Polycarbonate resin composition and molded article comprising the same

Abstract

To provide a polycarbonate resin composition and a molded article comprising the composition, the composition exhibiting superior surface hardness, thermal resistance, hue, and moisture-heat resistance.SOLUTION: This polycarbonate resin composition comprises 0.01-10 pts.wt. of a compound (B) having an epoxy group or a carbodiimide group per 100 pts.wt. of a polycarbonate resin (A), wherein the polycarbonate resin (A) comprises 70 mol% or more, based on all structural units, of a structural unit (a) represented by the following formula (1) and a structural unit (b) derived from a divalent phenol such as 4,4'-bis(2,6-dimethyl)diphenol or bisphenol C. (In formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1-3 carbon atoms; R4 represents an alkyl group having 1-12 carbon atoms, an aryl group having 6-12 carbon atoms, or an aryl-substituted alkyl group having 7-13 carbon atoms; and n and m each independently represent an integer of 1-4).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition having high surface hardness and excellent heat resistance, color and moist heat resistance, and to a molded article made from the same. [Background technology]

[0002] Polycarbonate resin has excellent transparency, impact resistance, heat resistance, and dimensional stability, and is therefore used as an engineering plastic in a wide range of fields, including housings for electrical and electronic devices, interior and exterior parts for automobiles, building materials, furniture, musical instruments, and miscellaneous goods. Furthermore, compared to inorganic glass, it has a lower specific gravity, allowing for lighter weight and excellent productivity, so it is used for windows in automobiles, etc.

[0003] Furthermore, sheets and films using polycarbonate resins are widely used as various display devices and protective parts for automobile interiors by being subjected to additional secondary processing such as coating, lamination, and surface modification.

[0004] However, when uncoated polycarbonate resin is measured in accordance with JIS K5600-5-4, General Test Methods for Paints - Part 5: Mechanical Properties of Coatings - Section 4: Scratch Hardness (Pencil Method), the pencil hardness of polycarbonate resin is only about 2B, which poses an issue for uncoated materials, as their surface is easily scratched.

[0005] Therefore, it is known to use copolymer polycarbonate resins with high surface hardness (for example, Patent Document 1). Also, methods have been described in which polycarbonates or copolycarbonates containing 2,2-bis(4-hydroxy-3-methylphenyl)propane as a structural unit are used (for example, Patent Documents 2 to 6). Although such polycarbonate resins have improved surface hardness, they have the problem of being inferior in heat resistance compared to polycarbonate resins.

[0006] Furthermore, Patent Document 7 describes that polycarbonate resins containing 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine as a structural unit have excellent abrasion resistance when used as binder resins for electrophotographic photoreceptors. However, the inventors' studies have found that polycarbonate resins containing 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine as a structural unit are subject to significant deterioration in a humid and hot environment. Therefore, no polycarbonate resin compositions containing 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine as a structural unit have been reported to date that have good surface hardness, heat resistance, color, and humid and heat resistance. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Patent No. 5173803 [Patent Document 2] Japanese Patent Application Publication No. 64-069625 [Patent Document 3] Japanese Patent Application Publication No. 08-183852 [Patent Document 4] Japanese Patent Application Publication No. 08-034846 [Patent Document 5] Japanese Patent Application Laid-Open No. 2002-117580 [Patent Document 6] Patent No. 3768903 [Patent Document 7] Patent No. 3297469 Summary of the Invention [Problem to be solved by the invention]

[0008] As described above, there is a demand for polycarbonate resin compositions having high surface hardness and excellent heat resistance, color and moist heat resistance, and for molded articles made from such compositions. Therefore, an object of the present invention is to provide a polycarbonate resin composition having high surface hardness and excellent heat resistance, color and moist heat resistance, and a molded article made from the same. [Means for solving the problem]

[0009] As a result of extensive research into achieving the above object, the present inventors have found that a polycarbonate resin composition comprising a polycarbonate resin having specific structural units and a compound having an epoxy group or a carbodiimide group, and a molded article comprising the same, can solve the above problems, and have arrived at the present invention. That is, according to the present invention, the following 1 to 10 are provided.

[0010] 1. A structural unit (a) represented by the following formula (1), and [ka] (In formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R4 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms; and n and m each independently represent an integer of 1 to 4.) Structural unit (b) represented by the following formula (2): [ka] (In formula (2), R5 and R6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; o and p each independently represent an integer of 1 to 4; and X is a single bond or at least one group selected from the group consisting of the following formula (3):) [ka] (In formula (3), R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14each independently represents at least one 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 15 and R 16 each independently represents at least one 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; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7. A polycarbonate resin composition comprising 100 parts by weight of a polycarbonate resin (A) containing 70 mol % or more of the above based on all structural units, and 0.01 to 10 parts by weight of a compound (B) having an epoxy group or a carbodiimide group.

