Polycarbonate resin composition and molded article comprising the same

Abstract

To provide a polycarbonate resin composition excellent in thermal stability, moist heat resistance, and molded article appearance.SOLUTION: The polycarbonate resin composition contains (B) 0.5-20 pts.wt. of polyoxyalkylene dibenzoate (component B) based on (A) 100 pts.wt. of a polycarbonate resin (component A).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition having excellent thermal stability, moist heat resistance and molded article appearance, and to a molded article made therefrom. [Background technology]

[0002] Polycarbonate resin and polyethylene terephthalate resin alloy polycarbonate Polyethylene terephthalate / polyethylene terephthalate alloys are widely used in the automotive industry due to their excellent mechanical properties and chemical resistance. In recent years, automotive exterior parts have become increasingly integrated to reduce assembly time, leading to active development of large parts. Therefore, there is a growing demand for resins with higher fluidity than conventional ones in order to obtain good molded appearances, even for large parts. One method for improving fluidity has been disclosed (see, for example, Patent Document 1). However, the effectiveness of improving molded appearance varies depending on the plasticizer component, and plasticizers generally have low molecular weights, which deteriorate the thermal stability and moist heat resistance of resin compositions. As a result, nonuniformity and unevenness occur, preventing satisfactory molded appearance. Furthermore, when the resin composition is maintained at high temperatures in a cylinder, the plasticizer decomposes, generating gases that result in a poor appearance known as "silvering." Furthermore, molded products are prone to deterioration under high temperature and high humidity. Another method for improving thermal stability has been disclosed (see, for example, Patent Document 2) in which a specific organic phosphate ester is added to a polyoxyalkylene bisphenol ether component as a plasticizer. However, although it is effective in improving thermal stability, it has the same problem as Patent Document 1 in that it is inferior in molded appearance and moist heat resistance, and molded articles tend to deteriorate under high temperature and high humidity conditions. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 6889221 [Patent Document 2] Japanese Patent Application Publication No. 2023-110208 Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, an object of the present invention is to provide a polycarbonate resin composition which is excellent in thermal stability, moist heat resistance and appearance of molded articles, and a molded article, particularly an automobile exterior part, made therefrom. [Means for solving the problem]

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

[0006] 1. A polycarbonate resin composition containing 0.5 to 20 parts by weight of (B) polyoxyalkylene dibenzoate (component B) per 100 parts by weight of (A) polycarbonate resin (component A). 2. The polycarbonate resin composition according to item 1 above, wherein component B has an average molecular weight of 300 to 600. 3. The polycarbonate resin composition according to item 1 above, which contains 0.01 to 100 parts by weight of (C) a thermoplastic resin other than component A (component C) per 100 parts by weight of component A. 4. The polycarbonate resin composition according to item 3 above, wherein component C is at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-styrene copolymer resin. 5. The polycarbonate resin composition according to item 3 above, wherein component C is at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin. 6. The polycarbonate resin composition according to any one of items 1 to 5 above, which contains 0.01 to 8 parts by weight of (D) a phosphorus-based stabilizer (Component D) per 100 parts by weight of Component A. 7. A molded article comprising the resin composition according to any one of the preceding items 1 to 6. 8. The molded article according to the preceding item 7, which is an automotive exterior part.

Advantages of the Invention

[0007] The polycarbonate resin composition of the present invention is excellent in thermal stability, heat and humidity resistance, and the appearance of molded articles, and thus is widely useful in various applications such as electric and electronic applications, mechanical applications, OA applications, automotive exterior parts, medical applications, and other applications. Among them, it provides a molded article that is extremely useful as an automotive exterior part, and the industrial effects achieved by the present invention are extremely large.

Modes for Carrying Out the Invention

[0008] Hereinafter, the details of the present invention will be further described.

[0009] <Component A: Polycarbonate Resin> The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include, for example, the interfacial polycondensation method, the melt transesterification method, the solid-phase transesterification method of a carbonate prepolymer, and the ring-opening polymerization method of a cyclic carbonate compound.

[0010] Representative examples of dihydric phenols used herein 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, 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)pentane, 1,1-bis(4-hydroxyphenyl)-4-methylpentane, 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-diisopropylbenzene Examples of the dihydroxydiphenyl ether include 4,4'-isopropylbenzene, 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, and these can be used alone 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, and 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 particularly preferred.

[0012] Carbonate precursors that can be used include carbonyl halides, carbonate esters, and haloformates, and specific examples include phosgene, diphenyl carbonate, and dihaloformates of dihydric phenols.

