Polycarbonate-based resin composition and molded article thereof

Abstract

Provided are: a polycarbonate-based resin composition which contains a polycarbonate-based resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A) and contains at least one selected from the group consisting of a light-resistant agent, an elastomer, a colorant, photoluminescent particles, an inorganic filler, a flame retardant, and an acrylic resin, the polycarbonate-based resin composition realizing an excellent balance between impact resistance and scratch resistance due to the resin (S) containing a polycarbonate block that contains the structural unit (A-1) represented by general formula (1) and containing a polyorganosiloxane block that contains a repeating structure (A-2) of the structure represented by general formula (XX), the content of the structural unit (A-1) in the resin (S) being 78.0 mass% or more, and the content of the structural unit represented by general formula (XX) in the resin (S) being 2.0 mass% to 25.0 mass%, inclusive; and a molded article thereof.

Description

Polycarbonate resin composition and molded article thereof

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

[0002] Polycarbonate resins are known to have excellent properties such as transparency, impact resistance, and flame retardancy. Therefore, they are expected to be widely used in various fields, such as electrical and electronic equipment and automobiles. In recent years, from the perspective of carbon neutrality, there has been a demand for the development of polycarbonate resins made from plant-derived monomers. As such polycarbonate resins, polycarbonate resins produced using isosorbide, a plant-derived raw material, have been developed (see, for example, Patent Document 1).

[0003] Patent Document 1 describes a polycarbonate resin that uses a compound produced from a plant-derived raw material and has excellent flexibility, hue, and thermal stability, and a polycarbonate resin composition that uses the polycarbonate resin and has excellent impact resistance and heat resistance, with the aim of providing a polycarbonate resin that is excellent in hue, thermal stability, and flexibility, and a polycarbonate resin composition that uses the polycarbonate resin as an impact modifier and has a high biomass content and excellent impact resistance and heat resistance.

[0004] Japanese Patent Application Laid-Open No. 2021-91900

[0005] According to the investigations of the present inventors, it has become clear that there is room for improvement in the impact resistance of the polycarbonate composition described in, for example, Patent Document 1. Furthermore, generally, substances with high hardness tend to be brittle, and therefore it is difficult to achieve both impact resistance and scratch resistance, but molded articles using polycarbonate resins are required to achieve both of these properties.

[0006] The present invention has been made in view of the above circumstances, and provides a polycarbonate resin composition that exhibits the effects of a functional secondary material and that can give molded articles that have an excellent balance between impact resistance and scratch resistance.

[0007] The present inventors have discovered that a polycarbonate resin composition containing a specific structural unit exhibits the effects of a functional secondary material and can provide a molded article that has an excellent balance between impact resistance and scratch resistance.

[0008] That is, according to the present invention, there are provided the following polycarbonate resin compositions and molded articles.

[0009] [1] A polycarbonate-based resin composition comprising a polycarbonate-based resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin, wherein the polycarbonate-based resin (S) contains a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a repeating structure (A-2) of a structure represented by the following general formula (XX), wherein the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-based resin (S) is 78.0% by mass or more, and the content of the structural unit represented by the following general formula (XX) in the polycarbonate-based resin (S) is 2.0% by mass or more and 25.0% by mass or less. [In general formula (XX), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.] [2] The polycarbonate-based resin composition according to [1], wherein the polycarbonate-based resin (S) further contains at least one structural unit (A-3) selected from structures represented by the following general formulas (3) and (4): [In general formulas (3) and (4), R １１ represents a divalent linear or branched aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms; R １２represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.] [3] The polycarbonate resin composition according to [2], wherein the structural unit (A-3) has at least one selected from structural units (A-31) to (A-34) represented by the following general formulas (31) to (34): [In the general formula (31), n ​​represents an integer of 2 to 18.] [4] The R １ and R ２is a methyl group. [5] The polycarbonate-based resin composition according to any one of [1] to [3], wherein the light-resistant agent comprises at least one selected from the group consisting of benzotriazole-based UV absorbers, benzoxazinone-based UV absorbers, salicylate-based UV absorbers, malonic acid ester-based UV absorbers, oxalyl alanide-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, cyanoacrylate-based UV absorbers, and amine-based light-resistance stabilizers. [6] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the elastomer comprises at least one selected from the group consisting of rubber-based graft polymers and rubber-based graft polymer latexes. [7] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the colorant comprises at least one selected from the group consisting of inorganic pigments, organic pigments, and organic dyes. [8] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the glittering particles comprise at least one selected from the group consisting of particles in which at least one selected from the group consisting of metal particles and optical interference pigments is coated with a thin metal film. [9] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the inorganic filler comprises at least one selected from the group consisting of glass filler, silica, and carbon fiber.

[10] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the flame retardant comprises at least one selected from the group consisting of phosphorus-based flame retardants and metal salt-based flame retardants.

[11] The polycarbonate-based resin composition according to any one of [1] to [4], wherein the acrylic resin comprises at least one selected from the group consisting of (co)polymers of a monomer selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, and methacrylonitrile.

[12] A molded article made from the polycarbonate resin composition according to any one of [1] to

[11] .

[0010] According to the present invention, it is possible to provide a polycarbonate resin composition that can give a molded article having an excellent balance between impact resistance and scratch resistance.

[0011] The polycarbonate resin composition and molded articles of the polycarbonate resin composition according to the present invention are described in detail below. In this specification, any preferred definition may be adopted at will, and combinations of preferred definitions are considered more preferable. In this specification, the term "XX to YY" means "XX or more and YY or less." When multiple lower limits, such as "x or more," exist for a single technical feature, or multiple upper limits, such as "y or less," are present, any combination of the upper and lower limits may be selected. When compounds and chemical structures described herein have multiple stereoisomers and structural isomers, all stereoisomers and structural isomers are included, unless otherwise specified.

[0012] 1. Polycarbonate-Based Resin Composition The polycarbonate-based resin composition according to the present invention comprises a polycarbonate-based resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light stabilizer, glittering particles, a colorant, an inorganic filler, an elastomer, a flame retardant, and an acrylic resin. The polycarbonate-based resin composition according to the present invention enables the production of molded articles that exhibit an excellent balance between impact resistance and scratch resistance.

[0013] [Polycarbonate-Based Resin (S)] The polycarbonate-based resin (S) contains a polycarbonate-polyorganosiloxane copolymer (A) and includes a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a repeating unit (A-2) of a structure represented by the following general formula (XX):

[0014]

[0015] In general formula (XX), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.

[0016] <Polycarbonate Block> The polycarbonate block contained in the polycarbonate resin (S) is represented by the following general formula (X) and contains a structural unit (A-1) represented by general formula (1).