[0011] 2. The polycarbonate resin composition according to item 1 above, wherein the content of the structural unit (a) is 10 mol % or more. 3. The polycarbonate resin composition according to item 1 or 2 above, wherein the structural unit (a) is a structural unit derived from 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine or 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine. 4. The polycarbonate resin composition according to any one of items 1 to 3 above, which has a pencil hardness of H or more as measured in accordance with JIS K5600. 5. The polycarbonate resin composition according to any one of items 1 to 4 above, which has a glass transition temperature of 130 to 300°C. 6. The polycarbonate resin composition according to any one of items 1 to 5 above, wherein the b* value measured on a molded plate having a thickness of 6.2 mm is 40 or less. 7. The polycarbonate resin composition according to any one of items 1 to 6 above, wherein the molecular weight retention after a wet heat test measured by the following test method is 72% or more. Test method: The molded plate was left to stand for 1000 hours at 85°C x 85% RH in a small environmental tester SH-242 manufactured by Espec Corp. After that, the viscosity average molecular weight of the treated molded plate was measured, and the molecular weight retention rate was calculated using the following formula. Molecular weight retention rate (%) = (viscosity average molecular weight after test / viscosity average molecular weight before test) × 100 8. A molded article obtained by injection molding the polycarbonate resin composition according to any one of items 1 to 7 above. 9. A sheet or film obtained by extrusion molding the polycarbonate resin composition according to any one of items 1 to 7 above. 10. An automobile interior part using the molded product described in the preceding paragraph 8 or the sheet or film described in the preceding paragraph 9. [Effects of the Invention]

[0012] The polycarbonate resin composition of the present invention and molded articles made therefrom are excellent in surface hardness, heat resistance, color, and moist heat resistance, and are therefore particularly suitable for use as automobile interior parts, and therefore have exceptional industrial effects. DETAILED DESCRIPTION OF THE INVENTION

[0013] The present invention will be described in detail below.

[0014] <Polycarbonate resin composition> The polycarbonate resin composition of the present invention comprises a structural unit (a) represented by the following formula (1), and

[0015] [ka]

[0016] (In formula (1), R1, R2, and R3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R4 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms; and n and m each independently represent an integer of 1 to 4.) Structural unit (b) represented by the following formula (2):

[0017] [ka]

[0018] (In formula (2), R5 and R6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; o and p each independently represent an integer of 1 to 4; and X is a single bond or at least one group selected from the group consisting of the following formula (3):)

[0019] [ka]

[0020] (In formula (3), R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 each independently represents at least one 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 15 and R 16each independently represents at least one 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; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7. The polycarbonate resin composition contains 100 parts by weight of a polycarbonate resin (A) containing 70 mol % or more of the above based on all structural units, and 0.01 to 10 parts by weight of a compound (B) having an epoxy group or a carbodiimide group.

[0021] <Polycarbonate resin (A)> Of all the structural units in the polycarbonate resin (A), the structural units (a) and (b) account for 70 mol % or more, preferably 80 mol % or more, and more preferably 90 mol % or more.

[0022] In the polycarbonate resin (A), the content of the structural unit (a) represented by the formula (1) is preferably 10 mol % or more, more preferably 10 to 75 mol %, even more preferably 15 to 60 mol % or more, and particularly preferably 20 to 50 mol % or more, relative to 100 mol % of all structural units excluding the terminals. If the content is below the lower limit, the pencil hardness and glass transition temperature may decrease, whereas if the content exceeds the upper limit, the glass transition temperature may increase and the flowability may decrease.

[0023] The proportion of the structural unit (a) may be achieved by a polycarbonate copolymer or by mixing polycarbonate resins with different compositional proportions (polycarbonate blend).

[0024] In the structural unit (a), R1, R2, and R3 are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R4 is an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and most preferably a phenyl group.

[0025] Examples of dihydric phenols from which the structural unit (a) is derived include 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxy-3,5-dimethylphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxy-3-isopropylphenyl)phthalimidine, etc. Preferred are 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine and 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine, and the most preferred dihydric phenol is 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.

[0026] In the structural unit (b) represented by the formula (2), R5 and R6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, or an n-propyl group, and more preferably a hydrogen atom or a methyl group.

[0027] In addition, the bonding positions of R5 and R6 in the formula (2) are preferably the 5-position relative to X.

[0028] In the formula (3), R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14are each independently at least one 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, and are preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0029] In addition, in the formula (3), R 15 and R 16 are each independently at least one 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, and are preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0030] In the formula (3), a is an integer of 1 to 10, preferably an integer of 1 to 4, and more preferably an integer of 1. b is an integer of 4 to 7, and preferably an integer of 5.

[0031] In the formula (3), an isopropylidene group, a cyclohexylidene group, a methyl-substituted cyclohexylidene group, and a fluorene group are preferred, with an isopropylidene group being particularly preferred.

[0032] Examples of dihydric phenols that can be used to derive the structural unit (b) represented by the formula (2) include 4,4'-bis(2,6-dimethyl)diphenol, 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter sometimes referred to as bisphenol C), 2,2-bis(2,3-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(3-methyl-4-hydroxyphenyl)decane, 1,1-bis(2,3-dimethyl-4-hydroxyphenyl)decane, α,α'-bis(4-hydroxy-3-methylphenyl)-o-diisopropylbenzene, α,α'-bis(4-hydroxy-3-methylphenyl)-m-diisopropylbenzene, α,α'-bis(4-hydroxy-3-methylphenyl)-p-diisopropylbenzene, and 1,1-bis(4-hydroxy-3-methylphenyl)-3,3,5 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 2,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4-hydroxy-3-methylphenyl-4-hydroxy-3-methylbenzoate, and the like.

[0033] Among the above dihydric phenols, bisphenol C, bisphenol OCTMC, bisphenol OCZ, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred, and bisphenol C is most preferred.

[0034] In the polycarbonate resin of the present invention, the proportion of structural units (b) relative to 100 mol % of all structural units excluding terminals is preferably 25 to 90 mol %, more preferably 40 to 85 mol %, and most preferably 50 to 80 mol %. A proportion of structural units (b) within the above range is preferred because it provides an excellent balance between surface hardness and heat resistance.

