Polycarbonate resin composition and molded article thereof

Abstract

The present invention relates to a polycarbonate resin composition, which contains a polycarbonate resin (S) and a copolymer (B), wherein the polycarbonate resin (S) contains a polycarbonate-polyorganosiloxane copolymer (A), the polycarbonate-polyorganosiloxane copolymer (A) contains a polycarbonate block (A-1) containing a specific repeating unit and a polyorganosiloxane block (A-2) containing a specific repeating unit, and the copolymer (B) has a structural unit (b-1) of a specific structure, a structural unit (b-2) of a specific structure, and a structural unit (b-3) of a specific structure.

Description

Technical Field

[0001] The present invention relates to a polycarbonate resin composition and a molded article thereof. Background Art

[0002] Polycarbonate-based resins are excellent in impact resistance, heat resistance, transparency, and the like, and are therefore used as materials for various parts in the electrical and electronic fields, the automotive field, and the like, making effective use of these characteristics.

[0003] Depending on where these components are used, sliding properties are sometimes required. For example, polycarbonate resins containing bisphenol A alone tend to have poor sliding properties, and attempts have been made to improve sliding properties. For example, polycarbonate resin compositions are known in which a rubber-reinforced styrene resin is blended with a polycarbonate resin, each containing a copolymer with a specific structure in specific amounts (Patent Document 1).

[0004] However, when such polycarbonate-based resin compositions are used as automobile components, particularly in an automobile interior environment, there arises a problem in that mechanical properties such as impact resistance are degraded.

[0005] Polycarbonate-polyorganosiloxane (hereinafter, sometimes abbreviated as PC-POS) copolymer is widely known as a polycarbonate resin having excellent impact resistance and flame retardancy (see Patent Document 2).

[0006] However, PC-POS copolymers tend to have inferior sliding properties compared to other polycarbonate resins, and attempts have been made to improve their sliding properties. For example, polycarbonate-polyorganosiloxane copolymers with a specific structure and chain length, as well as polycarbonate resin compositions containing specific compounds (Patent Document 3), are known to have room for improvement in their sliding properties.

[0007] In addition, PC-POS copolymers tend to have a stronger yellow tint compared to other polycarbonate resins, so there is room for improvement in color tone when used in automotive interiors.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2018-141078

[0011] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-037495

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 2020-7402 Summary of the Invention

[0013] Problems to be solved by the invention

[0014] An object of the present invention is to obtain a polycarbonate resin composition and a molded article thereof having excellent sliding properties and impact resistance and a good color tone.

[0015] Means for solving problems

[0016] The present inventors have discovered that a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer having a specific structure and a specific compound has excellent slidability and impact resistance, as well as excellent color tone. The present invention relates to the following [1] to [8].

[0017] [1] A polycarbonate resin composition comprising a polycarbonate resin (S) and a copolymer (B), wherein the polycarbonate resin (S) comprises a polycarbonate-polyorganosiloxane copolymer (A), wherein the polycarbonate-polyorganosiloxane copolymer (A) comprises a polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) comprising a repeating unit represented by the following general formula (II), and wherein the copolymer (B) comprises a structural unit (b-1) represented by the following general formula (X1), a structural unit (b-2) represented by the following general formula (X2), and a structural unit (b-3) represented by the following general formula (X3).

[0018] [Chemical Formula 1]

[0019]

[0020] [Chemical Formula 2]

[0021]

[0022] [Where R 1 and R 2 Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. R 3 and R 4 Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a and b each independently represent an integer of 0 to 4.

[0023] R 31 Each of them independently represents a halogen atom or an alkyl group having 1 to 10 carbon atoms. c represents an integer of 0 to 5.

[0024] [2] The polycarbonate resin composition according to [1] above, wherein the structural unit (b-1) represented by the general formula (X1) constitutes a side chain of the copolymer (B).

[0025] [3] The polycarbonate resin composition according to [1] or [2], wherein the structural unit (b-2) represented by the general formula (X2) and the structural unit (b-3) represented by the general formula (X3) constitute the main chain of the copolymer (B).

[0026] [4] The polycarbonate resin composition according to any one of [1] to [3] above, wherein the content of the copolymer (B) is 0.5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polycarbonate resin (S).

[0027] [5] The polycarbonate resin composition according to any one of [1] to [4] above, further comprising a release agent (C).

[0028] [6] The polycarbonate resin composition according to [5] above, wherein the release agent (C) is a fatty acid ester.

[0029] [7] The polycarbonate resin composition according to any one of [1] to [6] above, wherein the average chain length of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 50 or more.

[0030] [8] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [7].

[0031] Effects of the Invention

[0032] According to the present invention, a polycarbonate resin composition having excellent slidability and impact resistance and a good color tone and a molded article thereof can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram showing friction coefficient evaluation.

[0034] Figure 2 This shows an example of a friction and wear test. DETAILED DESCRIPTION

[0035] The polycarbonate resin composition of the present invention contains a polycarbonate resin (S) and a copolymer (B), wherein the polycarbonate resin (S) contains a polycarbonate-polyorganosiloxane copolymer (A), the polycarbonate-polyorganosiloxane copolymer (A) contains a polycarbonate block (A-1) containing a specific repeating unit and a polyorganosiloxane block (A-2) containing a specific repeating unit, and the copolymer (B) has a structural unit (b-1) represented by the general formula (X1), a structural unit (b-2) represented by the general formula (X2), and a structural unit (b-3) represented by the general formula (X3).

[0036] The polycarbonate resin composition and molded article of the present invention are described in detail below. In this specification, any preferred specification may be adopted, and a combination of preferred specifications is more preferred. In this specification, the term "XX to YY" means "XX or greater and YY or less."

[0037] [Polycarbonate resin composition]

[0038] The polycarbonate resin composition of the present invention contains a polycarbonate resin (S) and a copolymer (B). The polycarbonate resin (S) contains a polycarbonate-polyorganosiloxane copolymer (A), and the copolymer (B) contains structural units (b-1), structural units (b-2), and structural units (b-3).

[0039] <Polycarbonate Resin (S)>

[0040] The polycarbonate resin (S) constituting the polycarbonate resin composition of the present invention contains a polycarbonate-polyorganosiloxane copolymer (A), wherein the polycarbonate-polyorganosiloxane copolymer (A) contains a polycarbonate block (A-1) containing a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II).

[0041] [Chemical Formula 3]

[0042]

[0043] [Where R 1 and R 2 Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. R 3 and R 4Each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. a and b each independently represent an integer of 0 to 4.

[0044] In the above general formula (I), R 1 and R 2 Examples of the halogen atom independently represented include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0045] As R 1 and R 2 The alkyl groups independently represented by R include methyl, ethyl, n-propyl, isopropyl, various butyl groups ("various" means including straight-chain and all branched groups. The same shall apply in the following description.), various pentyl groups and various hexyl groups. 1 and R 2 Examples of the alkoxy groups independently represented include alkoxy groups having the above-mentioned alkyl groups as an alkyl moiety.

[0046] Examples of the alkylene group represented by X include methylene, ethylene, trimethylene, tetramethylene, and hexamethylene, preferably an alkylene group having 1 to 5 carbon atoms. Examples of the alkylidene group represented by X include ethylidene and isopropylidene. Examples of the cycloalkylene group represented by X include cyclopentanediyl, cyclohexanediyl, and cyclooctanediyl, preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the cycloalkylene group represented by X include cyclohexylidene, 3,5,5-trimethylcyclohexylidene, and 2-adamantanediyl, preferably a cycloalkylene group having 5 to 10 carbon atoms, more preferably a cycloalkylene group having 5 to 8 carbon atoms. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl, naphthyl, biphenylyl, and anthracenyl, and examples of the alkylene group include the above-mentioned alkylene groups. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl, naphthyl, biphenylyl, and anthracenyl. Examples of the alkylidene group include the aforementioned alkylidene groups.

[0047] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1.

[0048] Among them, the case where a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or the case where a and b are 0 and X is an alkylene group having 3 carbon atoms, particularly an isopropylidene group, is suitable.

[0049] In the above general formula (II), R 3 or R 4 Examples of the halogen atom represented by R include fluorine, chlorine, bromine and iodine. 3 or R 4Examples of the alkyl group represented by R include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 3 or R 4 The alkoxy group represented by , for example, includes the case where the alkyl portion is the above-mentioned alkyl group. 3 or R 4 The aryl group shown includes phenyl, naphthyl and the like.

[0050] R 3 and R 4 All of them are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and all of them are more preferably a methyl group.

[0051] More specifically, the polyorganosiloxane block (A-2) comprising the repeating unit represented by the above-mentioned general formula (II) preferably has a unit represented by at least any one of the following general formulae (II-I) to (II-III).