[0013] When producing a polycarbonate resin by reacting the dihydric phenol with a carbonate precursor by the interfacial polycondensation method or the melt transesterification method, a catalyst, a terminal terminator, an antioxidant for the dihydric phenol, etc. may be used as necessary. The polycarbonate resin may be a branched polycarbonate resin copolymerized with a trifunctional or higher 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] The reaction methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well known in various literatures and patent publications. The viscosity average molecular weight of the polycarbonate resin is not specified, but is generally within the range of 1×10 4 If it is less than 4×10 4 If it exceeds 1×10, the molding processability will decrease. 4 ~4×10 4 is preferably 1.4 × 10 4 ~3×10 4 , and more preferably 1.6×10 4 ~2.5×10 4 is.

[0015] Two or more polycarbonate resins may be mixed together, and 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 the specific viscosity (η) determined from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. SP ) into the following equation: 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] The polycarbonate resin of the present invention may be a branched polycarbonate resin. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4

[0043] Examples of the hydroxyphenyl ester include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0018] The structural units derived from polyfunctional aromatic compounds in the branched polycarbonate resin are preferably 0.01 to 1 mol%, more preferably 0.05 to 0.9 mol%, and even more preferably 0.05 to 0.8 mol% out of the total 100 mol% of the structural units derived from dihydric phenols and the structural units derived from such polyfunctional aromatic compounds. In particular, in the case of the melt transesterification method, branched structural units may be generated as a side reaction, and the amount of such branched structural units is 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% out of the total 100 mol% of the structural units derived from dihydric phenols. The proportion of such branched structures is 1 It can be calculated by H-NMR measurement.

[0019] The aliphatic bifunctional carboxylic acid is preferably an α,ω-dicarboxylic acid. Preferred examples of the aliphatic bifunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosane diacid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. The bifunctional alcohol is more preferably an alicyclic diol, such as cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

[0020] The reaction modes of the methods for producing the polycarbonate resin of the present invention, such as interfacial polymerization, melt transesterification, carbonate prepolymer solid-phase transesterification, and ring-opening polymerization of a cyclic carbonate compound, are well known in various literatures and patent publications.

[0021] The polycarbonate resin of the present invention may be a polycarbonate-polydiorganosiloxane copolymer resin, preferably prepared by copolymerizing a dihydric phenol represented by the following general formula (1) with a hydroxyaryl-terminated polydiorganosiloxane represented by the following general formula (3):

[0022] [ka]

[0023] [In the above general formula (1), R 1 and R 2each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula (2):

[0024] [ka]

[0025] [In the above general formula (2), R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple groups, they may be the same or different; g is an integer of 1 to 10, and h is an integer of 4 to 7.

[0026] [ka]

[0027] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0028] Examples of the dihydric phenol (I) represented by the general formula (1) include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2- Bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)propane 4,4'-dihydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'- Dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[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 is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0030] As the hydroxyaryl-terminated polydiorganosiloxane represented by the above general formula (3), for example, the compounds shown below are preferably used.

[0031] [ka]

[0032] Hydroxyaryl-terminated polydiorganosiloxanes (II) can be easily produced by hydrosilylation of a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol, at the end of a polysiloxane chain having a predetermined degree of polymerization. Among these, (2-allylphenol)-terminated polydiorganosiloxanes and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxanes are preferred, with (2-allylphenol)-terminated polydimethylsiloxanes and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxanes being particularly preferred. The molecular weight distribution (Mw / Mn) of the hydroxyaryl-terminated polydiorganosiloxanes (II) is preferably 3 or less. To achieve even better low outgassing properties during high-temperature molding and low-temperature impact resistance, the molecular weight distribution (Mw / Mn) is more preferably 2.5 or less, and even more preferably 2 or less. If the upper limit of this preferred range is exceeded, the amount of outgassing during high-temperature molding may be large, and low-temperature impact resistance may be poor.

[0033] Furthermore, in order to achieve high impact resistance, the diorganosiloxane degree of polymerization (p+q) of the hydroxyaryl-terminated polydiorganosiloxane (II) is suitably 10 to 300. The diorganosiloxane degree of polymerization (p+q) is preferably 10 to 200, more preferably 12 to 150, and even more preferably 14 to 100. Below the lower limit of this preferred range, the impact resistance that is a characteristic of polycarbonate-polydiorganosiloxane copolymers is not effectively exhibited, while above the upper limit of this preferred range, poor appearance appears.