[0017]

[0018] In the above general formula (X), R １０ represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. In this specification, the various "divalent" hydrocarbon groups refer to substituents obtained by removing two hydrogen atoms from a hydrocarbon.

[0019] The structural unit (A-1) represented by general formula (1) preferably contains a structural unit represented by the following general formula (11), and more preferably consists solely of a structural unit represented by the following general formula (11).

[0020]

[0021] The content of the structural unit (A-1) represented by general formula (1) in the polycarbonate resin (S) according to the present invention is 78.0% by mass or more, preferably 80.0% by mass or more, and more preferably 81.0% by mass or more, from the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof having excellent impact resistance. For example, the "content of the structural unit (A-1) represented by general formula (1) in the polycarbonate resin (S)" refers to the mass of the structural unit (A-1) represented by general formula (1) relative to the total mass of the structural unit (A-1) represented by general formula (1), the structural unit represented by general formula (XX), and the structural units (A-31) to (A-34) represented by general formulas (31) to (34). The method for measuring the content of the structural unit (A-1) represented by general formula (1) in the polycarbonate resin (S) is not particularly limited, and examples thereof include nuclear magnetic resonance (NMR) analysis.

[0022] The polycarbonate block contained in the polycarbonate resin (S) may further contain at least one structural unit (A-3) selected from structural units represented by the following general formulas (3) and (4): When the polycarbonate block contains the structural unit (A-3), the impact resistance of the molded article can be further improved.

[0023]

[0024] In the above general formula (3), R １１ represents a divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and is preferably a divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms. １２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, preferably a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and more preferably a divalent alicyclic hydrocarbon group having 5 to 15 carbon atoms.

[0025] From the viewpoint of reducing the melt flow rate of the polycarbonate resin (S) and improving the tensile modulus, tensile strength (yield), and glass transition temperature, R １１ and R １２ preferably contains at least one carbon atom selected from tertiary and quaternary carbon atoms, more preferably contains at least one carbon atom selected from tertiary and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, even more preferably contains at least one carbon atom selected from tertiary and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, and particularly from the viewpoint of availability of raw materials, still more preferably contains at least one carbon atom selected from tertiary and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms. １１ and R １２However, the reason why the inclusion of at least one carbon atom selected from tertiary and quaternary carbon atoms reduces the melt flow rate of the polycarbonate-polyorganosiloxane copolymer (A) and improves the tensile modulus, tensile strength (yield), and glass transition temperature is not clear, but it is thought that this is because tertiary and quaternary carbon atoms have low mobility, and structures containing these carbon atoms tend to be rigid. １１ and R １２ However, the reason why the inclusion of a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms reduces the melt flow rate of the polycarbonate resin (S) and improves the tensile modulus, tensile strength (yield), and glass transition temperature is not clear, but it is thought that this is because the cyclic structure restricts molecular mobility, and structures containing this tend to become rigid. Note that the structural unit (A-1) is not included in the structural unit (A-3).

[0026] R in the above general formula (3) １１ The divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms and the divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms represented by R in the above general formula (3) may be substituted with a substituent, and may contain at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms in the carbon chain of the hydrocarbon group. １１Examples of the divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms or the divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms represented by the formula (I) include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, a neopentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a 2-ethylhexylene group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, and an n-tetradecylene group. Examples of the alkylene group include an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, and an n-octadecylene group, and are preferably an n-propylene group, an n-butylene group, an n-pentylene group, a neopentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, or an n-decylene group, and more preferably an n-butylene group, an n-pentylene group, a neopentylene group, an n-hexylene group, an n-heptylene group, or an n-octylene group.

[0027] R in the above general formula (3) １１ The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by R may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. １１ Examples of the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by the formula (I) include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, a tricyclodecylene group, a spiro-bicyclohexylene group, a decahydronaphthylene group, a tricyclotetradecylene group, and a pentacyclopentadecylene group, among which a cyclohexylene group, a tricyclodecylene group, a pentacyclopentadecylene group, a decahydronaphthylene group, a tricyclotetradecylene group, a bicycloheptylene group, or an adamantylene group is preferred, and a cyclohexylene group or a tricyclodecylene group is more preferred.

[0028] R in the above general formula (3) １１The cyclohexylene group represented by the formula (3a) includes various isomers represented by the following general formula (3a): Specific examples include a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group.

[0029]

[0030] In general formula (3a), R １０１ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0031] R in the above general formula (3) １１ The tricyclodecylene group or pentacyclopentadecylene group represented by formula (3b) includes various isomers represented by the following general formula (3b): n′ is 0 or 1.

[0032]

[0033] R in the above general formula (3) １１ The decahydronaphthylene group or tricyclotetradecylene group represented by the formula (3c) includes various isomers represented by the following general formula (3c). Specific examples include a 2,6-decahydronaphthylene group, a 1,5-decahydronaphthylene group, and a 2,3-decahydronaphthylene group. n" is 0 or 1.

[0034]

[0035] R in the above general formula (3) １１ The bicycloheptylene group represented by the formula (3d) includes various isomers represented by the following general formula (3d). Specific examples include a 2,3-bicycloheptylene group and a 2,5-bicycloheptylene group.

[0036]

[0037] R in the above general formula (3) １１ The adamantylene group represented by the formula (3e) includes various isomers represented by the following general formula (3e). Specific examples include a 1,3-adamantylene group.

[0038]

[0039] R in the above general formula (3) １１The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. １１ Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (3f) below include an aromatic hydrocarbon group represented by the formula (3f) below, a 1,4-phenylene group, a 1,3-phenylene group, and a 1,2-phenylene group, and preferably an aromatic hydrocarbon group represented by the formula (3f) below:

[0040]

[0041] In the above general formula (3f), R １０２ and R １０３ 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-. s and t each independently represent an integer of 0 to 4.

[0042] In the above general formula (3f), R １０２ and R １０３ The halogen atoms independently represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １０２ and R １０３ Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" includes linear and branched groups, and the same applies hereinafter), various pentyl groups, and various hexyl groups. １０２ and R １０３ The alkoxy groups each independently represent include those in which the alkyl moiety is the above-mentioned alkyl group.

[0043] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group and a cyclohexanediyl group, and an cycloalkylene group having 5 to 10 carbon atoms is preferred. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3-methylcyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a cyclododecylidene group, and a 2-adamantylidene group, with a cycloalkylidene group having 5 to 12 carbon atoms being preferred, and a cycloalkylidene group having 5 to 8 carbon atoms being more preferred. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0044] s and t each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, preferred are those in which s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or those in which s and t are 0 and X is an alkylidene group, particularly an isopropylidene group.

[0045] R in the above general formula (4) １２ The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by R in general formula (3) is １１ and the like, preferably a cyclohexylene group, a tricyclodecylene group, a pentacyclopentadecylene group, a decahydronaphthylene group, a tricyclotetradecylene group, a bicycloheptylene group, or an adamantylene group, and more preferably a cyclohexylene group or a tricyclodecylene group.