[0052] [Chemical Formula 4]

[0053]

[0054] [Where R 3 ~R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. 3 ~R 6 Can be the same or different. Y represents -R 7 O-、-R 7 COO-、-R 7 NH-, -R 7 NR 8 -、-COO-、-S-、-R 7 COO-R 9 -O-, or -R 7 OR 10 -O-, multiple Ys may be the same or different from each other. 7 R represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 Represents a diarylene group. 10 represents a linear, branched, or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. n represents the average chain length of the polyorganosiloxane, n-1, p, and q each represent the number of repetitions of the organosiloxane unit, each being an integer greater than 1, and the sum of p and q is n-2.

[0055] As R 3 ~R 6 The halogen atoms independently represented by R include fluorine, chlorine, bromine and iodine atoms. 3 ~R 6 The alkyl groups independently represented by R include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 3 ~R 6 The alkoxy groups independently represented by each of them include the case where the alkyl moiety is the above-mentioned alkyl group. 3 ~R 6 Examples of the aryl group independently represented include phenyl and naphthyl.

[0056] As R 3 ~R 6 , are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0057] R in the general formula (II-I), (II-II) and / or (II-III) 3 ~R 6 Both are preferably methyl.

[0058] As shown by Y-R 7 O-、-R 7 COO-、-R 7 NH-, -R 7 NR 8 -、-R 7 COO-R 9 -O-, or -R 7 OR 10 -R in O- 7 The linear or branched alkylene group represented by can be exemplified by an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. 7 Examples of the cycloalkylene group include cycloalkylene groups having 5 to 15 carbon atoms, and preferably cycloalkylene groups having 5 to 10 carbon atoms.

[0059] As R 7 The aryl-substituted alkylene group shown in the figure may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring, and its specific structure may be, for example, the structure of the following general formula (i) or (ii). 7 When an alkylene group is substituted with an aryl group, the alkylene group is bonded to Si.

[0060] [Chemical Formula 5]

[0061]

[0062] (where c represents a positive integer, usually an integer from 1 to 6)

[0063] R 7 、R 9 and R 10 The diarylene group shown is a group formed by connecting two arylene groups directly or via a divalent organic group, specifically having -Ar 1 -W-Ar 2 - represents a group of the structure. Here, Ar 1 and Ar 2 represents an arylene group, and W represents a single bond or a divalent organic group. Examples of the divalent organic group represented by W include isopropylidene, methylene, dimethylene, and trimethylene.

[0064] As R 7 、Ar 1 and Ar 2 Examples of the arylene group include arylene groups having 6 to 14 ring carbon atoms, such as phenylene, naphthylene, biphenylene, and anthracene. These arylene groups may have an optional substituent such as an alkoxy group or an alkyl group.

[0065] As R 8 The alkyl group represented by is a linear or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. 8 The alkenyl group represented by , for example, is a linear or branched alkenyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. 8 The aryl group represented by , for example, phenyl, naphthyl, etc. 8 The aralkyl group represented by the above-mentioned group includes phenylmethyl and phenylethyl.

[0066] R 10 The straight chain, branched chain or cyclic alkylene group shown and R 7 same.

[0067] As Y, -R 7 O-, R 7 The aryl-substituted alkylene group is particularly a residue of a phenolic compound having an alkyl group, and more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.

[0068] In addition, regarding p and q in formula (II-II), it is preferable that p=q.

[0069] β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples thereof include divalent groups represented by the following general formulas (iii) to (vii).

[0070] [Chemical Formula 6]

[0071]

[0072] The average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably 20 or more and 500 or less. It should be noted that the average chain length n refers to the average number of repetitions of the repeating unit shown in formula (II). n in formula (II-I) and (II-III) is 20 or more and 500 or less. In the case of (II-II), the sum of p and q plus 2 is the above range. The average chain length is calculated by nuclear magnetic resonance (NMR) measurement. If the average chain length of the polycarbonate-polyorganosiloxane copolymer (A) is 20 or more and 500 or less, the impact resistance, sliding properties, etc. of the polycarbonate resin composition finally obtained are excellent, and an excellent color tone can be obtained.

[0073] The average chain length of the polyorganosiloxane block (A-2) is more preferably 35 or more, further preferably 45 or more, further preferably 50 or more, particularly preferably 70 or more, more preferably 300 or less, further preferably 150 or less, further preferably 100 or less.

[0074] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably from 0.1% to 60% by mass. When the amount of polyorganosiloxane in the PC-POS copolymer (A) is within this range, a polycarbonate resin composition having superior impact resistance, transparency, hue, and slip properties can be obtained. The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is calculated by nuclear magnetic resonance (NMR) measurement.

[0075] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, more preferably 50% by mass or less, further preferably 35% by mass or less, further preferably 15% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less.

[0076] The content of the polyorganosiloxane block (A-2) in the polycarbonate resin composition is preferably from 0.1% to 45% by mass. If the amount of polyorganosiloxane in the PC-POS copolymer (A) is within this range, a polycarbonate resin composition having superior impact resistance, color tone, and excellent sliding properties can be obtained. The content of the polyorganosiloxane block (A-2) in the polycarbonate resin composition is calculated by nuclear magnetic resonance (NMR) measurement, similar to the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A).

[0077] The content of the polyorganosiloxane block (A-2) in the polycarbonate resin composition is more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, more preferably 35% by mass or less, further preferably 25% by mass or less, particularly preferably 10% by mass or less, and most preferably 8% by mass or less.

[0078] The viscosity average molecular weight (Mv) of the PC-POS copolymer (A) can be appropriately adjusted to achieve the target molecular weight by using a molecular weight modifier (end-capping agent) or the like, depending on the intended application and product. The viscosity average molecular weight of the PC-POS copolymer (A) is preferably 9,000 to 50,000. A viscosity average molecular weight of 9,000 or greater provides sufficient molded product strength. A viscosity average molecular weight of 50,000 or less allows injection molding and extrusion molding at temperatures that do not cause thermal degradation.

[0079] The viscosity average molecular weight of the PC-POS copolymer (A) is more preferably 12,000 or more, further preferably 14,000 or more, particularly preferably 16,000 or more, more preferably 30,000 or less, further preferably 25,000 or less, further preferably 23,000 or less, particularly preferably 20,000 or less.

[0080] The viscosity average molecular weight (Mv) is a value calculated from the intrinsic viscosity [η] of a dichloromethane solution at 20°C using the following Schnell equation.

[0081] [Mathematical formula 1]

[0082] [η] = 1.23 × 10 -5 ×Mv 0.83

[0083] The PC-POS copolymer (A) can be produced by known manufacturing methods such as the interfacial polymerization method (phosgene method), the pyridine method, and the transesterification method. In particular, when the interfacial polymerization method is adopted, it is easy to carry out the separation process of the organic phase containing the PC-POS copolymer and the aqueous phase containing unreacted products, catalyst residues, etc., and it is easy to carry out the separation of the organic phase containing the PC-POS copolymer and the aqueous phase in each cleaning process such as alkali cleaning, acid cleaning, and pure water washing. Therefore, the PC-POS copolymer can be obtained efficiently. As a method for producing the PC-POS copolymer, for example, reference can be made to the method described in Japanese Patent Application Publication No. 2014-80462.

[0084] Specifically, the previously produced polycarbonate oligomer and polyorganosiloxane, described below, can be dissolved in a water-insoluble organic solvent (e.g., dichloromethane), an alkaline aqueous solution (e.g., sodium hydroxide solution) of a diphenolic compound (e.g., bisphenol A) can be added, and a tertiary amine (e.g., triethylamine) or a quaternary ammonium salt (e.g., trimethylbenzyl ammonium chloride) can be used as a polymerization catalyst to carry out an interfacial polycondensation reaction in the presence of an end-capping agent (e.g., monophenol such as p-tert-butylphenol). Alternatively, PC-POS copolymer (A) can be produced by copolymerizing polyorganosiloxane, diphenol, phosgene, carbonate, or chloroformate.

[0085] As the polyorganosiloxane used as a raw material, polyorganosiloxane represented by the following general formula (1), (2) and / or (3) can be used.

[0086] [Chemical Formula 7]

[0087]

[0088] Where R 3 ~R 6 , Y, β, n-1, p and q are as described above, and the same applies to the specific examples and preferred examples.

[0089] Z represents a hydrogen or halogen atom, and a plurality of Zs may be the same as or different from each other.

[0090] For example, examples of the polyorganosiloxane represented by the general formula (1) include compounds represented by the following general formulas (1-1) to (1-11).

[0091] [Chemical Formula 8]

[0092]

[0093] In the above general formulas (1-1) to (1-11), R 3 ~R 6 , n-1 and R 8 The same applies to the above definition and preferred examples. c represents a positive integer, and is usually an integer of 1 to 6.

