities were observed. △: Almost no surface unevenness or irregularities were observed. ×: Significant surface unevenness and irregularities were observed. 4. Evaluation of Rigidity Using an injection molding machine [ROBOSHOT α-S100iA, manufactured by FANUC], a test piece for evaluating the flexural modulus (80 mm x 10 mm x 4 mm thick) was molded under the conditions of cylinder temperature 280°C and mold temperature 70°C. Measurements were performed according to the ISO 178 standard and 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.

[0108]

[0109]

[0110]

[0111]

[0112] As shown in Tables 1 to 4, the present invention provides a polycarbonate resin composition and molded articles made therefrom, particularly automotive exterior parts, that exhibit excellent flow stability, thermal stability, and molded article appearance.

[0113] 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 resin component consisting of (A) 50.0 to 95.0 parts by weight of polycarbonate resin (component A) and (B) 50.0 to 5.0 parts by weight of polyester resin (component B), and containing 0.001 to 1.0 part by weight of (C) a phosphonic acid compound excluding phosphonic acid esters (component C).

2. The polycarbonate resin composition according to claim 1, wherein the composition contains 5.0 to 110.0 parts by weight of (D) an inorganic filler (component D) per 100 parts by weight of the resin component consisting of component A and component B.

3. The polycarbonate resin composition according to claim 1 or 2, wherein component B 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 C is a phosphonic acid compound represented by 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 4, wherein component C is at least one phosphonic acid compound selected from the group consisting of phenylphosphonic acid, nitrilotris (methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid.

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.

Images