[0046] From the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof having excellent impact resistance, the structural unit (A-3) preferably includes at least one selected from structural units (A-31) to (A-34) represented by the following general formulas (31) to (34), more preferably includes at least one selected from structural units (A-31) to (A-33), even more preferably includes at least one selected from structural units (A-31) to (A-33), and still more preferably includes structural unit (A-32).

[0047]

[0048] In the general formula (31), n ​​represents an integer of 2 to 18, preferably 3 to 10, and more preferably 4 to 8.

[0049] When the structural unit (A-3) contains at least one selected from the structural units (A-31) to (A-34), the total content of the structural units (A-31) to (A-34) in the structural unit (A-3) is preferably 90.0% by mass or more, more preferably 93.0% by mass or more, even more preferably 95.0% by mass or more, and is preferably 100.0% by mass or less, more preferably 100.0% by mass or less.

[0050] The polycarbonate block contained in the polycarbonate resin (S) preferably contains a structural unit (A-1) represented by general formula (1) and a structural unit (A-3) represented by general formula (3), more preferably contains a structural unit (A-1) represented by general formula (1) and at least one selected from structural units (A-31) to (A-34) represented by general formulas (31) to (34), and even more preferably contains a structural unit (A-1) represented by general formula (1) and a structural unit (A-32) represented by general formula (32).

[0051] From the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof having excellent impact resistance, the content of the structural unit (A-1) in the polycarbonate block is preferably 80.0 mol% or more, more preferably 82.0 mol% or more, even more preferably 84.0 mol% or more, and preferably 100.0 mol% or less, more preferably 98.0 mol% or less, even more preferably 96.0 mol% or less, and particularly preferably 92.0 mol% or less. When the polycarbonate block contains the structural unit (A-3), from the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof having even more excellent impact resistance, the content of the structural unit (A-3) in the polycarbonate block is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 4.0 mol% or more, and preferably 20.0 mol% or less, more preferably 18.0 mol% or less, even more preferably 16.0 mol% or less. The contents of the structural unit (A-1) and the structural unit (A-3) in the polycarbonate block are calculated by nuclear magnetic resonance (NMR) measurement.

[0052] <Polyorganosiloxane Block> The polyorganosiloxane block contained in the polycarbonate resin (S) contains at least a repeating structure (A-2) of a structure represented by the following general formula (XX): The polyorganosiloxane block is a structural unit containing at least one structure represented by the following general formula (XX) that is present between the two most adjacent polycarbonate bonds on the main chain of the polycarbonate-polyorganosiloxane copolymer (A), and is preferably a repeating structure of the structure represented by the general formula (XX) represented by the following general formula (2).

[0053]

[0054] In general formula (XX), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.

[0055]

[0056] In general formula (2), R １ and R ２ represents R in the general formula (XX). １ and R ２ a-1 is the number of repetitions of the structure represented by formula (XX), and a is an integer of 2 to 500.

[0057] In general formula (2), R １ and R ２ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １ and R ２ Examples of the alkyl group having 1 to 10 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. １ and R ２ Examples of the alkoxy group having 1 to 10 carbon atoms represented by the formula (I) include an alkoxy group in which the alkyl group moiety is the same as the alkyl group described above. １ and R ２ Examples of the aryl group having 6 to 12 carbon atoms represented by R include a phenyl group and a naphthyl group. １ and R ２ Examples of the alkylaryl group having 7 to 22 carbon atoms represented by the formula (I) include alkylaryl groups in which the alkyl group moiety is the same as the alkyl group described above and the aryl group moiety is the same as the aryl group described above. １ and R ２ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and further preferably a methyl group.

[0058] The polyorganosiloxane block preferably has a structure represented by the following general formula (21).

[0059]

[0060] In general formula (21), R １ , R ２ and a is R in the general formula (2). １, R ２ , and a have the same meaning. ３ and R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. ６ represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of a plurality of R ８ may be the same or different and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. a represents an integer of 2 to 500, and b represents an integer of 2 to 200. u and z represent 0 or 1.

[0061] The polyorganosiloxane block preferably has a structure represented by the following general formula (22).

[0062]

[0063] In general formula (22), R １ ~R ４ , R ６ , R ８ , a, b, u, and z are R in the general formula (2) and the general formula (21). １ ~R ４ , R ６ , R ８ , a, b, u, and z have the same meaning. ５represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of ７ represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents the same meaning as above. b1 represents an integer of 2 to 200. u1 and z1 represent 0 or 1.

[0064] The polyorganosiloxane block may have at least one of the structures represented by the following general formulas (23) to (26).

[0065]

[0066] In general formulas (23) to (26), R １ ~R ８ , a, b, b1, u, u1, z, and z1 are R in the general formula (2), the general formula (21), and the general formula (22). １ ~R ８ , a, b, b1, u, u1, z, and z1 have the same meaning as -(O) which is bonded to β. ｚ - and - (O) ｚ１ In the formula (I), z and z1 are 1. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid compound.

[0067] In general formulas (23) to (26), R ３ and R ４ The halogen atom represented by R １ and R ２ The halogen atoms are the same as those shown in R １ ~R ４ Examples of the alkyl group having 1 to 10 carbon atoms represented by R １ and R２ The alkyl group may be the same as the alkyl group shown in R ３ and R ４ The alkoxy group having 1 to 10 carbon atoms represented by R １ and R ２ The alkoxy group may be the same as that shown in R ３ and R ４ The aryl group having 6 to 12 carbon atoms represented by R １ and R ２ The aryl group may be the same as the aryl group shown in R ３ and R ４ The alkylaryl group having 7 to 22 carbon atoms represented by R １ and R ２ The alkylaryl group may be the same as the alkylaryl group shown in R ３ and R ４ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and R ３ and R ４ More preferably, all of are methyl groups.

[0068] R ５ , R ６ , R ７ , or R ８ Examples of the arylene group having 6 to 20 carbon atoms represented by the formula (R) include a phenylene group and a naphthylene group. ５ , R ６ , R ７ , or R ８ Examples of the alkylene group having 1 to 10 carbon atoms represented by the formula (R) include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and various butylene groups. The various butylene groups are preferably tetramethylene groups. ５ , R ６ , R ７ , or R ８Examples of the alkylarylene group having 7 to 22 carbon atoms and represented by the formula (I) include alkylarylene groups having the same alkyl group moiety as the alkylene group and the same arylene group moiety as the arylene group. However, these groups do not contain -O-, -COO-, -CO-, -S-, -NH-, or NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. １１１ Examples of the alkyl group having 1 to 10 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. １１１ The aryl group having 6 to 10 carbon atoms represented by the formula (I) includes a phenyl group and a naphthyl group.