[0034] The polydiorganosiloxane content of the total weight of the polycarbonate-polydiorganosiloxane copolymer resin used in component A is preferably 0.1 to 50% by weight. The polydiorganosiloxane content is more preferably 0.5 to 30% by weight, and even more preferably 1 to 20% by weight. At or above the lower limit of this preferred range, excellent impact resistance and flame retardancy are achieved, while at or below the upper limit of this preferred range, a stable appearance that is less susceptible to the effects of molding conditions is easily achieved. The polydiorganosiloxane polymerization degree and polydiorganosiloxane content are 1 It can be calculated by H-NMR measurement.

[0035] In the present invention, the hydroxyaryl-terminated polydiorganosiloxane (II) may be used alone or in combination of two or more.

[0036] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that this does not interfere with the present invention.

[0037] In the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an aqueous alkaline solution. When producing an oligomer of dihydric phenol (I), the entire amount of dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a portion of the oligomer may be added as a post-added monomer as a reaction raw material to the subsequent interfacial polycondensation reaction. The post-added monomer is added to facilitate the subsequent polycondensation reaction, and does not need to be added if not required.

[0038] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0039] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0040] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Similarly, the proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0041] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0042] The reaction pressure for oligomer formation is not particularly limited and may be atmospheric, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under atmospheric pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually carried out for 0.2 to 10 hours. The pH range for the oligomer formation reaction is similar to that of known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

[0043] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the mixed solution is stirred while adding a hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula (3), which has been highly purified to a molecular weight distribution (Mw / Mn) of 3 or less, to the dihydric phenol (I), and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0044] [ka]

[0045] [In the above general formula (3), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p+q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0046] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

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

[0048] In such a polymerization reaction, a terminal terminator or a molecular weight modifier is usually used. Examples of the terminal terminator include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is preferably in the range of 100 to 0.5 mol, more preferably 50 to 2 mol, relative to 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0049] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0050] The reaction time for such a polymerization reaction is preferably 30 minutes or more, more preferably 50 minutes or more. If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0051] A branching agent can be used in combination with the above-mentioned dihydric phenol compound to produce a branched polycarbonate-polydiorganosiloxane. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate-polydiorganosiloxane copolymer resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxydiphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1 Examples include trisphenols such as {1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, and among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred. The proportion of the polyfunctional compound in the branched polycarbonate-polydiorganosiloxane copolymer resin is preferably 0.001 to 1 mol %, more preferably 0.005 to 0.9 mol %, even more preferably 0.01 to 0.8 mol %, and particularly preferably 0.05 to 0.4 mol %, based on the total amount of the polycarbonate-polydiorganosiloxane copolymer resin. 1 It can be calculated by H-NMR measurement.

[0052] <Component B: Polyoxyalkylene dibenzoate> The polyoxyalkylene dibenzoate used in the present invention acts as a plasticizer. Specific examples of the polyoxyalkylene dibenzoate include compounds such as polyethylene glycol dibenzoate and polyethylene glycol - polypropylene glycol dibenzoate. These compounds can be used alone or in combination of two or more. When using a compound other than polyoxyalkylene dibenzoate as the plasticizer, the thermal stability and heat and humidity resistance deteriorate.

[0053] As the polyoxyalkylene dibenzoate of the present invention, those having a cyclic hydrocarbon group such as an aromatic hydrocarbon group or an alicyclic hydrocarbon group are preferred, and among them, the compound represented by the following general formula (4) is preferred from the viewpoint of the molding appearance.

[0054] [In Chemical formula,

[0055] [In general formula (4), A represents a group selected from the group consisting of an oxyalkylene group having 1 to 22 carbon atoms, an oxyaryl group having 1 to 22 carbon atoms, and an oxyalkylaryl group. n represents 0 to 100.]

[0056] The average molecular weight of Component B is preferably 300 to 600, more preferably 350 to 550, and even more preferably 350 to 450. When the molecular weight of Component B exceeds 600, the effect of improving the molding appearance is small, and when it is less than 300, the thermal stability and heat and humidity resistance may decrease. The average molecular weight of Component B is measured by gel permeation chromatography (GPC).

[0057] The content of Component B is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1.5 to 10 parts by weight with respect to 100 parts by weight of Component A. When the content of Component B is less than 0.5 parts by weight, the molding appearance deteriorates, and when it exceeds 20 parts by weight, the thermal stability and heat and humidity resistance deteriorate.

[0058] <Component C: Thermoplastic resin other than Component A> The resin composition of the present invention can contain a thermoplastic resin other than Component A as Component C. Component C is preferably at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-styrene copolymer resin, and more preferably at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin.