[0094] Among them, from the perspective of ease of polymerization of polyorganosiloxanes, phenol-modified polyorganosiloxanes represented by the above-mentioned general formula (1-1) are preferred. Furthermore, from the perspective of ease of availability, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above-mentioned general formula (1-2), and α,ω-bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above-mentioned general formula (1-3), are preferred.

[0095] As the polyorganosiloxane raw material, a polyorganosiloxane raw material having the following general formula (4) can be used.

[0096] [Chemical Formula 9]

[0097]

[0098] Where R 3 and R 4 The same as in the above example, the average chain length of the polyorganosiloxane block represented by the general formula (4) is (r×m), and the range of (r×m) is the same as that of n described above.

[0099] When the above-mentioned (4) is used as a polyorganosiloxane raw material, the polyorganosiloxane block (A-2) preferably has a unit represented by the following general formula (II-IV).

[0100] [Chemical Formula 10]

[0101]

[0102] [R in the formula 3 、R 4 , r and m as described above]

[0103] The polyorganosiloxane block (A-2) may have a structure represented by the following general formula (II-V).

[0104] [Chemical Formula 11]

[0105]

[0106] [Where R 18 ~R 21 Each independently represents a hydrogen atom or an alkyl group having 1 to 13 carbon atoms. 22 Q is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. 2 It is a divalent aliphatic group having 1 to 10 carbon atoms. n represents the average chain length, as described above.]

[0107] In the general formula (II-V), R 18 ~R 21 The alkyl groups having 1 to 13 carbon atoms each independently represents include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, 2-ethylhexyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, and various tridecyl groups. 18 ~R 21 It preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represents a methyl group.

[0108] As R 22 Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 22 Examples of the halogen atom represented by R include fluorine, chlorine, bromine and iodine. 22 The alkoxy group having 1 to 6 carbon atoms shown in the figure may be a case where the alkyl moiety is the above-mentioned alkyl group. 22 Examples of the aryl group having 6 to 14 carbon atoms include phenyl, tolyl, dimethylphenyl and naphthyl.

[0109] In the above, R 22 It preferably represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably represents a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and even more preferably represents a hydrogen atom.

[0110] As Q 2 The divalent aliphatic group having 1 to 10 carbon atoms represented by is preferably a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms. The saturated aliphatic group preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 3 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms. The average chain length n is as described above.

[0111] Preferred embodiments of the structural unit (II-V) include structures represented by the following formula (II-VI).

[0112] [Chemical Formula 12]

[0113]

[0114] [Where n-1 is as described above.]

[0115] The polyorganosiloxane block (A-2) represented by the general formula (II-V) or (II-VI) can be obtained by using a polyorganosiloxane raw material represented by the following general formula (5) or (6).

[0116] [Chemical Formula 13]

[0117]

[0118] [Where R 18 ~R 22 , Q 2 and n-1 as above.]

[0119] [Chemical Formula 14]

[0120]

[0121] [Where n-1 is as described above.]

[0122] The preparation method of the above-mentioned polyorganosiloxane is not particularly limited. For example, according to the method described in Japanese Patent Laid-Open No. 11-217390, cyclotrisiloxane and disiloxane can be reacted in the presence of an acidic catalyst to synthesize α, ω-dihydroorganopentasiloxane, and then a phenolic compound (such as 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) and the α, ω-dihydroorganopentasiloxane are subjected to an addition reaction to obtain a crude polyorganosiloxane. In addition, according to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane can be reacted in the presence of sulfuric acid (an acidic catalyst), and the resulting α, ω-dihydroorganopolysiloxane is subjected to an addition reaction to obtain a crude polyorganosiloxane in the presence of a hydrosilylation catalyst. The α,ω-dihydroorganopolysiloxane may be used by appropriately adjusting its chain length n by adjusting the polymerization conditions, and commercially available α,ω-dihydroorganopolysiloxane may be used. Specifically, the α,ω-dihydroorganopolysiloxane described in JP-A-2016-098292 may be used.

[0123] Polycarbonate oligomers can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as dichloromethane, chlorobenzene, or chloroform. When produced using the transesterification method, polycarbonate oligomers can also be produced by reacting a dihydric phenol with a carbonate precursor such as diphenyl carbonate.

[0124] As the dihydric phenol, a dihydric phenol represented by the following general formula (viii) is preferably used.

[0125] [Chemical Formula 15]

[0126]

[0127] Where R 1 、R 2 , a, b and X are as described above.

[0128] Examples of the dihydric phenol represented by the general formula (viii) include bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl)ethers, bis(4-hydroxyphenyl)sulfides, bis(4-hydroxyphenyl)sulfones, bis(4-hydroxyphenyl)sulfoxides, and bis(4-hydroxyphenyl)ketones. These dihydric phenols may be used alone or in combination of two or more.

[0129] Among them, bis(hydroxyphenyl)alkane-based diphenols are preferred, and bisphenol A is more preferred. When bisphenol A is used as the diphenol, a PC-POS copolymer is obtained in which X is an isopropylidene group and a=b=0 in the general formula (i).

[0130] Examples of dihydric phenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxybiphenyls, dihydroxydiarylfluorenes, and dihydroxydiaryladamantanes. These dihydric phenols may be used alone or in combination of two or more.

[0131] Examples of the bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane.

[0132] Examples of bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, and 1,1-bis(4-hydroxyphenyl)cyclododecane. Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.

[0133] Examples of dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide. Examples of dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide. Examples of dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

[0134] Examples of dihydroxybiphenyls include 4,4'-dihydroxybiphenyl. Examples of dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Examples of dihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0135] Examples of dihydric phenols other than those mentioned above include 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxolane.

[0136] To adjust the molecular weight of the resulting PC-POS copolymer, an end-capping agent (molecular weight modifier) ​​may be used. Examples of end-capping agents include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0137] After the above-mentioned interfacial polycondensation reaction, the mixture can be separated into an aqueous phase and an organic solvent phase by appropriately standing [separation step], the organic solvent phase can be washed (preferably using an alkaline aqueous solution, an acidic aqueous solution, and water in sequence) [washing step], the obtained organic phase can be concentrated [concentration step], and dried [drying step] to obtain PC-POS copolymer (A).

[0138] <Polycarbonate Resin (A')>

[0139] The polycarbonate resin (S) may contain a polycarbonate resin (A') other than the PC-POS copolymer (A). The polycarbonate resin (A') is not particularly limited, and various known polycarbonate resins can be used.

[0140] The viscosity average molecular weight (Mv) of the polycarbonate resin (A') is usually 10,000 to 50,000, preferably 13,000 to 35,000, more preferably 14,000 to 28,000, and even more preferably 16,000 to 25,000.

[0141] The viscosity average molecular weight (Mv) is a value calculated using the Schnell equation in the same manner as for the PC-POS copolymer (A).

[0142] Specifically, the polycarbonate resin (A') can be obtained by conventional polycarbonate production methods, such as an interfacial polymerization method in which a diphenol compound is reacted with phosgene in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, followed by polymerization with the addition of a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt, or a pyridine method in which a diphenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and then directly produced by the introduction of phosgene. During the above reaction, a molecular weight modifier (end-capping agent), a branching agent, etc. may be used as needed.

[0143] Examples of the dihydric phenol-based compound include dihydric phenol-based compounds represented by the following general formula (III').

[0144] [Chemical Formula 16]

[0145]

[0146] [Where R 1 、R 2 , X, a and b are as defined above, and preferred embodiments are also the same.]

[0147] Specific examples of the dihydric phenolic compound include the compounds described above in the method for producing the polycarbonate-polyorganosiloxane copolymer (A), and preferred examples are the same. Among them, bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, and bisphenol A is more preferred.

[0148] The polycarbonate resin (A') may be used alone or in combination of two or more. Unlike the polycarbonate-polyorganosiloxane copolymer (A), the polycarbonate resin (A') does not have a polyorganosiloxane block (A-2) such as that represented by formula (II). For example, the polycarbonate resin (A') may be a homopolycarbonate resin, preferably an aromatic polycarbonate resin.

[0149] The polycarbonate resin (S) contained in the polycarbonate resin composition of the present invention may be the above-mentioned PC-POS copolymer (A) alone, or may contain the PC-POS copolymer (A) and the polycarbonate resin (A').

[0150] From the viewpoint of impact resistance and sliding properties of the molded article, the content of the PC-POS copolymer (A) in the polycarbonate resin (S) contained in the polycarbonate resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 30% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass (i.e., no polycarbonate resin (A') is contained).

[0151] <Copolymer (B)>

[0152] The copolymer (B) contained in the polycarbonate resin composition of the present invention is a copolymer having a structural unit (b-1) represented by the following general formula (X1), a structural unit (b-2) represented by the following general formula (X2), and a structural unit (b-3) represented by the following general formula (X3).