[0069] R ５ and R ６ are preferably alkylene groups having 1 to 10 carbon atoms or alkylarylene groups having 7 to 22 carbon atoms, more preferably alkylene groups having 1 to 5 carbon atoms or alkylarylene groups having 7 to 11 carbon atoms, and are preferably trimethylene groups or trimethyleneylphenylene groups (—CH ２ CH ２ CH ２ -Ph-) is more preferred.

[0070] R ７ and R ８ are preferably alkylene groups having 1 to 10 carbon atoms, more preferably alkylene groups having 1 to 5 carbon atoms, and are preferably dimethylene groups, methyl-substituted dimethylene groups (—CH ２ CHMe-), a trimethylene group, or a tetramethylene group is more preferred, and all of them are more preferably a dimethylene group.

[0071] In general formula (2) and general formulas (21) to (26), a represents the number of repetitions of the structural unit represented by general formula (XX) plus 1, i.e., the number of repetitions of Si atoms, also referred to as the chain length. a is preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, still more preferably 20 or more, and is preferably an integer of 300 or less, more preferably 95 or less, even more preferably 70 or less, and still more preferably 50 or less. In general formula (2) and general formulas (21) to (26), a is preferably an integer of 2 to 300, more preferably 10 to 95, even more preferably 15 to 70, and even more preferably 20 to 50. The average value of a in the polycarbonate resin (S) is preferably 2 or more, more preferably 5 or more, even more preferably 10 or more, even more preferably 15 or more, particularly preferably 20 or more, and is preferably 300 or less, more preferably 95 or less, even more preferably 70 or less, and still more preferably 50 or less. The average value of a in the polycarbonate resin (S) is preferably 2 to 300, more preferably 10 to 95, even more preferably 15 to 70, still more preferably 15 to 50, and even more preferably 20 to 50. The average value of a in the polycarbonate resin (S) is calculated by nuclear magnetic resonance (NMR) measurement.

[0072] In general formulas (21) to (26), b and b1 represent the number of repeating units, and each independently represents an integer of preferably 2 or more, more preferably 5 or more, even more preferably 8 or more, even more preferably 10 or more, and even more preferably 12 or more, and preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 30 or less, even more preferably 25 or less, and even more preferably 20 or less. In general formulas (21) to (26), b and b1 each independently represent an integer of preferably 2 to 200, more preferably 5 to 100, even more preferably 8 to 50, even more preferably 10 to 30, even more preferably 12 to 25, and even more preferably 12 to 20. The average values ​​of b, b1, and the combined average value b2 of b and b1 in the polycarbonate-based resin (S) are preferably 2 or more, more preferably 5 or more, even more preferably 8 or more, even more preferably 10 or more, and even more preferably 12 or more, and are preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 30 or less, even more preferably 25 or less, and even more preferably 20 or less. The above ranges are preferable due to the ease of availability of raw materials. The average values ​​of b, b1, and the combined average value b2 of b and b1 in the polycarbonate-based resin (S) are preferably 2 to 200, more preferably 5 to 100, even more preferably 8 to 50, even more preferably 10 to 30, even more preferably 12 to 25, and even more preferably 12 to 20. The average value b2 in the polycarbonate-based resin (S) is calculated by nuclear magnetic resonance (NMR) measurement.

[0073] In general formula (21), u is preferably 1. In general formulas (22) to (26), u and u1 are each preferably 1, and it is more preferable that u and u1 are both 1. In general formula (21), z is preferably 1. In general formulas (22) to (26), z and z1 are each preferably 1, and it is more preferable that z and z1 are both 1.

[0074] In general formula (21), R １ ~R ４ are all methyl groups, and R６ is a trimethylene group, and R ８ is a dimethylene group, z is more preferably 1, and R １ ~R ４ are all methyl groups, and R ６ is a trimethylene group, and R ８ It is more preferable that R is a dimethylene group, z is 1, and u is 1. １ ~R ４ are all methyl groups, and R ５ and R ６ are both trimethylene groups, and R ７ and R ８ are both dimethylene groups, and z and z １ are both 1, and u and u １ It is more preferable that both are 1.

[0075] In general formulas (23) to (26), β is a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid compound. Examples of dicarboxylic acid compounds include dicarboxylic acids, dicarboxylic acid anhydrides, dicarboxylic acid halides, and diesters of dicarboxylic acids and lower alcohols. Examples of lower alcohols include methanol, ethanol, and propanol. Examples of β include divalent groups represented by the following general formulas (i) to (v).

[0076]

[0077] The polyorganosiloxane block preferably does not contain a branched structure in order to obtain a polycarbonate resin composition and a molded article thereof that are excellent in impact resistance.

[0078] From the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof having an excellent balance between impact resistance and scratch resistance, the content of the structural unit represented by general formula (XX) in the polycarbonate resin (S) according to the present invention is 2.0% by mass or more, preferably 3.0% by mass or more, more preferably 4.0% by mass or more, and even more preferably 5.0% by mass or more, and is 25.0% by mass or less, preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less. For example, "the content of the structural unit represented by general formula (XX) in the polycarbonate resin (S)" refers to the ratio of the mass of the structural unit represented by general formula (XX) to the total mass of the structural unit (A-1) represented by general formula (1), the structural unit represented by general formula (XX), and the structural units (A-31) to (A-34) represented by general formulas (31) to (34). The method for measuring the content of the structural unit represented by general formula (XX) in the polycarbonate resin (S) is not particularly limited, and may be, for example, nuclear magnetic resonance (NMR) analysis.

[0079] The polycarbonate-based resin (S) according to the present invention may consist solely of one or more of the following polycarbonate-polyorganosiloxane copolymers (A), or may contain the following polycarbonate-based resin (P) (hereinafter, sometimes referred to as "polycarbonate-based resin (P)") other than the following polycarbonate-polyorganosiloxane copolymer (A). From the viewpoint of improving the impact resistance of molded articles, the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin (S) is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more. The upper limit of the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin (S) is not particularly limited, but from the viewpoint of obtaining a polycarbonate-based resin composition having desired properties, it is, for example, 100% by mass or less.

[0080] The number average molecular weight (Mn) of the polycarbonate resin (S) is preferably 5,000 or more, more preferably 6,000 or more, even more preferably 7,000 or more, even more preferably 8,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 15,000 or less. The number average molecular weight (Mn) of the polycarbonate resin (S) is a weighted average of the number average molecular weights (Mn) of each copolymer or resin contained in the polycarbonate resin (S), and each number average molecular weight (Mn) can be measured by the same method as for the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer. The weight average molecular weight (Mw) of the polycarbonate resin (S) is preferably 20,000 or more, more preferably 23,000 or more, even more preferably 25,000 or more, and preferably 60,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, even more preferably 43,000 or less. The weight average molecular weight (Mw) of the polycarbonate resin (S) is a weighted average of the weight average molecular weights (Mw) of each copolymer or resin contained in the polycarbonate resin (S), and each weight average molecular weight (Mw) can be measured by the same method as for the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer.