[0059] Polyethylene terephthalate resin is a saturated polyester polymer or copolymer obtained by condensation reaction of terephthalic acid or its ester-forming derivative as the main component of the aromatic dicarboxylic acid component and ethylene glycol or its ester-forming derivative as the main component of the diol component, and is a thermoplastic polyester resin preferably containing 70 mol% or more, more preferably 80 mol% or more of ethylene terephthalate units as repeating units. The production of polyethylene terephthalate resin is carried out by reacting the above-mentioned dicarboxylic acid component and diol component while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. according to a conventional method, and discharging the by-produced water or lower alcohol out of the system. At this time, either a batch method or a continuous polymerization method can be adopted, and the degree of polymerization can also be increased by solid-phase polymerization.

[0060] In addition, the end group structure of the polyethylene terephthalate resin used is not particularly limited, and it may be a case where the ratio of one of them is large except when the ratio of the hydroxyl group and the carboxyl group in the end group is almost the same. Further, the end groups may be sealed by reacting a compound having reactivity with such end groups.

[0061] In the present invention, there are no limitations on the intrinsic viscosity of the polyethylene terephthalate resin, but it is preferably in the range of 0.4 to 1.2. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molded product obtained therefrom may also be high. The intrinsic viscosity is more preferably in the range of 0.45 to 1.1, and even more preferably 0.5 to 1.0. The intrinsic viscosity of the polyethylene terephthalate resin is measured by dissolving the polyethylene terephthalate resin in o-chlorophenol at a temperature of 35°C.

[0062] Polybutylene terephthalate resin is obtained by polycondensation of terephthalic acid or its ester-forming derivative with alkylene glycol having four carbon atoms or its ester-forming derivative. The polybutylene terephthalate resin may also be a copolymer containing 70% or more by weight of the polybutylene terephthalate resin itself.

[0063] Examples of dibasic acid components other than terephthalic acid and its lower alcohol esters include aliphatic and aromatic polybasic acids such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, and succinic acid, or ester-forming derivatives thereof. Examples of glycol components other than 1,4-butanediol include ordinary alkylene glycols, for example, lower alkylene glycols such as ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, and 1,3-octanediol; aromatic alcohols such as bisphenol A and 4,4'-dihydroxybiphenyl; alkylene oxide adduct alcohols such as an ethylene oxide 2-mol adduct of bisphenol A and a propylene oxide 3-mol adduct of bisphenol A; and polyhydroxy compounds such as glycerin and pentaerythritol, or ester-forming derivatives thereof.

[0064] In the present invention, there are no limitations on the intrinsic viscosity of the polybutylene terephthalate resin, but it is preferably in the range of 0.6 to 1.4. When the intrinsic viscosity is within this range, melt molding is easy and the strength of the molded product obtained therefrom may also be high. The intrinsic viscosity is more preferably in the range of 0.65 to 1.3, and even more preferably 0.7 to 1.2. The intrinsic viscosity of the polybutylene terephthalate resin is measured by dissolving the polybutylene terephthalate resin in o-chlorophenol at a temperature of 25°C.

[0065] Acrylonitrile-butadiene-styrene copolymer resin is a copolymer obtained by grafting acrylonitrile and styrene onto polybutadiene. Styrene and α-methylstyrene are particularly preferred as styrenes. The proportion of the component grafted onto the polybutadiene is preferably 95 to 20% by weight, and particularly preferably 90 to 50% by weight, based on 100% by weight of the ABS resin component. Furthermore, the proportion of acrylonitrile is preferably 5 to 50% by weight and styrene is preferably 95 to 50% by weight, based on 100% by weight of the total amount of acrylonitrile and styrene. Furthermore, methyl (meth)acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, etc., can be used as a part of the component grafted onto the polybutadiene, and the content of these compounds is preferably 15% by weight or less of the ABS resin component. Furthermore, various conventional initiators, chain transfer agents, emulsifiers, etc., can be used as needed. In the ABS resin of the present invention, the polybutadiene particle size is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.3 to 1.5 μm. The polybutadiene particle size distribution may be either a single distribution or a distribution with two or more peaks. Furthermore, the morphology may be either a single-phase distribution or a salami structure formed by the inclusion of an occluded phase around the particles. It is well known that ABS resins contain copolymers of acrylonitrile and styrene that are not grafted to a diene rubber component. The ABS resin of the present invention may also contain free polymer components generated during the polymerization. The reduced viscosity (30°C) of such a copolymer of free acrylonitrile and styrene is preferably 0.2 to 1.0 dL / g, more preferably 0.3 to 0.7 dL / g. The ratio of grafted acrylonitrile and styrene to polybutadiene is preferably 20 to 200%, more preferably 20 to 70%, in terms of graft ratio (% by weight).Such ABS resin may be produced by any of bulk polymerization, suspension polymerization, and emulsion polymerization, with bulk polymerization being particularly preferred.In the case of bulk polymerization, since it substantially does not contain alkali metal salts and the like derived from emulsifiers and the like, it becomes possible to better maintain the thermal stability of the polycarbonate resin composition. Also, the copolymerization method may be carried out in one stage or in multiple stages. Further, a blend obtained by separately copolymerizing acrylonitrile and styrene with the ABS resin obtained by such a production method can also be preferably used.