[0153] [Chemical Formula 17]

[0154]

[0155] [Where R 31 Each of them independently represents a halogen atom or an alkyl group having 1 to 10 carbon atoms. c represents an integer of 0 to 5.

[0156] The structural unit (b-1) is represented by the above-mentioned general formula (X1).

[0157] In the above general formula (X1), R 31 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0158] As R 31 Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups.

[0159] c represents an integer of 0 to 5, preferably 0 to 3, more preferably 0 or 1. c=0 is particularly preferred.

[0160] The structural unit (b-2) is represented by the above-mentioned general formula (X2). The structural unit (b-3) is represented by the above-mentioned general formula (X3).

[0161] The copolymer (B) is not particularly limited as long as it has the structural unit (b-1) represented by the general formula (X1), the structural unit (b-2) represented by the general formula (X2), and the structural unit (b-3) represented by the general formula (X3). The copolymer (B) may be any one of a random copolymer or a block copolymer having the structural unit (b-1), the structural unit (b-2), and the structural unit (b-3). In addition, the copolymer (B) may be a copolymer in which the three structural units (b-1), the structural unit (b-2), and the structural unit (b-3) constitute a straight or branched main chain, or a copolymer in which one or two selected from the structural units (b-1), the structural unit (b-2), and the structural unit (b-3) constitute a main chain, and at least one other is polymerized (e.g., grafted) to constitute a side chain.

[0162] From the viewpoint of excellent slip properties and color tone, it is preferred that the structural unit (b-1) constitutes a side chain of the copolymer (B), and / or the structural unit (b-2) and the structural unit (b-3) constitute the main chain of the copolymer (B). It is more preferred that the structural unit (b-1) constitutes a side chain of the copolymer (B) and the structural units (b-2) and the structural units (b-3) constitute the main chain of the copolymer (B).

[0163] In the copolymer (B), the content of the structural unit (b-1), the structural unit (b-2), and the structural unit (b-3) in the copolymer is not particularly limited, and examples thereof include the following.

[0164] The content of the structural unit (b-1) represented by the above general formula (X1) is preferably 10% by mass or more and 50% by mass or less relative to 100% by mass of the total of the structural unit (b-2) represented by the above general formula (X2) and the structural unit (b-3) represented by the above general formula (X3).

[0165] The content of the structural unit (b-2) represented by the above-mentioned general formula (X2) is preferably 80 mass% or more and 99 mass% or less, and more preferably 90 mass% or more and 97 mass% or less relative to the total of 100 mass% of the structural unit (b-2) represented by the above-mentioned general formula (X2) and the structural unit (b-3) represented by the above-mentioned general formula (X3).

[0166] The content of the structural unit (b-3) represented by the above-mentioned general formula (X3) is preferably 1 mass % or more and 20 mass % or less relative to the total of 100 mass % of the structural unit (b-2) represented by the above-mentioned general formula (X2) and the structural unit (b-3) represented by the above-mentioned general formula (X3), and more preferably 3 mass % or more and 10 mass % or less.

[0167] <Ethylene-vinyl acetate copolymer (B') having a styrene-based (co)polymer segment>

[0168] Preferred embodiments of the copolymer (B) include ethylene-vinyl acetate copolymers (B') having styrene-based (co)polymer segments. The ethylene-vinyl acetate copolymer (B') having styrene-based (co)polymer segments is not limited as long as it is a copolymer comprising a styrene-based (co)polymer portion (segment) and an ethylene-vinyl acetate copolymer portion (segment). Preferably, it is a graft copolymer comprising a styrene-based (co)polymer segment and an ethylene-vinyl acetate copolymer segment. Furthermore, a graft copolymer having an ethylene-vinyl acetate copolymer segment as the main chain and a styrene-based (co)polymer segment as the side chain is preferred.

[0169] (Styrene (co)polymer segment)

[0170] The styrene-based (co)polymer segment includes the structural unit (b-1) represented by the above-mentioned general formula (X1). The styrene-based (co)polymer segment is a polymer consisting solely of the structural unit (b-1) represented by the above-mentioned general formula (X1), or a copolymer consisting of the structural unit (b-1) represented by the above-mentioned general formula (X1) and the structural unit (b-4) represented by the following general formula (X4) or the following general formula (X5).

[0171] [Chemical Formula 18]

[0172]

[0173] [Where R 41 and R 43 Each independently represents a hydrogen atom or a methyl group. 42 represents an alkyl group having 1 to 8 carbon atoms or an epoxypropyl group.]

[0174] In the above general formula (X4), R 42 Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups.

[0175] In the above general formula (X4), R 41 Preferably, R 42 Preferred is glycidyl group.

[0176] In the above general formula (X5), R 43 Preferred is methyl.

[0177] There is no particular restriction on the content of the structural unit (b-1) represented by the above-mentioned general formula (X1) and the structural unit (b-4) represented by the above-mentioned general formula (X4) or the above-mentioned general formula (X5) in the styrene-based (co)polymer chain segment. Based on the total of 100 mass % of the structural unit (b-1) represented by the above-mentioned general formula (X1) and the structural unit (b-4) represented by the above-mentioned general formula (X4) or the above-mentioned general formula (X5), the content of the structural unit (b-1) represented by the above-mentioned general formula (X1) is preferably 50 mass % or more and 100 mass % or less.

[0178] (ethylene-vinyl acetate copolymer)

[0179] The ethylene-vinyl acetate copolymer is a copolymer comprising the structural unit (b-2) represented by the general formula (X2) and the structural unit (b-3) represented by the general formula (X3). The ethylene-vinyl acetate copolymer may be a random copolymer of ethylene and vinyl acetate or a block copolymer.

[0180] The proportion of the structural unit (b-3) represented by the above general formula (X3) in the ethylene-vinyl acetate copolymer is preferably 1 to 20 mass %, more preferably 2 to 15 mass %, and even more preferably 3 to 10 mass %, relative to the total mass of the structural unit (b-2) represented by the above general formula (X2) and the structural unit (b-3) represented by the above general formula (X3).

[0181] In a preferred embodiment of the ethylene-vinyl acetate copolymer (B') having a styrene-based (co)polymer segment, the copolymer is a graft copolymer having an ethylene-vinyl acetate copolymer segment as the main chain and styrene-based (co)polymer segments as side chains. Here, the main chain refers to the longest chain structure in the copolymer molecule.

[0182] The ethylene-vinyl acetate copolymer (B') having a styrene-based (co)polymer chain segment can be produced by various known methods. A suitable method includes mixing a styrene-based monomer, or further another vinyl-based monomer, and a radically polymerizable organic peroxide in an aqueous suspension prepared by adding a suspending agent to the ethylene-vinyl acetate copolymer, followed by heating and stirring, impregnating the ethylene-vinyl acetate copolymer with the above components, and then further heating to polymerize the mixture.

[0183] The ethylene-vinyl acetate copolymer (B') having a styrene-based (co)polymer segment is commercially available and can be selected and obtained from, for example, the "MODIPER" series of products manufactured by NOF Corporation. For example, "MODIPER AS100" is mentioned.

[0184] From the viewpoint of excellent slidability and color tone (YI value) of the molded article, the content of the copolymer (B) is preferably from 0.5 parts by mass to 20 parts by mass, more preferably from 1 part by mass to 15 parts by mass, further preferably from 2 parts by mass to 10 parts by mass, and even more preferably from 2 parts by mass to 7 parts by mass, relative to 100 parts by mass of the polycarbonate resin (S).

[0185] <Release Agent (C)>

[0186] From the viewpoint of excellent sliding properties, the polycarbonate resin composition of the present invention may further contain a release agent (C).

[0187] Examples of the release agent (C) include fatty acid esters, and more specifically, full esters of pentaerythritol and aliphatic carboxylic acids are preferably used. Full esters of pentaerythritol and aliphatic carboxylic acids are obtained by esterifying pentaerythritol and aliphatic carboxylic acids to form full esters.

[0188] As the aliphatic carboxylic acid constituting the full ester, an aliphatic carboxylic acid having 12 to 30 carbon atoms can be preferably used.

[0189] Aliphatic carboxylic acids can be those produced from various vegetable oils and animal fats. These oils are ester compounds containing various fatty acids as components. For example, stearic acid produced from these vegetable oils and animal fats typically contains large amounts of other fatty acid components such as palmitic acid. In the present invention, mixed fatty acids containing multiple fatty acids produced from such vegetable oils and animal fats can be used, as can purified and separated fatty acids.