[0035] The polycarbonate resin of the present invention may further contain other copolymerization units in an amount of 30 mol % or less, preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less of all structural units, as long as the effects of the present invention are not impaired.

[0036] Other dihydroxy compounds that can lead to copolymerization units include hydroquinone, resorcinol, orcinol, 2,2-bis(4-hydroxyphenyl)norbornene, 1,3-bis(4-hydroxyphenyl)adamantane; 2,2-bis(4-hydroxyphenyl)adamantane; 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentaenebisphenoxyethanolfluorene, and the like.

[0037] Other diol compounds that can be used to derive copolymerization units include isosorbide:1,4:3,6-dianhydro-D-sorbitol, tricyclodecane dimethanol (TCDDM), 4,8-bis(hydroxymethyl)tricyclodecane, tetramethylcyclobutanediol (TMCBD), 2,2,4,4-tetramethylcyclobutane-1,3-diol, mixed isomers, cis / trans-1,4-cyclohexanedimethanol (CHDM), cis / trans-1,4-bis(hydroxymethyl)cyclohexane, and cyclohex-1,4-yl ethene. Examples of suitable cyclohexanedimethanol include trans-1,4-cyclohexanedimethanol (tCHDM), trans-1,4-bis(hydroxymethyl)cyclohexane, cis-1,4-cyclohexanedimethanol (cCHDM), cis-1,4-bis(hydroxymethyl)cyclohexane, cis-1,2-cyclohexanedimethanol, 1,1'-bi(cyclohexyl)-4,4'-diol, spiroglycol, dicyclohexyl-4,4'-diol, 4,4'-dihydroxybicyclohexyl, and poly(ethylene glycol).

[0038] <Compound (B) Having an Epoxy Group or a Carbodiimide Group> In the polycarbonate resin composition of the present invention, a compound (B) having an epoxy group or a carbodiimide group is used from the viewpoints of wet heat resistance, molding stability and color.

[0039] Examples of the compound having an epoxy group include poly(styrene-glycidyl methacrylate), poly(ethylene-glycidyl methacrylate), 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and a mixture of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Poly(styrene-glycidyl methacrylate) and poly(ethylene-glycidyl methacrylate) are preferred, and poly(styrene-glycidyl methacrylate) is more preferred.

[0040] Examples of compounds having a carbodiimide group include aliphatic carbodiimides, aliphatic polycarbodiimides, aromatic carbodiimides, aromatic polycarbodiimides, and cyclic carbodiimides, with aliphatic carbodiimides and aliphatic polycarbodiimides being preferred, and aliphatic polycarbodiimides being more preferred.

[0041] Specific examples of the compound having an epoxy group include poly(styrene-glycidyl methacrylate) (e.g., G-0250SP, G-0130SP, and G-0105SA manufactured by NOF Corporation), poly(ethylene-glycidyl methacrylate) (e.g., BF-2C, BF-E, and BF-30C manufactured by Sumitomo Chemical Co., Ltd.), and CG5001), poly(ethylene-glycidyl methacrylate-vinyl acetate) (e.g., BF-2B manufactured by Sumitomo Chemical Co., Ltd., BF-7B manufactured by Sumitomo Chemical Co., Ltd.), poly(ethylene-glycidyl methacrylate-methyl acrylate) (e.g., BF-7L manufactured by Sumitomo Chemical Co., Ltd., MF-7M manufactured by Sumitomo Chemical Co., Ltd.), 3',4'-epoxycyclohexylmethyl-3,4 ... hexanecarboxylate (e.g., CELLOXIDE 2021P, manufactured by Daicel Corporation), a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150, manufactured by Daicel Corporation), and a mixture of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (e.g., EHPE3150CE, manufactured by Daicel Corporation).

[0042] Specific examples of the compound having a carbodiimide group include aliphatic polycarbodiimides (e.g., HMV-15CA manufactured by Nisshinbo Chemical Inc., LA-1 manufactured by Nisshinbo Chemical Inc.), carbodiimide-modified isocyanates (e.g., V-05 manufactured by Nisshinbo Chemical Inc.), aromatic carbodiimides (e.g., Stbaxol I manufactured by LANXESS), aromatic polycarbodiimides (e.g., Stbaxol P manufactured by LANXESS, Stbaxol P100 manufactured by LANXESS), and cyclic carbodiimides (e.g., TCC-NP manufactured by Teijin Limited).

[0043] The amount of compound (B) having an epoxy group or a carbodiimide group to be blended is in the range of 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, even more preferably 0.08 to 1 part by weight, and particularly preferably 0.1 to 0.8 parts by weight, per 100 parts by weight of polycarbonate resin (A) from the viewpoints of moist heat resistance, molding stability, and color.

[0044] <Manufacturing method of polycarbonate resin> The raw material monomers for the polycarbonate resin (A) used in the polycarbonate resin composition of the present invention are dihydric phenols represented by the following formula (4) and

[0045] [ka]

[0046] (In formula (4), R1, R2, and R3 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R4 represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms; and n and m each independently represent an integer of 1 to 4.) A dihydric phenol represented by the following formula (5):

[0047] [ka]

[0048] (In formula (5), R5 and R6 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, o and p each independently represent an integer of 1 to 4, and X is a single bond or at least one group selected from the group consisting of the following formula (3):

[0049] [ka]

[0050] (In formula (3), R7, R8, R9, R 10 , R 11 , R 12 , R 13 and R 14 each independently represents at least one 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 15 and R 16 each independently represents at least one 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; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7. Includes.