[0081] [Polycarbonate-Polyorganosiloxane Copolymer (A)] The polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) contains a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) above and a polyorganosiloxane block containing the repeating unit (A-2) of the structure represented by the general formula (XX) above.

[0082] (Polycarbonate Block) Examples of the polycarbonate block containing the structural unit (A-1) represented by general formula (1) contained in the polycarbonate-polyorganosiloxane copolymer (A) include the polycarbonate block containing the structural unit (A-1) represented by general formula (1) shown in the polycarbonate resin (S). The preferred embodiments are also the same.

[0083] From the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having excellent impact resistance, the content of the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 75.0 mass% or more, more preferably 80.0 mass% or more, even more preferably 85.0 mass% or more, and preferably 100.0 mass% or less, more preferably 95.0 mass% or less, even more preferably 90.0 mass% or less. From the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having excellent impact resistance, the content of the structural unit (A-1) in the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 73.0 mass% or more, more preferably 80.0 mass% or more, even more preferably 85.0 mass% or more, and preferably 100.0 mass% or less, more preferably 97.0 mass% or less, even more preferably 95.0 mass% or less.

[0084] When the polycarbonate-polyorganosiloxane copolymer (A) contains the structural unit (A-3) represented by the following general formula (3) or (4), the content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, from the viewpoint of obtaining a polycarbonate resin composition and a molded article thereof that are more excellent in impact resistance, and is preferably 25.0% by mass or less, more preferably 20.0% by mass or less, even more preferably 15.0% by mass or less. When the polycarbonate-polyorganosiloxane copolymer (A) contains the structural unit (A-3) represented by the following general formula (3) or (4), the content of the structural unit (A-3) in the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 1.0 mass% or more, more preferably 3.0 mass% or more, even more preferably 5.0 mass% or more, and is preferably 25.0 mass% or less, more preferably 20.0 mass% or less, even more preferably 15.0 mass% or less, from the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having superior impact resistance. The contents of the polycarbonate block, the structural unit (A-1), and the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer (A) are calculated by nuclear magnetic resonance (NMR) measurement.

[0085] In this specification, the "content of the structural unit (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)" refers to the content of the structural unit (A-1), the structural unit represented by the general formula (XX), the structural unit represented by the following general formula (Y), -OR Ｔ and the structural unit (A-3) contained as needed. The same applies to the "content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer (A)."

[0086]

[0087] In general formula (Y), R Ｙ is R ５ , R ６, R ７ , or R ８ It is. Ｙ is R ５ If z ０ is u1, and R Ｙ is R ６ If z ０ is u and R Ｙ is R ７ If z ０ is z1, and R Ｙ is R ８ If z ０ is z2. R ５ , R ６ , R ７ , R ８ , u1, u, z1, and z2 are R shown in the <Polyorganosiloxane Block> below. ５ , R ６ , R ７ , R ８ , u1, u, z1, and z2 have the same meaning.

[0088] (Polyorganosiloxane Block) The polyorganosiloxane block containing the repeating unit (A-2) of the structure represented by general formula (XX) contained in the polycarbonate-polyorganosiloxane copolymer (A) can be similarly exemplified by the polyorganosiloxane block containing the repeating unit (A-2) of the structure represented by general formula (XX) shown in the polycarbonate resin (S). The preferred embodiments are also the same.

[0089] From the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having excellent impact resistance, the content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, and is preferably 25.0% by mass or less, more preferably 20.0% by mass or less, even more preferably 15.0% by mass or less, and still more preferably 10.0% by mass or less.

[0090] In this specification, the term "content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (A)" refers to the content of the structural unit (A-1), the structural unit represented by general formula (XX), the structural unit represented by the above general formula (Y), -OR Ｔ and the structural unit (A-3) contained as needed.

[0091] From the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having an excellent balance between impact resistance and scratch resistance, the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, even more preferably 4.0% by mass or more, still more preferably 7.5% by mass or more, particularly preferably 9.5% by mass or more, and preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 13.0% by mass or less.

[0092] In this specification, the "content of polyorganosiloxane blocks in the polycarbonate-polyorganosiloxane copolymer (A)" refers to the content of the structural unit (A-1), the structural unit represented by general formula (XX), the structural unit represented by general formula (Y), -OR Ｔ The content of the polyorganosiloxane block and the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (A) is calculated by nuclear magnetic resonance (NMR) measurement.

[0093] (Terminal Structure of Polycarbonate-Polyorganosiloxane Copolymer (A)) In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) has the following terminal structure: -OR Ｔ It may contain a terminal structure represented by R Ｔ is Ar, which will be described later. １ , Ar ２ , Ar ３ , Ar４ , Ar ５ , Ar ６ , R ２１ , R ２２ , R ２３ , R ２４ , R ２５ , R ２６ , p-cumylphenyl group or p-(tert-butyl)phenyl group, and preferably Ar １ , Ar ２ , Ar ３ , Ar ４ , Ar ５ , Ar ６ , or a p-(tert-butyl)phenyl group. １ , Ar ２ , Ar ３ , Ar ４ , Ar ５ , or Ar ６ is preferably a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a chlorophenyl group, or a naphthyl group, and more preferably a phenyl group. Ｔ The content of the terminal structure represented by the formula (I) is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less. Ｔ The content of the terminal structure represented by the formula (I) is preferably 0.01 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, and even more preferably 0.5 to 2.0% by mass. Ｔ The more terminal structures represented by the formula -OR, the fewer terminal hydroxyl groups derived from the diol monomer, and the higher the heat resistance and glass transition temperature of the resin. Ｔ The content of the terminal structure represented by the formula (I) is calculated by nuclear magnetic resonance (NMR) measurement.

[0094] From the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having excellent impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 15,000 or less. The number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 to 30,000, more preferably 8,000 to 25,000, even more preferably 8,000 to 20,000, even more preferably 8,000 to 15,000. In particular, from the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having superior impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 8,000 or more, more preferably 9,000 or more, and even more preferably 10,000 or more.

[0095] The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 20,000 or more, more preferably 23,000 or more, even more preferably 25,000 or more, and is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, even more preferably 43,000 or less. The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 20,000 to 60,000, more preferably 23,000 to 50,000, even more preferably 25,000 to 45,000, even more preferably 25,000 to 43,000. In particular, from the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having superior impact resistance, the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 25,000 or more, more preferably 26,000 or more, and even more preferably 27,000 or more.