[0190] Among aliphatic carboxylic acids having 12 to 30 carbon atoms, aliphatic carboxylic acids having 12 to 22 carbon atoms are preferred. Among aliphatic carboxylic acids, saturated fatty acids are preferred, and saturated fatty acids having 12 to 22 carbon atoms are particularly preferred. Among saturated fatty acids having 12 to 22 carbon atoms, stearic acid, palmitic acid, and behenic acid are preferred.

[0191] Preferred compounds of full esters of pentaerythritol and aliphatic carboxylic acids include pentaerythritol stearate, pentaerythritol palmitate, and pentaerythritol behenate. From the perspective of European REACH compliance, a mixture of pentaerythritol palmitate and pentaerythritol stearate in a mass ratio of 9:1 to 1:9, preferably 5:5 to 3:7, is particularly preferred. For example, pentaerythritol stearate has been widely used as a mold release agent and is therefore pre-registered as an existing substance under REACH. In contrast, pentaerythritol palmitate, as a new substance, requires new pre-registration, but registration is expensive and more complex. Therefore, a mixture with a high pentaerythritol stearate composition ratio that can be treated as pentaerythritol stearate is preferred. Another reason why a higher proportion of pentaerythritol stearate is preferred is that pentaerythritol stearate with a carbon chain of C18 exhibits superior mold release properties when prepared as a resin composition compared to pentaerythritol palmitate with a carbon chain of C16.

[0192] The content of the release agent (C) is preferably 0.10 part by mass or more, more preferably 0.15 part by mass or more, further preferably 0.20 part by mass or more, further preferably 0.25 part by mass or more, relative to 100 parts by mass of the polycarbonate resin (S), and is preferably 0.45 part by mass or less, more preferably 0.40 part by mass or less, further preferably 0.35 part by mass or less, further preferably 0.30 part by mass or less.

[0193] <Other additives>

[0194] The polycarbonate resin composition of the present invention may further contain other additives within a range that does not impair the effects of the present invention. Examples of these other ingredients include anti-hydrolysis agents, antioxidants, ultraviolet absorbers, flame retardants, flame retardant aids, reinforcing materials, fillers, elastomers for improving impact resistance, pigments, and dyes. Some of these ingredients are described in detail below.

[0195] <Antioxidants>

[0196] The polycarbonate resin composition of the present invention preferably further comprises an antioxidant. By adding an antioxidant to the polycarbonate resin composition, oxidative degradation of the polycarbonate resin composition during melting can be suppressed, and coloration caused by oxidative degradation can be suppressed. Phosphorus-based antioxidants and / or phenolic antioxidants can be suitably used as antioxidants.

[0197] Examples of the phenolic antioxidant include hindered phenols such as n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].

[0198] Among these antioxidants, preferred are substances having a pentaerythritol diphosphite structure such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and bis(2,6-di-tert-butylphenyl)pentaerythritol diphosphite, and triphenylphosphine.

[0199] Examples of commercially available phenolic antioxidants include Irganox 1010 (trademark manufactured by BASF Japan Co., Ltd.), Irganox 1076 (trademark manufactured by BASF Japan Co., Ltd.), Irganox 1330 (trademark manufactured by BASF Japan Co., Ltd.), Irganox 3114 (trademark manufactured by BASF Japan Co., Ltd.), BHT (trademark manufactured by Takeda Pharmaceutical Company, Ltd.), CYANOX 1790 (trademark manufactured by SOLVAY Co., Ltd.), and Sumilizer GA-80 (trademark manufactured by Sumitomo Chemical Co., Ltd.).

[0200] Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylnonyl phosphite, diphenyl(2-ethylhexyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, diphenylisooctylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, diphenylisodecylphosphite, diphenylmono(tridecyl)phosphite, phenyldiisodecylphosphite, phenyldi(tridecyl)phosphite, tris(2-ethylhexyl)phosphite, Phosphites, tris(isodecyl)phosphite, tris(tridecyl)phosphite, dibutyl hydrogenphosphite, trilauryl trithiophosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 4,4'-isopropylidene diphenol dodecylphosphite, 4,4'-isopropylidene diphenol tridecylphosphite, 4,4'-isopropylidene diphenol tetradecylphosphite, 4,4'-isopropylidene diphenol pentadecylphosphite, 4,4'-butylene bis(3-methyl)bis(1,2-diol ... -6-tert-butylphenyl) ditridecyl phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris(2-methyl-4-ditridecylphosphite-5-tert-butylphenyl) butane, 3,4,5,6 -dibenzo-1,2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tri(p-tolyl)phosphine, tri(p-nonylphenyl)phosphine, tri(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tri(p-chlorophenyl)phosphine, tri(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, and the like.

[0201] Examples of commercially available phosphorus-based antioxidants include Irgafos 168 (trademark manufactured by BASF Japan Co., Ltd.), Irgafos 12 (trademark manufactured by BASF Japan Co., Ltd.), Irgafos 38 (trademark manufactured by BASF Japan Co., Ltd.), ADEKA STAB 2112 (trademark manufactured by ADEKA Co., Ltd.), ADEKA STAB C (trademark manufactured by ADEKA Co., Ltd.), ADEKA STAB 329K (trademark manufactured by ADEKA Co., Ltd.), ADEKA STAB PEP36 (trademark manufactured by ADEKA Co., Ltd.), JC-263 (trademark manufactured by Johoku Chemical Industry Co., Ltd.), Sandstab P-EPQ (trademark manufactured by Clarion Co., Ltd.), and Doverphos S-9228PC (trademark manufactured by Dover Chemical Co., Ltd.).

[0202] The above-mentioned antioxidants may be used alone or in combination. The amount of the antioxidant in the polycarbonate resin composition of the present invention is preferably 0.001 to 0.5 parts by mass, preferably 0.01 to 0.3 parts by mass, and more preferably 0.05 to 0.3 parts by mass, per 100 parts by mass of the polycarbonate resin (S). If the amount of the antioxidant is within the above range relative to 100 parts by mass of the polycarbonate resin (S), sufficient antioxidant effect can be obtained and mold contamination during molding can be suppressed.

[0203] The polycarbonate resin composition of the present invention can have both excellent sliding properties and impact resistance and an excellent color tone by having the above-mentioned composition.

[0204] It should be noted that slidability refers to the state in which the contact portion and / or movable portion of an article moves smoothly. Slidability can be evaluated based on, for example, the coefficient of kinetic friction and the coefficient of static friction.

[0205] In this specification, a good color tone means a low yellowish tint. The color tone can be evaluated, for example, by the YI value.

[0206] In one embodiment of the polycarbonate resin composition of the present invention, the total content of the polycarbonate resin (S) and the copolymer (B) is preferably 80% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the polycarbonate resin composition, more preferably 95% by mass or more and 100% by mass or less, further preferably 97% by mass or more and 100% by mass or less, even more preferably 98% by mass or more and 100% by mass or less, and particularly preferably 99% by mass or more and 100% by mass or less.

[0207] In another aspect of the polycarbonate resin composition of the present invention, the total content of the polycarbonate resin (S), the copolymer (B), and the other above-mentioned components is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, further preferably 97% by mass or more and 100% by mass or less, still more preferably 98% by mass or more and 100% by mass or less, and particularly preferably 99% by mass or more and 100% by mass or less, based on 100% by mass of the total amount of the polycarbonate resin composition.

[0208] In the polycarbonate resin composition of the present invention, the content of the polycarbonate resin (S) is preferably 65% by mass or more and 99.5% by mass or less, more preferably 80% by mass or more and 99% by mass or less, further preferably 85% by mass or more and 98% by mass or less, still more preferably 90% by mass or more and 98% by mass or less, based on 100% by mass of the total amount of the polycarbonate resin composition.

[0209] In the polycarbonate resin composition of the present invention, the content of the PC-POS copolymer (A) is preferably 20% by mass or more and 99.5% by mass or less, more preferably 40% by mass or more and 99% by mass or less, further preferably 60% by mass or more and 98% by mass or less, still more preferably 80% by mass or more and 98% by mass or less, based on 100% by mass of the total amount of the polycarbonate resin composition.

[0210] In the polycarbonate resin composition of the present invention, the content of the copolymer (B) is preferably 0.4% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, further preferably 1.5% by mass or more and 10% by mass or less, still more preferably 2% by mass or more and 10% by mass or less, based on totality of the polycarbonate resin composition.

[0211] [Method for producing polycarbonate resin composition]

[0212] The polycarbonate resin composition of the present invention can be obtained by mixing the above-mentioned components in the above-mentioned proportions and, if necessary, mixing various optional components in appropriate proportions and then performing kneading.

[0213] The mixing and kneading can be carried out by the following method: after pre-mixing using commonly used equipment such as a ribbon mixer, a drum roller, etc., methods using a Henschel mixer, a Banbury mixer, a single-screw extruder, a double-screw extruder, a multi-screw extruder, and a two-way kneader (Japanese: コニ一ダ), etc. The heating temperature during kneading is usually appropriately selected within the range of 240°C or more and 320°C or less. For this melt kneading, an extruder is preferably used, and an exhaust-type extruder is particularly preferably used.