[0051] Examples of the dihydric phenol represented by the above formula (4) include the dihydric phenols that derive the above-mentioned structural unit (a).

[0052] Examples of the dihydric phenol represented by the above formula (5) include the dihydric phenols that derive the above-mentioned structural unit (b).

[0053] The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention may be copolymerized with other dihydroxy compounds or diol compounds to the extent that the properties of the polycarbonate resin composition are not impaired. Examples of other dihydroxy compounds include the dihydroxy compounds and diol compounds that derive the above-mentioned other copolymerization units.

[0054] The polycarbonate resin (A) used in the polycarbonate resin composition of the present invention is obtained by reacting the dihydric phenol compound with a carbonate precursor. Examples of reaction methods include interfacial polycondensation, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds. In the case of interfacial polycondensation, a monohydric phenol-based end-capping agent is usually used.

[0055] The polycarbonate resin (A) used in the polycarbonate resin composition contains a polyester carbonate copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid. 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 dicarboxylic acid, as well as alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These carboxylic acids may be copolymerized to the extent that the objective is not impaired. Furthermore, the polycarbonate copolymer may also be copolymerized with a structural unit containing a polyorganosiloxane unit, if necessary.

[0056] The polycarbonate resin (A) used in the polycarbonate resin composition can also be made into a branched polycarbonate by copolymerizing a structural unit containing a trifunctional or higher polyfunctional aromatic compound, if necessary.

[0057] Suitable examples of trifunctional or higher polyfunctional aromatic compounds used in branched polycarbonates include 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 trisphenols such as 4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol. Of these, 1,1,1-tris(4-hydroxyphenyl)ethane is preferred. The structural units derived from such polyfunctional aromatic compounds preferably account for 0.03 to 1.5 mol %, more preferably 0.1 to 1.2 mol %, and particularly preferably 0.2 to 1.0 mol %, of a total of 100 mol % including structural units derived from other dihydric phenol components.

[0058] The branched structural units may be derived not only from polyfunctional aromatic compounds but also from side reactions occurring during polymerization by melt transesterification without using polyfunctional aromatic compounds. 1 It can be calculated by H-NMR measurement.

[0059] In reactions using, for example, phosgene as a carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent. Examples of acid binders include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine. Examples of solvents include halogenated hydrocarbons such as methylene chloride and chlorobenzene. To promote the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can also be used. The reaction temperature is usually 0 to 40°C, and the reaction time is several minutes to 5 hours.

[0060] Transesterification using, for example, a carbonate diester as a carbonate precursor is carried out by stirring a predetermined proportion of aromatic dihydroxy component with the carbonate diester under heating in an inert gas atmosphere, and distilling off the resulting alcohol or phenol. The reaction temperature varies depending on the boiling point of the resulting alcohol or phenol, but is typically in the range of 120 to 300°C. The reaction is completed by reducing the pressure from the beginning of the reaction to distill off the resulting alcohol or phenol. A catalyst typically used in transesterification can also be used to promote the reaction. Examples of carbonate diesters used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred.

[0061] Commonly used monofunctional phenols can be used as end-capping agents. In particular, in reactions using phosgene as a carbonate precursor, monofunctional phenols are commonly used as end-capping agents to control molecular weight. Furthermore, the resulting polycarbonate copolymers have superior thermal stability compared to those without end-capping, since their ends are blocked with groups based on monofunctional phenols. Specific examples of the monofunctional phenols include phenol, 3-methylphenol, 4-methylphenol, 3-propylphenol, 4-propylphenol, 1-phenylphenol, 2-phenylphenol, p-tert-butylphenol, p-cumylphenol, isooctylphenol, 4-octylphenol, 4-nonylphenol, 4-dodecylphenol, 4-pentadecylphenol, and 3-pentadecylphenol.

[0062] <Method for producing polycarbonate resin composition> The polycarbonate resin composition of the present invention is preferably prepared by blending the polycarbonate resin (A) and the compound (B) having an epoxy group or a carbodiimide group in a molten state. As a method for blending in a molten state, an extruder is generally used, and the molten resin is kneaded at a temperature of 200 to 400°C and pelletized. This produces a polycarbonate resin composition in which the polycarbonate resin (A) and the compound (B) having an epoxy group or a carbodiimide group are uniformly blended. The configuration of the extruder and the screw are not particularly limited.

[0063] (Other ingredients) The polycarbonate resin composition of the present invention may contain additives other than the compound (B) having an epoxy group or a carbodiimide group, such as a heat stabilizer, a mold release agent, an ultraviolet absorber, a bluing agent, an antistatic agent, a flame retardant, a heat ray shielding agent, a fluorescent dye (including a fluorescent brightener), a pigment, a light diffusing agent, a reinforcing filler, a sliding modifier, other resins, or elastomers.

[0064] Examples of heat stabilizers include phosphorus-based heat stabilizers, sulfur-based heat stabilizers, and hindered phenol-based heat stabilizers. Phosphorus-based heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and their esters. Specific examples include bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, [1,1-biphenyl]-4,4-diylbis[bis(2,4-di-tert-butylphenoxy)phosphine], 3,9-bis(2,6-di-tert-butylphenyl)propionate ... butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane is preferred, and tris(2,4-di-tert-butylphenyl)phosphite, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate stearyl, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane are more preferred.