[0066] The acrylonitrile-styrene copolymer resin may have high stereoregularity such as syndiotactic polystyrene by using a catalyst such as a metallocene catalyst during its production. Further, in some cases, polymers, copolymers, block copolymers, and polymers and copolymers with high stereoregularity having a narrow molecular weight distribution obtained by methods such as anionic living polymerization and radical living polymerization can also be used.

[0067] The content of component C is preferably 0.01 to 100 parts by weight, more preferably 3 to 98 parts by weight, and even more preferably 5 to 89 parts by weight with respect to 100 parts by weight of component A. If the content of component C exceeds 100 parts by weight, the thermal stability and the resistance to moist heat may deteriorate, and if it is less than 0.01 part by weight, the effect of improving the molding appearance may decrease. [[ID=IO]]

[0068] <Component D: Phosphorus stabilizer> Examples of the phosphorus stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and its ester, triorganophosphate compound, acid phosphate compound and its metal salt are particularly preferable. Note that the organic group in the acid phosphate compound includes any of monosubstituted, disubstituted, and mixtures thereof. The same shall apply to the following exemplified compounds corresponding to the compound, including any of them.

[0069] Examples of triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphates are preferred. The number of carbon atoms in such trialkyl phosphates is preferably 1 to 22, more preferably 2 to 20. A particularly preferred trialkyl phosphate is trimethyl phosphate.

[0070] Examples of acid phosphate compounds include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxypolyethylene glycol acid phosphate, and bisphenol A acid phosphate. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are preferred because they are effective in improving thermal stability and the acid phosphate itself is highly stable.

[0071] As the acid phosphate metal salt, monostearyl phosphate zinc salt and distearyl phosphate zinc salt are preferred.

[0072] Examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert- butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

[0073] Other phosphite compounds that can be used include those that react with dihydric phenols to form a cyclic structure, such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0074] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples of suitable phosphonite compounds include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Among these, tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with, and are preferred for, the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0075] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0076] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, diphenylbenzylphosphine, etc. A particularly preferred tertiary phosphine is triphenylphosphine.

[0077] Phosphonate ester compounds include phosphonic acid monoesters, phosphonic acid diesters, and phosphonic acid triesters, with phosphonic acid triesters being preferred. Various combinations of esters with carbon numbers from 1 to 22 can be used, with triethylphosphonoacetate being the most preferred.

[0078] Suitable phosphorus-based stabilizers are phosphonite compounds represented by the following formula (5), acid phosphate compounds represented by the following formula (6), acid phosphate metal salts represented by the following formula (7), phosphonate ester compounds represented by the following formula (8), and phosphonate ester compounds represented by the following formula (9).

[0079] [ka]

[0080] [In general formula (5), R and R' represent a group selected from the group consisting of an alkyl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an alkylaryl group, and may be the same or different.]

[0081] [ka]

[0082] In the general formula (6), R represents an alkyl group or an aryl group, and may be the same or different. m is an integer of 0 to 2.]

[0083] [ka]

[0084] [In general formula (7), R and R′ represent a group selected from the group consisting of an alkyl group having 6 to 30 carbon atoms, an aryl group having 1 to 22 carbon atoms, and an alkylaryl group, and may be the same or different.]

[0085] [ka]

[0086] [In general formula (8), R represents a group selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, and an alkylaryl group.]

[0087] [ka]

[0088] [In general formula (9), R, R', and R'' represent a group selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, and an alkylaryl group, and may be the same or different.]

[0089] Stabilizers containing the above as the main components are commercially available and can be used as SONGNOX6260PW (trademark, manufactured by SONGWON), AX-71 (trademark, manufactured by ADEKA), JP-518Zn (trademark, manufactured by Johoku Chemical), and JC-224 (trademark, manufactured by Johoku Chemical).

[0090] The content of component D is preferably 0.01 to 8 parts by weight, more preferably 0.05 to 7 parts by weight, and even more preferably 0.1 to 5 parts by weight, per 100 parts by weight of component A. If the content of component D is less than 0.01 part by weight, the thermal stability may decrease, and if it exceeds 8 parts by weight, the thermal stability and moist heat resistance may deteriorate.