[0214] [molded body]

[0215] The polycarbonate resin composition of the present invention after melt kneading or the resulting pellets can be used as a raw material to produce various molded articles by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum forming, and foam molding. In particular, the pellets obtained by melt kneading can be suitably used to produce injection molded articles by injection molding and injection compression molding.

[0216] The molded article formed from the polycarbonate resin composition of the present invention can be suitably used as, for example, exterior and interior parts of parts for electrical and electronic equipment such as televisions, radios, cameras, video cameras, audio players, DVD players, air conditioners, mobile phones, smartphones, walkie-talkies, displays, computers, tablet terminals, portable game devices, desktop game devices, wearable electronic devices, cash registers, calculators, copiers, printers, fax machines, communication base stations, batteries, robots, etc., as well as exterior and interior parts of automobiles, railways, ships, aircraft, aerospace industry equipment, medical equipment, and building materials.

[0217] Example

[0218] The present invention will be further specifically described with reference to Examples, but the present invention is not limited to these Examples. The characteristic values ​​and evaluation results in each example were obtained according to the following procedures.

[0219] (1) Polydimethylsiloxane chain length and content

[0220] The amount was calculated from the integrated value ratio of the methyl group of polydimethylsiloxane by NMR measurement.

[0221] In addition, in this specification, polydimethylsiloxane may be abbreviated as PDM S.

[0222] <Quantitative Method for Determining the Chain Length of Polydimethylsiloxane>

[0223] 1H-NMR measurement conditions

[0224] NMR apparatus: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0225] Probe: 50TH5AT / FG2

[0226] Observation range: -5~15ppm

[0227] Observation center: 5ppm

[0228] Pulse repetition time: 9 seconds

[0229] Pulse width: 45°

[0230] NMR sample tube: 5φ

[0231] Sample size: 30-40 mg

[0232] Solvent: deuterated chloroform

[0233] Measurement temperature: room temperature

[0234] Cumulative times: 256 times

[0235] Allylphenol-terminated polydimethylsiloxane

[0236] A: Integrated value of the methyl group of the dimethylsiloxane moiety observed around δ-0.02 to 0.5

[0237] B: Integrated value of the methylene group of allylphenol observed near δ 2.50 to 2.75. Polydimethylsiloxane chain length = (A / 6) / (B / 4)

[0238] Eugenol-terminated polydimethylsiloxane

[0239] A: Integrated value of the methyl group of the dimethylsiloxane moiety observed around δ-0.02 to 0.5

[0240] B: Integrated value of the methylene group of eugenol observed around δ 2.40 to 2.70

[0241] Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0242] <Quantitative Method for Polydimethylsiloxane Content>

[0243] Method for Quantifying the Amount of Polydimethylsiloxane Copolymer in PTBP-Terminated Polycarbonate Prepared by Copolymerizing Allylphenol-Terminated Polydimethylsiloxane

[0244] NMR apparatus: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0245] Probe: 50TH5AT / FG2

[0246] Observation range: -5~15ppm

[0247] Observation center: 5ppm

[0248] Pulse repetition time: 9 seconds

[0249] Pulse width: 45°

[0250] Cumulative times: 256 times

[0251] NMR sample tube: 5φ

[0252] Sample size: 30-40 mg

[0253] Solvent: deuterated chloroform

[0254] Measurement temperature: room temperature

[0255] A: Integrated value of the methyl group of the BPA moiety observed near δ1.5 to 1.9

[0256] B: Integrated value of the methyl group of the dimethylsiloxane moiety observed around δ-0.02 to 0.3

[0257] C: Integrated value of the butyl group in the p-tert-butylphenyl moiety observed near δ 1.2 to 1.4

[0258] a=A / 6

[0259] b=B / 6

[0260] c=C / 9

[0261] T=a+b+c

[0262] f=a / T×100

[0263] g=b / T×100

[0264] h=c / T×100

[0265] TW=f×254+g×74.1+h×149

[0266] PDMS (mass %) = g × 74.1 / TW × 100

[0267] (2) Viscosity average molecular weight

[0268] The viscosity average molecular weight (Mv) was determined by measuring the viscosity of a dichloromethane solution at 20° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η], which was then calculated using the following formula (Schnell formula).

[0269] [Mathematical formula 2]

[0270] [η] = 1.23 × 10 -5 ×Mv 0.83

[0271] (3) Friction coefficient evaluation

[0272] The coefficient of friction between test pieces was evaluated using a sliding inclination angle measuring machine (manufactured by Toyo Seiki Co., Ltd., AN). The inclination method calculates the static friction coefficient based on the angle at which the test piece starts sliding when the inclination angle of the inclined plate is gradually increased. The test pieces were kept under the following measurement conditions for at least 24 hours before being tested.

[0273] exist Figure 1 Schematic diagram of friction coefficient evaluation is shown in FIG. Regarding the upper test piece, two positions on both sides of the test piece were fixed on a weight (slider (Japanese: スレツド)) with double-sided tape (Sumitomo 3M Co., Ltd., transparent double-sided tape Cat. No. 665-3-12), and regarding the lower test piece, two positions on both sides of the test piece were fixed on an inclined plate with double-sided tape (Sumitomo 3M Co., Ltd., transparent double-sided tape Cat. No. 665-3-12). In addition, the orientation of the test pieces was set so that each became the flow direction (MD direction). The inclination angle θ of the inclined plate was measured when the sliding distance of the upper test piece reached 10 mm.

[0274] [Mathematical formula 3]

[0275] μ S =tanθ

[0276] In this evaluation, the value of θ measured according to the above formula (Moran's law) was substituted and the result was calculated as the static friction coefficient μ S The smaller the value of the static friction coefficient is, the smaller the friction is and the better it is.

[0277] The static friction coefficient was measured 5 times and the average value was calculated.

[0278] [Measurement conditions]

[0279] Upper test piece shape: 70mm in length, 100mm in width, 3.0mm in thickness

[0280] Lower test piece: same material (common material), 150mm long, 150mm wide, 3.0mm thick

[0281] The changing speed of the tilt angle of the tilt plate: 2.7° / S

[0282] Sliding body cross-sectional area: 65cm 2 (i.e., inter-surface pressure 15g / cm 2 )

[0283] Slider weight: 1.0kg

[0284] Measurement direction: MD direction

[0285] Number of measurements: 5 times

[0286] Measurement temperature: 23±1℃, relative humidity 50±5%

[0287] Measurement conditions: No lubrication.

[0288] (4) Friction and wear evaluation

[0289] A constant load measuring machine (HEIDON TYPE-40, manufactured by Shinto Scientific Co., Ltd.) was used. The lower flat plate test piece was fixed to the apparatus side so that the surface cut by a gate cutter (manufactured by DUMBBELL Co., Ltd.) became the contact surface with the lower flat plate test piece, and then the two were set perpendicularly.

[0290] In the return stroke of the 200th reciprocating sliding, in the range of 240.5 to 241 (seconds), the maximum value of the friction coefficient is set as μ M1 、μ M2 、μ M3 , followed by μ M1 、μ M2 、μ M3 The subsequent minimum values ​​are set to μ m1 、μ m2 、μ m3 .exist Figure 2 An example is shown in FIG.

[0291] Use the following formula to calculate the maximum friction coefficient μ M The results of rounding off to 3 decimal places are shown in Table 3.

[0292] Maximum friction coefficient μ M =(μ M1 +μ M2 +μ M3 ) / 3

[0293] Friction coefficient μ after stick-slip m =(μ m1 +μ m2 +μ m3 ) / 3

[0294] Δμ=μ M -μ m

[0295] [Measurement conditions]

[0296] Upper strip test piece shape: 40mm in length, 10mm in width, 4.0mm in thickness

[0297] Lower flat test piece shape: same material (common material), 80mm in length, 80mm in width, 3.0mm in thickness

[0298] Load condition: 500g

[0299] Measuring speed: 500mm / min

[0300] Measuring length: 10mm

[0301] Reciprocating times: 200 times.

[0302] (5) Abnormal noise evaluation

[0303] The noise generated during the friction and wear test was measured using a sound level meter (DT-805L, manufactured by Shenzhen Everbest Machinery Industry Co., Ltd.). The sound level meter, mounted on a pedestal fixture, was brought 10 mm close to the long test piece secured to the upper vise. The maximum volume (dB) during the measurement is reported as the result.

[0304] [Measurement conditions]

[0305] Response speed: FAST

[0306] Range: Low.