[0065] The amount of the heat stabilizer to be added is preferably in the range of 0.001 to 0.5 parts by weight, more preferably 0.005 to 0.4 parts by weight, and even more preferably 0.01 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0066] Preferably, the release agent is one that is composed of 90% by weight or more of an ester of alcohol and fatty acid. Specific examples of the ester of alcohol and fatty acid include ester of monohydric alcohol and fatty acid, and partial or complete ester of polyhydric alcohol and fatty acid. Specific examples of the ester of monohydric alcohol and saturated fatty acid include stearyl stearate, palmityl palmitate, butyl stearate, methyl laurate, and isopropyl palmitate. Stearyl stearate is preferred. Examples of partial or full esters of polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride, stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetrapelargonate, propylene glycol monostearate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate, and full or partial esters of dipentaerythritol such as dipentaerythritol hexastearate. Among these esters, stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and mixtures of stearic acid triglyceride and stearyl stearate are preferred, with stearic acid monoglyceride and pentaerythritol tetrastearate being more preferred.

[0067] The amount of the release agent to be added is preferably in the range of 0.05 to 0.5 parts by weight, more preferably 0.1 to 0.4 parts by weight, and even more preferably 0.12 to 0.3 parts by weight, relative to 100 parts by weight of the polycarbonate resin.

[0068] (viscosity average molecular weight) The viscosity average molecular weight of the polycarbonate resin composition of the present invention is preferably 6,000 to 30,000, more preferably 8,000 to 28,000, and even more preferably 10,000 to 25,000. A molecular weight within the above range is preferred because it provides excellent mechanical properties, productivity, and processability.

[0069] The viscosity average molecular weight of the polycarbonate resin composition in the present invention is determined by first determining the specific viscosity (η SP ) was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of the resin composition in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0070] (Pencil hardness) The pencil hardness of the polycarbonate resin composition of the present invention is preferably H or higher, more preferably 2H or higher, and even more preferably 3H or higher. Pencil hardness refers to the hardness at which no scratch marks remain when the polycarbonate resin composition of the present invention is scratched with a pencil having a specific pencil hardness. The pencil hardness used in the surface hardness test for coating films, which can be measured according to JIS K-5600, is preferably used as an index. Pencil hardness decreases in the following order: 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B, 5B, and 6B, with the hardest being 9H and the softest being 6B.

[0071] (glass transition temperature: Tg) The glass transition temperature (Tg) of the polycarbonate resin composition of the present invention is preferably in the range of 130 to 300°C, more preferably 135 to 250°C, even more preferably 140 to 200°C, and particularly preferably 145 to 180°C. A temperature within the above range is preferred, as it provides excellent heat resistance and flowability. The glass transition temperature (Tg) is measured using a Model 2910 DSC manufactured by TA Instruments Japan, Inc., at a heating rate of 20°C / min.

[0072] (b* value) The b* value measured on a 2 mm thick molded plate of the polycarbonate resin composition of the present invention is preferably 40 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, or 5 or less.

[0073] (Moisture and heat resistance (molecular weight retention rate (%))) The moist heat resistance of the polycarbonate resin composition of the present invention is measured by the following method, and the molecular weight retention is preferably 72% or more, more preferably 75% or more, even more preferably 80% or more, and particularly preferably 85% or more.

[0074] Test method: The molded plate was left to stand for 1000 hours at 85°C x 85% RH in a small environmental tester SH-242 manufactured by Espec Corp. After that, the viscosity average molecular weight of the treated molded plate was measured, and the molecular weight retention rate was calculated using the following formula. Molecular weight retention rate (%) = (viscosity average molecular weight after test / viscosity average molecular weight before test) × 100

[0075] (Molding method and molded product) The polycarbonate resin composition of the present invention can be molded by any of the general methods used for molding polycarbonate resin compositions, such as injection molding, extrusion molding, compression molding, solution casting, etc. In particular, injection molding to form a molded product and extrusion molding to form a sheet or film are preferably used.

[0076] The polycarbonate resin composition of the present invention and molded articles made thereof have excellent surface hardness, heat resistance, hue, and moist heat resistance, and are therefore particularly suitable for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dial plates, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts. [Example]

[0077] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Evaluation was performed according to the following methods. (1) Composition ratio 40 mg of the sample was dissolved in 0.6 mL of deuterated chloroform, and the polymer composition ratio (molar ratio) was calculated from the integral ratio of each structural unit by proton NMR using a JNM-AL400 manufactured by JEOL Ltd. (2) Pencil hardness Measurements were carried out using a resin plate according to JIS K5600 under the conditions of load: 750 g, measurement speed: 50 mm / min, measurement distance: 7 mm, and pencil: Hi-uni manufactured by Mitsubishi Pencil Co., Ltd., and the surface condition was evaluated visually. (3) Glass transition temperature Using 8 mg of sample, measurements were performed using a thermal analysis system DSC-2910 manufactured by TA Instruments Co., Ltd. in accordance with JIS K7121 under conditions of a nitrogen atmosphere (nitrogen flow rate: 40 ml / min) and a heating rate of 20°C / min. (4) b* value The b* value at a 2 mm thick section of the resin plate was evaluated using a color and turbidity simultaneous measurement meter COH400 manufactured by Nippon Denshoku Industries Co., Ltd. (5) Viscosity average molecular weight The specific viscosity (η SP ) was measured using an Ostwald viscometer from a solution of 0.7 g of sample dissolved in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7 (6) Moisture and heat resistance (molecular weight retention rate (%)) The resin plate was subjected to static treatment for 1000 hours under conditions of 85°C x 85% RH in a small environmental tester SH-242 manufactured by Espec Corp. Thereafter, the viscosity average molecular weight of the treated molded plate was measured, and the molecular weight retention rate was calculated using the following formula. Molecular weight retention rate (%) = (viscosity average molecular weight after test / viscosity average molecular weight before test) × 100