[0091] <Other ingredients> <Inorganic fillers> The resin composition of the present invention can contain an inorganic filler. The inorganic filler is preferably a silicate mineral such as mica, wollastonite, or talc, more preferably mica or wollastonite, and even more preferably wollastonite. The number-average fiber length of wollastonite is preferably 2 to 10 μm, more preferably 3 to 9 μm, and even more preferably 3 to 8 μm. If the average diameter is less than 2 μm, the effect of improving rigidity may be small, and if it exceeds 10 μm, the impact resistance may be significantly reduced.

[0092] Wollastonite may be surface-treated with a coupling agent such as a silane coupling agent or a titanate coupling agent. Examples of silane coupling agents include epoxysilane, aminosilane, and vinylsilane. Examples of titanate coupling agents include monoalkoxy, chelate, and coordinate types. The method for surface-treating wollastonite with a coupling agent is not particularly limited, and can be carried out by a conventional method. For example, it can be carried out by adding 0.1 to 10% by weight of the coupling agent to the wollastonite and mixing it at high speed while heating. The content of the inorganic filler is preferably 0 to 65 parts by weight, more preferably 0.01 to 55 parts by weight, and even more preferably 5 to 50 parts by weight, per 100 parts by weight of Component A. If the content exceeds 65 parts by weight, thermal stability and moist heat resistance may be reduced.

[0093] <Impact modifier> The resin composition of the present invention can be blended with an impact modifier. Examples of impact modifiers include core-shell types in which a vinyl monomer is graft-polymerized onto a composite rubber composed of an acrylic polymer and polyorganosiloxane, butadiene rubber-containing methyl methacrylate graft copolymer rubber, methyl methacrylate-butadiene-styrene copolymer rubber, and acrylic rubber. These are commercially available as "Metablen S2001" and "Metablen S2030" manufactured by Mitsubishi Chemical Corporation, "Kane Ace M711" and "Kane Ace M724" manufactured by Kaneka Corporation, and "Kurariti LA2250" and "Kurariti LA4285" manufactured by Kuraray Co., Ltd. The content of the impact modifier is preferably 0 to 10 parts by weight, more preferably 1 to 8 parts by weight, per 100 parts by weight of Component A. If the content exceeds 10 parts by weight, rigidity may decrease.

[0094] <Release agent> The resin composition of the present invention may further contain a known mold release agent such as a fatty acid ester, a polyolefin wax, a silicone compound, a fluorine compound (such as a fluorine oil represented by polyfluoroalkyl ether), paraffin wax, or beeswax, for the purpose of improving productivity during molding and improving the dimensional accuracy of the molded product.

[0095] Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or dihydric or higher polyhydric alcohols. The carbon number of 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, more preferably 10 to 30 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Fatty acid esters are preferred because the full esters have excellent thermal stability at high temperatures. The acid value of the fatty acid ester is preferably 20 or less (can be 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 (can be substantially 0). These properties can be determined by the method specified in JIS K0070.

[0096] Examples of polyolefin waxes include those with a molecular weight of 1,000 to 10,000, such as 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. These molecular weights are number-average molecular weights measured in terms of standard polystyrene by gel permeation chromatography (GPC). The upper limit of the number-average molecular weight is preferably 6,000, and even more preferably 3,000. The carbon number of the α-olefin component in the polyolefin wax is preferably 60 or less, more preferably 40 or less. More preferred examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. Suitable polyolefin waxes are ethylene homopolymers or copolymers of ethylene and α-olefins having 3 to 60 carbon atoms. The proportion of the α-olefins having 3 to 60 carbon atoms is preferably 20 mol % or less, more preferably 10 mol % or less. A commercially available polyethylene wax is preferably used.

[0097] The content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and even more preferably 0.02 to 3 parts by weight, per 100 parts by weight of component A.

[0098] <Colorant> The resin composition of the present invention can further contain various coloring materials to provide molded articles exhibiting a variety of designs. Examples of dyes and pigments that can be 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, and carbon black.

[0099] The resin composition of the present invention can also be blended with a metallic pigment to achieve a better metallic color. Aluminum powder is a suitable metallic pigment. Furthermore, blending a fluorescent brightening agent or other luminescent fluorescent dye can provide an even better design effect by utilizing the luminescent color. Examples of fluorescent dyes (including fluorescent brightening agents) used in the present invention include coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, perylene-based fluorescent dyes, anthraquinone-based fluorescent dyes, thioindigo-based fluorescent dyes, xanthene-based fluorescent dyes, xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based fluorescent dyes. Among these, coumarin-based fluorescent dyes, benzopyran-based fluorescent dyes, and perylene-based fluorescent dyes are preferred because of their excellent heat resistance and minimal degradation during molding of polycarbonate resins.