[0307] (6) Performance evaluation

[0308] <Impact Resistance Evaluation>

[0309] (Charpy impact strength)

[0310] Using the pellets obtained for evaluation in each of the Examples, Comparative Examples, and Reference Examples, test pieces were prepared in accordance with JIS K 7139:2009 from 4 mm thick molded articles formed under the following conditions in accordance with JIS K 6719-2:2011. Using the prepared test pieces, Charpy impact strength was measured at 23°C and -40°C in accordance with JIS K 7111-1:2012.

[0311] (forming conditions)

[0312] Granule drying: 120℃, 5 hours

[0313] Injection molding machine: EC100SX (manufactured by Toshiba Machine Co., Ltd.)

[0314] Barrel temperature: 280℃

[0315] Test piece shape: length 80±2mm, width 10±0.2mm

[0316] <Color tone evaluation>

[0317] (YI value)

[0318] The evaluation pellets obtained in each example, comparative example, and reference example were injection molded using an injection molding machine (MD50XB, manufactured by NIIGATA MACHINE TECHNO CO., LTD.) under the conditions of a cylinder temperature of 280°C, a mold temperature of 80°C, and a cycle time of 40 seconds into flat test pieces measuring 50 × 30 × 3 μm thick.

[0319] The YI value of the obtained test piece was measured five times by a reflectance method using a spectrophotometer under the conditions of illuminant C, a 2-degree field of view, and a measurement aperture of 30 mmφ, and the average value was determined.

[0320] SE2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used as a spectrophotometer in Examples 1 to 6, Comparative Examples 1 to 3, and Reference Examples 1 to 3. SE7700 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used as a spectrophotometer in Examples 7 to 11 and Comparative Examples 4 to 6.

[0321] <Production Example 1: Production of Polycarbonate Oligomer>

[0322] Sodium dithionite was added to a 5.6 mass % aqueous sodium hydroxide solution at 2000 ppm relative to bisphenol A (BPA) (which was later dissolved), and BPA was dissolved therein to a BPA concentration of 13.5 mass %, thereby preparing a BPA aqueous sodium hydroxide solution.

[0323] The BPA sodium hydroxide aqueous solution, 40 L / hr, dichloromethane, 15 L / hr, and 4.0 kg / hr of phosgene were continuously introduced into a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m. The tubular reactor had a jacket portion, through which cooling water was passed to maintain the reaction liquid temperature below 40°C. The reaction liquid exiting the tubular reactor was continuously introduced into a 40 L baffled tank reactor equipped with swept blades. A sodium hydroxide aqueous solution of BPA was further added at a rate of 2.8 L / hr, a 25% by mass sodium hydroxide aqueous solution was added at a rate of 0.07 L / hr, water was added at a rate of 17 L / hr, and a 1% by mass triethylamine aqueous solution was added at a rate of 0.64 L / hr to allow the reaction to proceed. The reaction liquid overflowing from the tank reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the dichloromethane phase was collected.

[0324] The concentration of the polycarbonate oligomer thus obtained was 341 g / L, and the chloroformate group concentration was 0.71 mol / L.

[0325] <Polycarbonate-polyorganosiloxane copolymer (A1)>

[0326] In a 50 L tank reactor equipped with a baffle, a paddle-type stirring blade, and a cooling jacket, 15 L of the polycarbonate oligomer solution produced in Production Example 1 above, 10.1 L of dichloromethane, 407 g of o-allylphenol-terminated modified polydimethylsiloxane (PDMS) having an average chain length n of 37, and 8.4 mL of triethylamine were added. 1065 g of an aqueous sodium hydroxide solution prepared by dissolving 85 g of sodium hydroxide in 980 mL of pure water was added with stirring, and the polycarbonate oligomer and the allylphenol-terminated modified PDMS were reacted for 20 minutes.

[0327] To this polymerization liquid, a dichloromethane solution of p-tert-butylphenol (PTBP) (prepared by dissolving 147 g of PTBP in 1.0 L of dichloromethane) and a sodium hydroxide aqueous solution of bisphenol A (prepared by dissolving 1093 g of bisphenol A in an aqueous solution prepared by dissolving 618 g of sodium hydroxide and 2.1 g of sodium dithionite in 9.0 L of pure water) were added, and a polymerization reaction was carried out for 40 minutes.

[0328] 13 L of dichloromethane was added for dilution and the mixture was stirred for 20 minutes, followed by separation into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer (PC-PDMS copolymer) and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was separated.

[0329] The thus obtained dichloromethane solution of the PC-PDMS copolymer was washed sequentially with a 0.03 mol / L aqueous sodium hydroxide solution and 0.2 mol / L hydrochloric acid at 15% by volume relative to the solution, and then repeatedly washed with pure water until the conductivity of the aqueous phase after washing was 5 μS / cm or less.

[0330] The dichloromethane solution of the PC-PDMS copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120° C. under reduced pressure to produce a PC-PDMS copolymer (A1).

[0331] The content of the PDMS block portion of the obtained PC-PDMS copolymer (A1) determined by NMR was 6.0% by mass, and the viscosity average molecular weight Mv was 17,700.

[0332] <Polycarbonate-polyorganosiloxane copolymer (A2)>

[0333] A PC-PDMS copolymer (A2) was produced in the same manner as in the polycarbonate-polyorganosiloxane copolymer (A1) except that an o-allylphenol-terminated modified PDMS having an average chain length n of 88 was used.

[0334] The content of the PDMS block portion of the obtained PC-PDMS copolymer (A2) determined by nuclear magnetic resonance (NMR) was 6.0% by mass, and the viscosity average molecular weight Mv was 17,700.

[0335] <Polycarbonate Resin (A')>

[0336] Aromatic homopolycarbonate resin [manufactured by Idemitsu Kosan Co., Ltd., TARFLO NFN1700 (trade name), viscosity average molecular weight = 17700]

[0337] <Copolymer (B)>

[0338] "MODIPERAS100 (trade name)" [manufactured by NOF Corporation]

[0339] <Release Agent (C)>

[0340] A mixture of pentaerythritol stearate and pentaerythritol palmitate (mixing ratio: C16:C18 = 1:1.1) [manufactured by RIKEN VITAMIN CO., LTD., EW440A]

[0341] <Other ingredients>

[0342] Antioxidant: "IRGAFOS 168 (trade name)" [tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Japan Co., Ltd.]

[0343] Examples 1 to 6, Comparative Examples 1 to 3, Reference Examples 1 to 3

[0344] The PC-POS copolymer (A1) or (A2), an ethylene-vinyl acetate copolymer (B) having a styrene-based (co)polymer segment, a release agent (C), and an antioxidant were mixed in the proportions shown in Tables 1 and 2, supplied to a vented twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at a screw speed of 250 rpm, a discharge rate of 25 kg / hr, and a resin temperature of 280°C to obtain pellet samples for evaluation.

[0345] After drying the pellet sample for evaluation at 120°C for 5 hours, injection molding was performed using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS150E-5A) at a barrel temperature of 280°C and a mold temperature of 80°C to produce two flat test pieces (150 mm long, 150 mm wide, and 3 mm thick) for evaluating the coefficient of friction. One piece was used as the lower test piece. The other piece was then cut using a band saw (Vz-300 manufactured by Y Skoki Co., Ltd.), and the burrs on the cut surface were removed with sandpaper to produce an upper test piece (70 mm long, 100 mm wide, and 3 mm thick).

[0346] Tables 1 and 2 show the results of the friction coefficient test, impact properties, and color tone evaluation.

[0347] [Table 1]

[0348]

[0349] [Table 2]

[0350]

[0351] Examples 7 to 11, Comparative Examples 4 to 7

[0352] The PC-POS copolymer (A1) or (A2), an ethylene-vinyl acetate copolymer (B) having a styrene-based (co)polymer segment, a release agent (C), and an antioxidant were mixed in the proportions shown in Table 3, supplied to a vented twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at a screw speed of 250 rpm, a discharge rate of 25 kg / hr, and a resin temperature of 280°C to obtain pellet samples for evaluation.

[0353] After drying the pellet sample at 120°C for 5 hours, it was injection molded using an injection molding machine (EC100SX, manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 280°C and a mold temperature of 80°C to produce a dumbbell-shaped tensile test piece (Type A) in accordance with JIS K7139:2009 and ISO 20753:2008. Subsequently, a gate cutter (manufactured by DUMBBELL CO., LTD.) set at 88°C was used to cut the sample into a long strip (80 mm long, 10 mm wide, 4 mm thick). This was then cut in half using a band saw (Vz-300, manufactured by YSkoki Co., Ltd.). The surface cut by the gate cutter was deburred using a razor or the like to produce a long strip test piece (40 mm long, 10 mm wide, 4 mm thick) used as the upper test piece for friction and wear evaluation.