[0096] The viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, even more preferably 15,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 18,000 or less. The viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 to 30,000, more preferably 8,000 to 25,000, even more preferably 10,000 to 23,000, even more preferably 14,000 to 20,000, even more preferably 16,000 to 18,000. In particular, from the viewpoint of obtaining a polycarbonate-based resin composition and a molded article thereof having superior impact resistance, the viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 12,000 or more.

[0097] The reason why impact resistance is improved by adjusting the number-average molecular weight, weight-average molecular weight, and viscosity-average molecular weight to fall within the above ranges is unclear, but is presumed to be as follows: When the number-average molecular weight, weight-average molecular weight, and viscosity-average molecular weight are at or above a certain level, the entanglement and interaction between polymer chains is strengthened, which is thought to improve impact resistance.

[0098] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 1.8 or more, more preferably 2.2 or more, even more preferably 2.5 or more, and is preferably 3.2 or less, more preferably 3.0 or less, even more preferably 2.9 or less. The ratio (Mw / Mn) is preferably 1.8 to 3.2, more preferably 2.2 to 3.0, even more preferably 2.5 to 2.9.

[0099] In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) and the structural unit (A-31) represented by the general formula (31), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), and the molar ratio (A-31 / A-1) of the structural unit (A-31) to the structural unit (A-1) and the content x of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (A) satisfy the following condition (C1) or (D1), and may be a polycarbonate-polyorganosiloxane copolymer (S-1). Condition (C1): A-31 / A-1 is 1.0 / 99.0 or more and 25.0 / 75.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D1): A-31 / A-1 is 1.0 / 99.0 or more and 30.0 / 70.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C1), A-31 / A-1 is preferably 20.0 / 80.0 or less, more preferably 17.0 / 83.0 or less. In condition (C1), A-31 / A-1 is preferably 1.0 / 99.0 to 20.0 / 80.0, more preferably 1.0 / 99.0 to 17.0 / 83.0. The A-31 / A-1 ratio in the condition (D1) is preferably 25.0 / 75.0 or less, more preferably 17.0 / 83.0 or less. The A-31 / A-1 ratio in the condition (D1) is preferably 1.0 / 99.0 to 25.0 / 75.0, more preferably 1.0 / 99.0 to 17.0 / 83.0. In the polycarbonate-polyorganosiloxane copolymer (S-1), the total content of the structural units (A-1) and (A-31) in the polycarbonate block is preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 100.0 mol%.

[0100] In one embodiment, the polycarbonate-based resin (S) contains a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) and the structural unit (A-32) represented by the general formula (32), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2). The total content of the structural units (A-1) and (A-32) in the polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer (A) is 90.0 mol% or more, and the molar ratio (A-32 / A-1) of the structural unit (A-32) to the structural unit (A-1) and the content x of the general formula (XX) satisfy the following condition (C2) or (D2), which may be a polycarbonate-polyorganosiloxane copolymer (S-2). Condition (C2): A-32 / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D2): A-32 / A-1 is 1.0 / 99.0 or more and 27.0 / 73.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C2), A-32 / A-1 is preferably 32.0 / 68.0 or less, more preferably 28.0 / 72.0 or less. In condition (C2), A-32 / A-1 is preferably 1.0 / 99.0 to 32.0 / 68.0, more preferably 1.0 / 99.0 to 28.0 / 72.0. The ratio A-32 / A-1 in the condition (D2) is preferably 24.0 / 76.0 or less, more preferably 21.0 / 79.0 or less. The ratio A-32 / A-1 in the condition (D2) is preferably 1.0 / 99.0 to 24.0 / 76.0, more preferably 1.0 / 99.0 to 21.0 / 79.0. In the polycarbonate-polyorganosiloxane copolymer (S-2), the total content of the structural units (A-1) and (A-32) in the polycarbonate block is preferably 100.0 mol%.

[0101] In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) and the structural unit (A-33) represented by the general formula (33), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), and the molar ratio (A-33 / A-1) of the structural unit (A-33) to the structural unit (A-1) and the content x of the general formula (XX) satisfy the following condition (C3) or (D3), which may be a polycarbonate-polyorganosiloxane copolymer (S-3). Condition (C3): A-33 / A-1 is 1.0 / 99.0 or more and 40.0 / 60.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D3): A-33 / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C3), A-33 / A-1 is preferably 35.0 / 65.0 or less, more preferably 30.0 / 70.0 or less. In condition (C3), A-33 / A-1 is preferably 1.0 / 99.0 to 35.0 / 65.0, more preferably 1.0 / 99.0 to 30.0 / 70.0. In condition (D3), A-33 / A-1 is preferably 33.0 / 67.0 or less, more preferably 31.0 / 69.0 or less. In the condition (D3), the ratio A-33 / A-1 is preferably 1.0 / 99.0 to 33.0 / 67.0, more preferably 1.0 / 99.0 to 31.0 / 69.0. In the polycarbonate-polyorganosiloxane copolymer (S-3), the total content of the structural units (A-1) and (A-33) in the polycarbonate block is preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 100.0 mol%.

[0102] In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1), the structural unit (A-32) represented by the general formula (32), and the structural unit (A-33) represented by the general formula (33), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), The polycarbonate-polyorganosiloxane copolymer (S-4) may be a polycarbonate-polyorganosiloxane copolymer (S-4) in which the molar ratio of the sum of the structural units (A-32) and (A-33) to the structural unit (A-33) ((total of A-32 and A-33) / A-1)), the molar ratio of the structural unit (A-32) to the structural unit (A-33) (A-32 / A-33), and the content x of the general formula (XX) satisfy the following condition (C41), (C42), (C43), (D41), (D42), or (D43): Condition (C41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 39.0 / 61.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 31.0 / 69.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 46.0 / 54.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 32.0 / 68.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. Condition (D42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 36.0 / 64.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less.Condition (D43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (the total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 41.0 / 59.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C41), (the total of A-32 and A-33) / A-1 is preferably 35.0 / 65.0 or less, more preferably 31.0 / 69.0 or less. In condition (C41), (the total of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 35.0 / 65.0, more preferably 1.0 / 99.0 to 31.0 / 69.0. In the condition (C42), the ratio (total of A-32 and A-33) / A-1 is preferably 30.0 / 70.0 or less, more preferably 25.0 / 75.0 or less. In the condition (C42), the ratio (total of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 30.0 / 70.0, more preferably 1.0 / 99.0 to 25.0 / 75.0. In the condition (C43), the ratio (total of A-32 and A-33) / A-1 is preferably 42.0 / 58.0 or less, more preferably 37.0 / 63.0 or less. In the condition (C43), the ratio (total of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 42.0 / 58.0, more preferably 1.0 / 99.0 to 37.0 / 63.0. In the condition (D41), (the sum of A-32 and A-33) / A-1 is preferably 28.0 / 72.0 or less, more preferably 25.0 / 75.0 or less. In the condition (D41), (the sum of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 28.0 / 72.0, more preferably 1.0 / 99.0 to 25.0 / 75.0. In the condition (D42), (the sum of A-32 and A-33) / A-1 is preferably 31.0 / 69.0 or less, more preferably 28.0 / 72.0 or less. In the condition (D42), (the sum of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 31.0 / 69.0, more preferably 1.0 / 99.0 to 28.0 / 72.0.In the condition (D43), the ratio (total of A-32 and A-33) / A-1 is preferably 35.0 / 65.0 or less, more preferably 32.0 / 68.0 or less. In the condition (D43), the ratio (total of A-32 and A-33) / A-1 is preferably 1.0 / 99.0 to 35.0 / 65.0, more preferably 1.0 / 99.0 to 32.0 / 68.0. In the polycarbonate-polyorganosiloxane copolymer (S-4), the total content of the structural units (A-1), (A-32), and (A-33) in the polycarbonate block is preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 100.0 mol%.