[0100] The content of the coloring material is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, relative to 100 parts by weight of the A component.

[0101] <Regarding the manufacturing method of the resin composition> The polycarbonate resin composition of the present invention can be produced by any method. For example, it can be produced by kneading using a single-screw or multi-screw extruder. The polycarbonate resin, polyoxyalkylene dibenzoate, and other components can be mixed all at once, or some of the components can be mixed first and then mixed and kneaded with the rest. The polycarbonate resin composition thus obtained can be molded into automotive parts, electrical and electronic parts, and the like by various known methods, such as injection molding and extrusion molding. [Example]

[0102] The polycarbonate resin composition of the present invention will be specifically described below based on examples. In the following measurement conditions and examples, "parts" respectively represent "parts by weight."

[0103] <Materials used> <Component A: Polycarbonate Resin> A-1: L-1225WX (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 19,700, linear polycarbonate resin) A-2: L-1250WQ (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 25,100, linear polycarbonate resin) A-3: CM1000 (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 16,000, linear polycarbonate resin) A-4: W-0052 (trade name) (manufactured by Teijin Limited, viscosity average molecular weight 19,700, polycarbonate-polydiorganosiloxane copolymer resin) A-5: PC-WB101A (trade name) (manufactured by NINGBO TOPCENTRAL NEW MATERIAL Co., Ltd., viscosity average molecular weight 23,500, recycled branched polycarbonate resin) A-6: PC116A (trade name) (manufactured by Fenghua Hongyu Plastics Co., Ltd., viscosity average molecular weight 20,500, recycled linear polycarbonate resin)

[0104] <Component B: Polyoxyalkylene Dibenzoate> B-1: EB-200 (trade name) (manufactured by Sanyo Chemical Industries, polyethylene glycol dibenzoate, viscosity (25°C): 100 mPa·s, specific gravity (20°C / 4°C): 1.17, molecular weight 350) B-2: EB-300 (trade name) (manufactured by Sanyo Chemical Industries, polyethylene glycol dibenzoate, viscosity (25°C): 130 mPa·s, specific gravity (20°C / 4°C): 1.16, molecular weight 450) B-3: EB-400 (trade name) (manufactured by Sanyo Chemical Industries, polyethylene glycol dibenzoate, viscosity (25°C): 160 mPa·s, specific gravity (20°C / 4°C): 1.15, molecular weight 550) B-4: Ethylene Glycol Dibenzoate (manufactured by Tokyo Chemical Industry Co., Ltd., polyethylene glycol dibenzoate, molecular weight 270) B-5 (comparative example): Bisol 18EN (trade name) (manufactured by Toho Chemical Industry, average molecular weight 1010, polyalkylene bisphenol ether)

[0105] <Component C: Thermoplastic resin> C-1: TRN-MTJ (trade name) (manufactured by Teijin Limited, polyethylene terephthalate) C-2: Juranex 700FP EF201X (trade name) (manufactured by Polyplastics Co., Ltd., polybutylene terephthalate) C-3: Clarastic UT-61 (trade name) (manufactured by Nippon A & L Co., Ltd., acrylonitrile-butadiene-styrene copolymer resin) C-4: Rytec-A BS-207 (trade name) (manufactured by Nippon A & L Co., Ltd., acrylonitrile-styrene copolymer resin)

[0106] <Component D: Phosphorus stabilizer> D-1: 6260PW (trade name) (manufactured by SNGWON Co., Ltd., bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite) D-2: JC-224 (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., ethyl diethylphosphonoacetate) D-3: JP-518Zn (trade name) (manufactured by Johoku Chemical Industry Co., Ltd., zinc stearyl acid phosphate salt) D-4: AX-71 (trade name) (manufactured by ADEKA Corporation, octadecyl phosphate)

[0107] <Other components> (Inorganic filler) E-1: KGP-H40 (trade name) (manufactured by Kansai Mattech Co., Ltd., average fiber length 6.5μm, wollastonite) E-2: GM-6 (trade name) (manufactured by GreaMinerals Co., Ltd., average fiber length 17μm, mica) E-3: Victolite TK-RC (trade name) (manufactured by Koseki Mining Co., Ltd., average fiber length 7.5μm, talc)

[0108] (Impact modifier) F-1: S2030 (trade name) (manufactured by Mitsubishi Chemical Corporation, silicone-acrylic impact modifier)<000​ F-3: LA-4285 (product name) (Kuraray Co., Ltd., acrylic impact modifier)