[0354] In addition, the above-mentioned evaluation pellet sample was dried at 120°C for 5 hours and then injection molded using an injection molding machine (NEX110, manufactured by Nissei Plastic Industry Co., Ltd.) at a cylinder temperature of 280°C and a mold temperature of 80°C to produce a flat test piece (80 mm in length, 80 mm in width, and 3 mm in thickness) used as the lower test piece for friction and wear evaluation.

[0355] It should be noted that Examples 7 to 11 and Comparative Examples 4 to 7 were performed independently of Examples 1 to 6, Comparative Examples 1 to 3, and Reference Examples 1 to 3 described above.

[0356] Table 3 shows the evaluation results of friction and wear, noise, impact properties, and color tone.

[0357] [Table 3]

[0358]

[0359] Industrial applicability

[0360] According to the present invention, a polycarbonate resin composition and a molded article thereof can be obtained with improved sliding properties and excellent color tone without compromising the excellent impact resistance of polycarbonate resins. The molded article obtained by the present invention has excellent sliding properties, thereby suppressing, for example, friction noise.

Claims

1. A polycarbonate resin composition comprising a polycarbonate resin S and a copolymer B, The polycarbonate resin S contains a polycarbonate-polyorganosiloxane copolymer A, The polycarbonate-polyorganosiloxane copolymer A comprises a polycarbonate block A-1 comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block A-2 comprising a repeating unit represented by the following general formula (II). The average chain length of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 20 or more and 100 or less, The copolymer B has a structural unit b-1 represented by the following general formula (X1), a structural unit b-2 represented by the following general formula (X2), and a structural unit b-3 represented by the following general formula (X3). Where R 1 and R 2 Each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms, X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-, and R 3 and R 4 each independently represents hydrogen, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a and b each independently represent an integer of 0 to 4. R 31 Each of them independently represents a halogen atom or an alkyl group having 1 to 10 carbon atoms, and c represents an integer of 0 to 5.

2. The polycarbonate resin composition according to claim 1, wherein The structural unit b-1 represented by the general formula (X1) constitutes the side chain of the copolymer B.

3. The polycarbonate resin composition according to claim 1 or 2, wherein The structural unit b-2 represented by the general formula (X2) and the structural unit b-3 represented by the general formula (X3) constitute the main chain of the copolymer B.

4. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the structural unit b-1 represented by the general formula (X1) is 10% by mass or more and 50% by mass or less relative to 100% by mass of the total of the structural unit b-2 represented by the general formula (X2) and the structural unit b-3 represented by the general formula (X3).

5. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the structural unit b-2 represented by the general formula (X2) is 90 mass% or more and 97 mass% or less relative to 100 mass% of the total of the structural unit b-2 represented by the general formula (X2) and the structural unit b-3 represented by the general formula (X3).

6. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the structural unit b-3 represented by the general formula (X3) is 3 mass% or more and 10 mass% or less relative to 100 mass% of the total of the structural unit b-2 represented by the general formula (X2) and the structural unit b-3 represented by the general formula (X3).

7. The polycarbonate resin composition according to claim 1 or 2, wherein The copolymer B is a graft copolymer with an ethylene-vinyl acetate copolymer segment as the main chain and a styrene (co)polymer segment as the side chain.

8. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the copolymer B is 0.5 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S.

9. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the copolymer B is 1 part by mass or more and 15 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S.

10. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the copolymer B is 2 parts by mass or more and 7 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S. The polycarbonate resin composition according to claim 1 or 2, further comprising a release agent C.

12. The polycarbonate resin composition according to claim 11, wherein The release agent C is a fatty acid ester.

13. The polycarbonate resin composition according to claim 11, wherein The release agent C is a full ester of pentaerythritol and aliphatic carboxylic acid.

14. The polycarbonate resin composition according to claim 13, wherein The full ester of pentaerythritol and aliphatic carboxylic acid is at least one selected from the group consisting of pentaerythritol stearic acid full ester, pentaerythritol palmitic acid full ester and pentaerythritol behenic acid full ester.

15. The polycarbonate resin composition according to claim 13, wherein The full ester of pentaerythritol and aliphatic carboxylic acid is a mixture of pentaerythritol palmitic acid full ester and pentaerythritol stearic acid full ester in a mass ratio of 5:5 to 3:

7.

16. The polycarbonate resin composition according to claim 11, wherein The content of the release agent C is 0.10 parts by mass or more and 0.45 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S.

17. The polycarbonate resin composition according to claim 11, wherein The content of the release agent C is 0.25 parts by mass or more and 0.30 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S.

18. The polycarbonate resin composition according to claim 1 or 2, wherein Also contains antioxidants.

19. The polycarbonate resin composition according to claim 18, wherein The antioxidant is a phosphorus antioxidant and / or a phenolic antioxidant.

20. The polycarbonate resin composition according to claim 18, wherein The amount of the antioxidant blended is 0.05 parts by mass or more and 0.3 parts by mass or less relative to 100 parts by mass of the polycarbonate resin S.

21. The polycarbonate resin composition according to claim 1 or 2, wherein The average chain length of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 50 or more and 100 or less.

22. The polycarbonate resin composition according to claim 1 or 2, wherein The average chain length of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 70 or more and 100 or less.

23. The polycarbonate resin composition according to claim 1 or 2, wherein In the general formula (I), a and b are 0, and X is a single bond or an alkylene group having 1 to 8 carbon atoms; or a and b are 0, and X is an isopropylidene group.

24. The polycarbonate resin composition according to claim 1 or 2, wherein In the general formula (II), R 3 and R 4 Each of them is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

25. The polycarbonate resin composition according to claim 1 or 2, wherein In the general formula (II), R 3 and R 4 All are methyl.

26. The polycarbonate resin composition according to claim 1 or 2, wherein The polyorganosiloxane block A-2 containing the repeating unit represented by the general formula (II) has a unit represented by at least one of the following general formulas (II-I) to (II-III): Where R 3 ~R 6 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. 3 ~R 6 Optional same or different, Y represents -R 7 O-、-R 7 COO-、-R 7 NH-, -R 7 NR 8 -、-COO-、-S-、-R 7 COO-R 9 -O-, or -R 7 OR 10 -O-, multiple Y are optionally the same or different from each other, the R 7 represents a single bond, a linear alkylene group, a branched alkylene group or a cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group, R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, R 9 represents a diarylene group, R 10 represents a linear, branched, or cyclic alkylene group, or a diarylene group, β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, n represents the average chain length of the polyorganosiloxane, n-1, p, and q each represent the number of repetitions of the organosiloxane unit, each being an integer greater than 1, and the sum of p and q is n-2.

27. The polycarbonate resin composition according to claim 26, wherein R in the general formula (II-I), (II-II) and / or (II-III) 3 ~R 6 Each of them is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

28. The polycarbonate resin composition according to claim 26, wherein R in the general formula (II-I), (II-II) and / or (II-III) 3 ~R 6 All are methyl.

29. The polycarbonate resin composition according to claim 26, wherein In the general formula (II-I), (II-II) and / or (II-III), Y is -R 7 O-, R 7 It is an aryl-substituted alkylene group.

30. The polycarbonate resin composition according to claim 26, wherein In the general formula (II-I), (II-II) and / or (II-III), Y is an organic residue derived from allylphenol or an organic residue derived from eugenol.

31. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 0.1% by mass or more and 60% by mass or less.

32. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 2% by mass or more and 50% by mass or less.

33. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polyorganosiloxane block A-2 in the polycarbonate-polyorganosiloxane copolymer A is 4% by mass or more and 8% by mass or less.

34. The polycarbonate resin composition according to claim 1 or 2, wherein The viscosity average molecular weight of the polycarbonate-polyorganosiloxane copolymer A is 9,000 to 50,000.

35. The polycarbonate resin composition according to claim 1 or 2, wherein The viscosity average molecular weight of the polycarbonate-polyorganosiloxane copolymer A is 16,000 or more and 20,000 or less.

36. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polycarbonate-polyorganosiloxane copolymer A in the polycarbonate resin S contained in the polycarbonate resin composition is 50% by mass or more.

37. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polycarbonate-polyorganosiloxane copolymer A in the polycarbonate resin S contained in the polycarbonate resin composition is 90% by mass or more.

38. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polycarbonate-polyorganosiloxane copolymer A in the polycarbonate resin S contained in the polycarbonate resin composition is 100% by mass.

39. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polycarbonate-based resin S is 65% by mass or more and 99.5% by mass or less based on 100% by mass of the total amount of the polycarbonate-based resin composition.

40. The polycarbonate resin composition according to claim 1 or 2, wherein The content of the polycarbonate-based resin S is 90% by mass or more and 98% by mass or less based on 100% by mass of the total amount of the polycarbonate-based resin composition. 41 . A molded article obtained by molding the polycarbonate resin composition according to claim 1 .

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