[0078] [Example 1] <Production of polycarbonate resin> A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 17,508 parts by weight of ion-exchanged water and 10,475 parts by weight of 25% aqueous sodium hydroxide solution under a nitrogen atmosphere. 2,573 parts by weight of 2-phenyl-3,3-bis(p-hydroxyphenyl)phthalimidine (manufactured by Shanxi Liuqing Phenol Co., Ltd., hereafter referred to as PPPBP) as a dihydric phenol, 3,113 parts by weight of 2,2-bis(4-hydroxy-3-methylphenyl)propane (manufactured by Honshu Chemical Co., Ltd., hereafter referred to as BPC), and 11.37 parts by weight of hydrosulfite (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved therein. 20,670 parts by weight of methylene chloride was added, and 2,500 parts by weight of phosgene was bubbled in over 70 minutes at 18-20°C with stirring. Then, 1,496 parts by weight of 25% aqueous sodium hydroxide solution and 89.79 parts by weight of p-tert-butylphenol (manufactured by DIC, hereafter referred to as PTBP) were added and stirred. During the reaction, 4.723 parts by weight of triethylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) was added, and the reaction was terminated after stirring at 25-30°C for 1.5 hours. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the organic phase was washed with acidic hydrochloric acid water. After that, the organic phase was repeatedly washed with ion-exchanged water until the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water. The aqueous phase was then dropped into warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The resulting solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 1.0 part by weight of G-0250SP (NOF Corporation, poly(styrene-glycidyl methacrylate)), a compound with an epoxy group, and 0.05 parts by weight of Irganox 1076 (BASF, hindered phenol-based antioxidant) as a thermal stabilizer were added. The mixture was then melt-kneaded in a vented twin-screw extruder (Technovel Corporation, KZW15-25MG) at a cylinder and die temperature of 290°C to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for at least 12 hours and then molded into a resin plate (2 mm thick) for evaluation using an injection molding machine. The evaluation results are shown in Table 1.

[0079] [Example 2] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> This was produced in the same manner as in Example 1, except that 1.0 part by weight of BF-2C (poly(ethylene-glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd.), a compound having an epoxy group, was used instead of G-0250SP. The evaluation results are shown in Table 1.

[0080] [Example 3] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> This was produced in the same manner as in Example 1, except that 1.0 part by weight of BF-E (poly(ethylene-glycidyl methacrylate) manufactured by Sumitomo Chemical Co., Ltd.), a compound having an epoxy group, was used instead of G-0250SP. The evaluation results are shown in Table 1.

[0081] [Example 4] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> The production was carried out in the same manner as in Example 1, except that 1.0 part by weight of HMV-15CA (aliphatic polycarbodiimide, manufactured by Nisshinbo Chemical Inc.), a compound having a carbodiimide group, was used instead of G-0250SP. The evaluation results are shown in Table 1.

[0082] [Example 5] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> This was produced in the same manner as in Example 1, except that 1.0 part by weight of Stabaxol P (manufactured by LANXESS, aromatic polycarbodiimide), a compound having a carbodiimide group, was used instead of G-0250SP. The evaluation results are shown in Table 1.

[0083] [Reference example 1] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.05 parts by weight of Irganox 1076 was added as a heat stabilizer. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 1.

[0084] [Table 1]

[0085] [Example 6] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> Except for using 0.10 parts by weight of G-0250SP, the production was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0086] [Example 7] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> Except for using 0.25 parts by weight of G-0250SP, the production was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0087] [Example 8] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> Except for using 0.50 parts by weight of G-0250SP, the production was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0088] [Example 9] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> Except for using 0.75 parts by weight of G-0250SP, the production was carried out in the same manner as in Example 1. The evaluation results are shown in Table 2.

[0089] [Example 10] <Production of polycarbonate resin> It was produced in the same manner as in Example 1. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 1, except that 0.10 parts by weight of HMV-15CA was used instead of G-0250SP. The evaluation results are shown in Table 2.

[0090] [Table 2]

[0091] [Example 11] <Production of polycarbonate resin> A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 13,091 parts by weight of ion-exchanged water and 7,832 parts by weight of 25% aqueous sodium hydroxide solution under a nitrogen atmosphere. 1,374 parts by weight of dihydric phenols PPPBP, 2,685 parts by weight of BPC, and 8.119 parts by weight of hydrosulfite were dissolved therein. Then, 15,455 parts by weight of methylene chloride was added, and 1,800 parts by weight of phosgene was bubbled in over 80 minutes at 18-20°C with stirring. Subsequently, 1,119 parts by weight of 25% aqueous sodium hydroxide solution and 67.13 parts by weight of PTBP were added and stirred. During the reaction, 3.531 parts by weight of triethylamine was added, and the mixture was stirred at 25-30°C for 1.5 hours, at which point the reaction was terminated. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, the mixture was washed with acidic hydrochloric acid water. After that, it was repeatedly washed with ion-exchanged water, and when the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50-80°C to evaporate off the solvent, and a flaky solid was obtained. The obtained solid was filtered and dried at 120°C for 24 hours, and a white flaky polycarbonate resin was obtained. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 1.0 part by weight of G-0250SP and 0.05 part by weight of Irganox 1076 as a heat stabilizer were added. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 3.