[0103] In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1), the structural unit (A-31) represented by the general formula (31), and the structural unit (A-33) represented by the general formula (33), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), The polycarbonate-polyorganosiloxane copolymer (S-5) may be a polycarbonate-polyorganosiloxane copolymer (S-5) in which the molar ratio of the sum of the structural units (A-31) and (A-33) to the structural unit (A-33) ((total of A-31 and A-33) / A-1)), the molar ratio of the structural unit (A-31) to the structural unit (A-33) (A-31 / A-33), and the content x of the general formula (XX) satisfy the following conditions (C51), (C52), (C53), (D51), (D52), or (D53): Condition (C51): A-31 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 39.0 / 61.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C52): A-31 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 43.0 / 57.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C53): A-31 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 46.0 / 54.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D51): A-31 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 34.0 / 66.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. Condition (D52): A-31 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (the total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 38.0 / 62.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less.Condition (D53): A-31 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 41.0 / 59.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C51), (total of A-31 and A-33) / A-1 is preferably 34.0 / 66.0 or less, more preferably 29.0 / 71.0 or less. In condition (C51), (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 34.0 / 66.0, more preferably 1.0 / 99.0 to 29.0 / 71.0. In the condition (C52), the ratio (total of A-31 and A-33) / A-1 is preferably 38.0 / 62.0 or less, more preferably 33.0 / 67.0 or less. In the condition (C52), the ratio (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 38.0 / 62.0, more preferably 1.0 / 99.0 to 33.0 / 67.0. In the condition (C53), the ratio (total of A-31 and A-33) / A-1 is preferably 41.0 / 59.0 or less, more preferably 36.0 / 64.0 or less. In the condition (C53), the ratio (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 41.0 / 59.0, more preferably 1.0 / 99.0 to 36.0 / 64.0. In the condition (D51), the ratio (total of A-31 and A-33) / A-1 is preferably 28.0 / 72.0 or less, more preferably 22.0 / 78.0 or less. In the condition (D51), the ratio (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 28.0 / 72.0, more preferably 1.0 / 99.0 to 22.0 / 78.0. In the condition (D52), the ratio (total of A-31 and A-33) / A-1 is preferably 32.0 / 68.0 or less, more preferably 26.0 / 74.0 or less. In the condition (D52), the ratio (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 32.0 / 68.0, more preferably 1.0 / 99.0 to 26.0 / 74.0.In the condition (D53), the ratio (total of A-31 and A-33) / A-1 is preferably 35.0 / 65.0 or less, more preferably 31.0 / 69.0 or less. In the condition (D53), the ratio (total of A-31 and A-33) / A-1 is preferably 1.0 / 99.0 to 35.0 / 65.0, more preferably 1.0 / 99.0 to 31.0 / 69.0. In the polycarbonate-polyorganosiloxane copolymer (S-5), the total content of the structural units (A-1), (A-31), and (A-33) in the polycarbonate block is preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 100.0 mol%.

[0104] In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1), the structural unit (A-31) represented by the general formula (31), and the structural unit (A-32) represented by the general formula (32), and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), The polycarbonate-polyorganosiloxane copolymer (S-6) may be a polycarbonate-polyorganosiloxane copolymer (S-6) in which the molar ratio of the sum of the structural units (A-31) and (A-32) to the structural unit (A-32) ((total of A-31 and A-32) / A-1)), the molar ratio of the structural unit (A-31) to the structural unit (A-32) (A-31 / A-32), and the content x of the general formula (XX) satisfy the following condition (C61), (C62), (C63), (D61), (D62), or (D63): Condition (C61): A-31 / A-32 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C62): A-31 / A-32 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and less than 35.0 / 65.0, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (C63): A-31 / A-32 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and less than 43.0 / 57.0, and x is 1.0 mass% or more and less than 4.0 mass%. Condition (D61): A-31 / A-32 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (the total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 29.0 / 71.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. Condition (D62): A-31 / A-32 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (the total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 29.0 / 71.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less.Condition (D63): A-31 / A-32 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 37.0 / 63.0 or less, and x is 4.0 mass% or more and 10.0 mass% or less. In condition (C61), (total of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, more preferably 26.0 / 74.0 or less. In condition (C61), (total of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 31.0 / 69.0, more preferably 1.0 / 99.0 to 26.0 / 74.0. In the condition (C62), (the sum of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, more preferably 27.0 / 73.0 or less. In the condition (C62), (the sum of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 31.0 / 69.0, more preferably 1.0 / 99.0 to 27.0 / 73.0. In the condition (C63), (the sum of A-31 and A-32) / A-1 is preferably 38.0 / 62.0 or less, more preferably 33.0 / 67.0 or less. In the condition (C63), (the sum of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 38.0 / 62.0, more preferably 1.0 / 99.0 to 33.0 / 67.0. In the condition (D61), (the sum of A-31 and A-32) / A-1 is preferably 25.0 / 75.0 or less, more preferably 18.0 / 82.0 or less. In the condition (D61), (the sum of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 25.0 / 75.0, more preferably 1.0 / 99.0 to 18.0 / 82.0. In the condition (D62), (the sum of A-31 and A-32) / A-1 is preferably 25.0 / 75.0 or less, more preferably 19.0 / 81.0 or less. In the condition (D62), (the sum of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 25.0 / 75.0, more preferably 1.0 / 99.0 to 19.0 / 81.0.In the condition (D63), the ratio (total of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, more preferably 27.0 / 73.0 or less. In the condition (D63), the ratio (total of A-31 and A-32) / A-1 is preferably 1.0 / 99.0 to 31.0 / 69.0, more preferably 1.0 / 99.0 to 27.0 / 73.0. In the polycarbonate-polyorganosiloxane copolymer (S-6), the total content of the structural units (A-1), (A-31), and (A-32) in the polycarbonate block is preferably 70.0 mol% or more, more preferably 80.0 mol% or more, even more preferably 90.0 mol% or more, and even more preferably 100.0 mol%.