[0109] (mold release agent) G-1: EW-400 (product name) (Riken Vitamin Co., Ltd., special fatty acid ester) (ultraviolet absorber) H-1: SEESORB701 (product name) (Shipro Chemical Co., Ltd.) (carbon masterbatch) I-1: ROYAL BLACK 90003S (product name) (manufactured by Koshigaya Chemical Industry Co., Ltd., a masterbatch consisting of carbon black and polystyrene resin)

[0110] <Production of Resin Composition> (Examples 1 to 42, Comparative Examples 1 to 3) The components shown in Tables 1 to 3 were premixed in the proportions shown in Tables 1 to 3 and melt-kneaded using a twin-screw extruder [TEX30α-31, manufactured by The Japan Steel Works, Ltd.] at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum of 0 kPa to obtain pellets. The extrusion temperature was 280°C from the first feed port to the die.

[0111] <Evaluation method> The obtained pellets were dried in a hot air circulation dryer at 120° C. for 5 hours or more, and then evaluated by the following evaluation method. The results are shown in Tables 1 to 3.

[0112] 1. Molding appearance evaluation Using an injection molding machine [EC130SX2-4Y manufactured by Toshiba Machine Engineering], square plates (150mm long x 150mm wide x 2.5mm thick) were molded without applying dwell pressure under conditions of a cylinder temperature of 280°C, a mold temperature of 60°C, and an injection speed of 70mm / sec. The appearance of the plates was observed with the naked eye and judged according to the following criteria. ◯: No unevenness or irregularities are observed on the surface. △: Virtually no unevenness or irregularities are observed on the surface. ×: The surface is significantly uneven and rough.

[0113] 2. Thermal stability evaluation Using an injection molding machine [ROBOSHOT α-S100iA manufactured by FANUC], the resin was allowed to remain in the cylinder for 10 minutes at a cylinder temperature of 280°C and a mold temperature of 80°C, after which a plate (50mm wide x 90mm long x 2mm thick) was molded, and the appearance of the third plate was observed with the naked eye and judged according to the following criteria. ◎: The area where silver appeared is 1cm 2 is less than. ○: The area where silver occurred is 1cm 2 More than 5cm 2 is less than. △: The area where silver occurred is 5cm 2 More than 10cm 2 is less than. ×: The area where silver occurred is 10cm 2 That's all.

[0114] 3. Moisture and heat resistance evaluation Using a highly accelerated life tester [EHS-412MD, manufactured by ESPEC], the pellets were subjected to a 24-hour moist heat treatment at 110°C and 100% RH. The MVR of the pellets was then measured before and after treatment at 280°C and 1.2 kgf. The ΔMVR (MVR after treatment - MVR before treatment) was calculated and evaluated according to the following criteria. ○: ΔMVR is less than 20. △: ΔMVR is 20 or more and less than 35. ×: ΔMVR is 35 or more.

[0115] [Table 1]

[0116] [Table 2]

[0117] [Table 3]

[0118] As shown in Tables 1 to 3, the resin composition of the present invention can provide a polycarbonate resin composition that is excellent in thermal stability, moist heat resistance, and appearance of molded products. [Industrial Applicability]

[0119] The resin composition and molded article of the present invention can be used for housings for electrical, electronic and office automation equipment, interior panels, and automotive exterior parts such as roof spoilers, window garnishes and roof panels.

Claims

1. A polycarbonate resin composition containing 0.5 to 20 parts by weight of (B) polyoxyalkylene dibenzoate (component B) per 100 parts by weight of (A) polycarbonate resin (component A).

2. 2. The polycarbonate resin composition according to claim 1, wherein the average molecular weight of component B is 300 to 600.

3. 2. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 100 parts by weight of a thermoplastic resin (C) other than component A, per 100 parts by weight of component A.

4. 4. The polycarbonate resin composition according to claim 3, wherein component C is at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin, polybutylene terephthalate resin, acrylonitrile-butadiene-styrene copolymer resin, and acrylonitrile-styrene copolymer resin.

5. 4. The polycarbonate resin composition according to claim 3, wherein component C is at least one thermoplastic resin selected from the group consisting of polyethylene terephthalate resin and polybutylene terephthalate resin.

6. 6. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 8 parts by weight of a phosphorus-based stabilizer (D) (Component D) per 100 parts by weight of Component A.

7. A molded article made from the resin composition according to any one of claims 1 to 5.

8. The molded article according to claim 7, which is an exterior part for an automobile.

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