[0092] [Example 12] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> The product was produced in the same manner as in Example 11, except that 1.0 part by weight of BF-2C was used instead of G-0250SP. The evaluation results are shown in Table 3.

[0093] [Example 13] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> The product was produced in the same manner as in Example 11, except that 1.0 part by weight of BF-E was used instead of G-0250SP. The evaluation results are shown in Table 3.

[0094] [Example 14] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 11, except that 1.0 part by weight of HMV-15CA was used instead of G-0250SP. The evaluation results are shown in Table 3.

[0095] [Example 15] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> This was produced in the same manner as in Example 11, except that 1.0 part by weight of Stabaxol I (aromatic carbodiimide, manufactured by LANXESS), a compound having a carbodiimide group, was used instead of G-0250SP. The evaluation results are shown in Table 3.

[0096] [Example 16] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 11, except that 1.0 part by weight of Stabaxol P was used instead of G-0250SP. The evaluation results are shown in Table 3.

[0097] [Reference example 2] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.05 parts by weight of Irganox 1076 was added as a heat stabilizer. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 3.

[0098] [Table 3]

[0099] [Example 17] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> Except for using 0.10 parts by weight of G-0250SP, the preparation was carried out in the same manner as in Example 11. The evaluation results are shown in Table 4.

[0100] [Example 18] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> Except for using 0.25 parts by weight of G-0250SP, the preparation was carried out in the same manner as in Example 11. The evaluation results are shown in Table 4.

[0101] [Example 19] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> Except for using 0.50 parts by weight of G-0250SP, the preparation was carried out in the same manner as in Example 11. The evaluation results are shown in Table 4.

[0102] [Example 20] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> Except for using 0.75 parts by weight of G-0250SP, the preparation was carried out in the same manner as in Example 11. The evaluation results are shown in Table 4.

[0103] [Example 21] <Production of polycarbonate resin> Produced in the same manner as in Example 11. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 11, except that 0.10 parts by weight of HMV-15CA was used instead of G-0250SP. The evaluation results are shown in Table 4.

[0104] [Table 4]

[0105] [Example 22] <Production of polycarbonate resin> A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 17,508 parts by weight of ion-exchanged water and 8,145 parts by weight of 25% aqueous sodium hydroxide under a nitrogen atmosphere. 2,000 parts by weight of dihydric phenols PPPBP, 2,420 parts by weight of BPC, and 8.842 parts by weight of hydrosulfite were dissolved in the reaction mixture. 16,072 parts by weight of methylene chloride was added, and 1,800 parts by weight of phosgene was bubbled in over 80 minutes at 18-20°C with stirring. Subsequently, 1,163 parts by weight of 25% aqueous sodium hydroxide and 121.95 parts by weight of 4-dodecylphenol (Sigma-Aldrich, hereafter referred to as 4DDP) were added and stirred. After adding 3.67 parts by weight of triethylamine, the reaction was continued for 1.5 hours at 25-30°C, whereupon the reaction was terminated. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, and repeatedly washed with ion-exchanged water. When the washings became neutral, they were washed with hydrochloric acid-acidic water. After that, the solution was repeatedly washed with ion-exchanged water. When the conductivity of the aqueous phase became almost the same as that of the ion-exchanged water, it was dropped into warm water maintained at 50-80°C, and the solvent was evaporated to obtain a flaky solid. The obtained solid was filtered and dried at 120°C for 24 hours to obtain a white flaky polycarbonate resin. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 1.0 part by weight of G-0250SP and 0.05 part by weight of Irganox 1076 as a heat stabilizer were added. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 5.

[0106] [Example 23] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The product was produced in the same manner as in Example 22, except that 1.0 part by weight of BF-2C was used instead of G-0250SP. The evaluation results are shown in Table 5.

[0107] [Example 24] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The product was produced in the same manner as in Example 22, except that 1.0 part by weight of BF-E was used instead of G-0250SP. The evaluation results are shown in Table 5.

[0108] [Example 25] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 22, except that 1.0 part by weight of HMV-15CA was used instead of G-0250SP. The evaluation results are shown in Table 5.

[0109] [Example 26] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> Production was carried out in the same manner as in Example 22, except that 1.0 part by weight of Stabaxol P was used instead of G-0250SP. The evaluation results are shown in Table 5.

[0110] [Reference example 3] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.05 parts by weight of Irganox 1076 was added as a heat stabilizer. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 5.

[0111] [Table 5]

[0112] [Example 27] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 22, except that 0.10 parts by weight of G-0250SP was used. The evaluation results are shown in Table 6.

[0113] [Example 28] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 22, except that 0.25 parts by weight of G-0250SP was used. The evaluation results are shown in Table 6.

[0114] [Example 29] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The product was produced in the same manner as in Example 22, except that 0.50 parts by weight of G-0250SP was used. The evaluation results are shown in Table 6.

[0115] [Example 30] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 22, except that 0.75 parts by weight of G-0250SP was used. The evaluation results are shown in Table 6.

[0116] [Example 31] <Production of polycarbonate resin> Produced in the same manner as in Example 22. <Production of Polycarbonate Resin Composition> The preparation was carried out in the same manner as in Example 22, except that 0.10 parts by weight of HMV-15CA was used instead of G-0250SP. The evaluation results are shown in Table 6.

[0117] [Table 6]

[0118] [Example 32] <Production of polycarbonate resin> Production was carried out in the same manner as in Example 11, except that 117.3 parts by weight of 4DDP was used instead of 67.13 parts by weight of PTBP. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 11. The evaluation results are shown in Table 7.

[0119] [Example 33] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 12. The evaluation results are shown in Table 7.

[0120] [Reference example 4] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.05 parts by weight of Irganox 1076 was added as a heat stabilizer. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 7.

[0121] [Table 7]

[0122] [Example 34] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 17. The evaluation results are shown in Table 8.

[0123] [Example 35] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 18. The evaluation results are shown in Table 8.

[0124] [Example 36] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 19. The evaluation results are shown in Table 8.

[0125] [Example 37] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 20. The evaluation results are shown in Table 8.

[0126] [Example 38] <Production of polycarbonate resin> Produced in the same manner as in Example 32. <Production of Polycarbonate Resin Composition> It was produced in the same manner as in Example 21. The evaluation results are shown in Table 8.

[0127] [Table 8]

[0128] [Comparative Example 1] <Production of polycarbonate resin> The production was carried out in the same manner as in Example 1, except that 1,470 parts by weight of PPPBP and 3,411 parts by weight of 2,2-bis(4-hydroxyphenyl)propane (manufactured by Nippon Steel Chemical & Material Co., Ltd., hereinafter referred to as BPA) were used as the dihydric phenol. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.05 parts by weight of Irganox 1076 was added as a heat stabilizer. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 9.

[0129] Comparative Example 2 <Production of polycarbonate resin> It was produced in the same manner as in Comparative Example 1. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.50 parts by weight of G-0250SP and 0.05 parts by weight of Irganox 1076 as a heat stabilizer were added. The mixture was then melt-kneaded at a cylinder and die temperature of 290°C using a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 9.

[0130] Comparative Example 3 <Production of polycarbonate resin> It was produced in the same manner as in Comparative Example 1. <Production of Polycarbonate Resin Composition> To 100 parts by weight of the resulting polycarbonate resin, 0.50 parts by weight of HMV-15CA and 0.05 parts by weight of Irganox 1076 as a heat stabilizer were added. The mixture was then melt-kneaded in a vented twin-screw extruder (KZW15-25MG, manufactured by Technovel Co., Ltd.) at a cylinder and die temperature of 290°C to obtain a polycarbonate resin composition. The resulting polycarbonate resin composition was dried at 120°C for 12 hours or more and then molded into a resin plate for evaluation using an injection molding machine. The evaluation results are shown in Table 9.

[0131] [Table 9] [Industrial Applicability]

[0132] The polycarbonate resin composition of the present invention and molded articles made thereof have excellent surface hardness, heat resistance, hue, and moist heat resistance, and therefore do not require a coating treatment. They can be used for automobile interior parts such as lamp lenses for interior lighting, display meter covers, meter dial plates, various switch covers, display covers, heat control panels, instrument panels, center clusters, center panels, room lamp lenses, various display devices such as head-up displays, protective parts, and light-transmitting parts.

Claims

1. A structural unit (a) represented by the following formula (1), and 【Chemical 1】 (In formula (1), R １ , R ２ and R ３ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms; R ４ represents an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aryl-substituted alkyl group having 7 to 13 carbon atoms, and n and m each independently represent an integer of 1 to 4. A structural unit (b) represented by the following formula (2): 【Chemistry 2】 (In formula (2), R ５ and R ６ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms, o and p each independently represent an integer of 1 to 4, and X is a single bond or at least one group selected from the group consisting of the following formula (3): 【Chemistry 3】 (In formula (3), R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ and R １４ each independently represents at least one 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 １５ and R １６ each independently represents at least one 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; when there are a plurality of groups, they may be the same or different, a is an integer from 1 to 10, and b is an integer from 4 to 7. A polycarbonate resin composition comprising 100 parts by weight of a polycarbonate resin (A) containing 70 mol % or more of the above based on all structural units, and 0.01 to 10 parts by weight of a compound (B) having an epoxy group or a carbodiimide group.

2. 2. The polycarbonate resin composition according to claim 1, wherein the content of the structural unit (a) is 10 mol % or more.

3. 2. The polycarbonate resin composition according to claim 1, wherein the structural unit (a) is a structural unit derived from 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine or 2-phenyl-3,3-bis(4-hydroxy-3-methylphenyl)phthalimidine.

4. 2. The polycarbonate resin composition according to claim 1, which has a pencil hardness of H or more as measured in accordance with JIS K5600.

5. 2. The polycarbonate resin composition according to claim 1, which has a glass transition temperature of 130 to 300°C.

6. 2. The polycarbonate resin composition according to claim 1, wherein the b* value measured on a molded plate having a thickness of 2 mm is 40 or less.

7. 2. The polycarbonate resin composition according to claim 1, which has a molecular weight retention of 72% or more after a wet heat test measured by the following test method. Test method: The molded plate was subjected to static treatment for 1000 hours under conditions of 85°C x 85% RH in a small environmental tester SH-242 manufactured by Espec Corp. Thereafter, the viscosity average molecular weight of the treated molded plate was measured, and the molecular weight retention rate was calculated using the following formula. Molecular weight retention (%) = (viscosity average molecular weight after test / viscosity average molecular weight before test) × 100

8. A molded article obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 7.

9. A sheet or film obtained by extrusion molding the polycarbonate resin composition according to any one of claims 1 to 7.

10. An automobile interior part using the molded article according to claim 8 or the sheet or film according to claim 9.

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