[0105] The content x under the conditions (C1), (C2), (C3), (C41), (C42), (C43), (C51), (C52), (C53), (C61), (C62), and (C63) is preferably 2.0% by mass or more, more preferably 3.0% by mass or more. The content x under the conditions (D1), (D2), (D3), (D41), (D42), (D43), (D51), (D52), (D53), (D61), (D62), and (D63) is preferably 4.3% by mass or more, more preferably 4.5% by mass or more, and preferably 9.0% by mass or less, more preferably 6.0% by mass or less. The content x under these conditions is preferably 4.3 to 9.0% by mass, more preferably 4.5 to 6.0% by mass.

[0106] <Polycarbonate-Based Resin (P)> Examples of the polycarbonate-based resin (P) include polycarbonate-based resins that do not contain the repeating structure (A-2) of the structure represented by general formula (XX), but contain the structural unit (A-1) represented by general formula (1), and may contain at least one structural unit (A-3) selected from the structures represented by general formulas (3) and (4). Further, examples of the polycarbonate-based resin (P) include polycarbonate-polyorganosiloxane copolymers that contain a polycarbonate block that does not contain the structural unit (A-1) represented by general formula (1) and a polyorganosiloxane block that contains the repeating structure (A-2) of the structure represented by general formula (XX). The structural unit (A-1), structural unit (A-3), and repeating structure (A-2) contained in the polycarbonate-based resin (P) include the same structural units (A-1), structural unit (A-3), and repeating structure (A-2) contained in the polycarbonate-based resin (S) and the polycarbonate-polyorganosiloxane copolymer (A). Preferred embodiments are also the same.

[0107] <Method for producing polycarbonate-polyorganosiloxane copolymer (A)> The polycarbonate-polyorganosiloxane copolymer (A) contained in the polycarbonate resin (S) can be produced, for example, by using a diol monomer (a1) and a polyorganosiloxane (a2), and optionally a diol monomer (a3), as raw material monomers.

[0108] <<Diol Monomer (a1)>> The diol monomer (a1) has a structure represented by the following general formula (1a): The diol monomer (a1) preferably contains a diol represented by the following general formula (11a), and more preferably consists of a diol represented by the following general formula (11a):

[0109]

[0110]

[0111] <<Diol Monomer (a3)>> When the polycarbonate-polyorganosiloxane copolymer (A) contains the structural unit (A-3), it further contains a diol monomer (a3) ​​as a raw material monomer. The diol monomer (a3) ​​is preferably at least one diol selected from structures represented by general formulas (3a) and (4a).

[0112]

[0113] In general formulas (3a) and (4a), R １１ and R １２ The diol monomer (a1) is not included in the diol monomer (a3).

[0114] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably contains a polyorganosiloxane structure represented by the following general formula (21a).

[0115] In general formula (21a), R １ ~R ８ , a, b, u, and z are as described above, and the preferred values ​​are also the same, provided that z at the terminals is 1, that is, the hydrogen atoms at both terminals are bonded to oxygen atoms.

[0116] The polyorganosiloxane (a2) preferably contains a polyorganosiloxane represented by the following general formula (22a):

[0117] In general formula (22a), R １ ~R ８ , a, b, u, u1, z, and z1 are as described above, and the preferred values ​​are also the same. However, z and z1 at both ends are 1, that is, the hydrogen atoms at both ends are bonded to oxygen atoms.

[0118] The polyorganosiloxane (a2) preferably contains at least one of the polyorganosiloxanes represented by the following general formulas (23a) to (26a).

[0119]

[0120] In general formulas (23a) to (26a), R １ ~R ８ , a, b, b1, u, u1, z, z1, and β are as described above, and the preferred values ​​are also the same. However, in general formulas (23a) to (26a), z and z1 at the terminals are 1, that is, the hydrogen atom at the terminal is bonded to an oxygen atom.

[0121] The method for producing polyorganosiloxane (a2) is not particularly limited. For example, according to the method described in JP-A-11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α,ω-dihydrogenorganopentasiloxane, and then, in the presence of a hydrosilylation catalyst, the α,ω-dihydrogenorganopentasiloxane is subjected to an addition reaction with an oligomer or polymer (e.g., polyalkylene ether, polyester, polycarbonate, etc.) whose one end is modified with an allyl group. According to the method described in Japanese Patent No. 2,662,310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (an acidic catalyst), and the resulting α,ω-dihydrogenorganopolysiloxane is then subjected to an addition reaction with an oligomer or polymer having one end modified with an allyl group in the presence of a hydrosilylation catalyst, as described above. The α,ω-dihydrogenorganopolysiloxane can be used by adjusting the average chain length appropriately depending on the polymerization conditions, or a commercially available α,ω-dihydrogenorganopolysiloxane can be used. The oligomer having one end modified with an allyl group can be used by adjusting the average number of repeating units appropriately depending on the polymerization conditions, or a commercially available oligomer modified with an allyl group at one end. Among the oligomers modified with an allyl group at one end, polyethylene glycol modified with an allyl group at one end can be produced by referring to Japanese Patent No. 5,652,691, etc. Commercially available allyl-modified polyethylene glycols include Uniox PKA-5001, Uniox PKA-5002, Uniox PKA-5003, Uniox PKA-5004, and Uniox PKA-5005 manufactured by NOF Corporation.

[0122] The polycarbonate-polyorganosiloxane copolymer (A) can be produced by polymerizing a mixture of raw material monomers using an interfacial polymerization method or a melt polymerization method (transesterification method). When producing by interfacial polymerization, for example, the method described in JP 2014-80462 A can be adopted. The polycarbonate-polyorganosiloxane copolymer (A) can be produced by reacting the raw material monomers polyorganosiloxane (a2), diol monomer (a1), and a carbonate ester compound described below by a melt polymerization method, preferably in the presence of a basic catalyst. A diol monomer (a3) ​​may also be used as a raw material monomer, if necessary. Furthermore, the polymerization reaction may be carried out by further adding a terminal capping agent. The melt polymerization method does not require a solvent such as methylene chloride, which is required in the interfacial polymerization method, and is therefore advantageous from an environmental and economic perspective. In addition, since the highly toxic phosgene used in the interfacial polymerization method is not used, it is also advantageous in terms of production. Therefore, it is preferable to produce the polycarbonate-polyorganosiloxane copolymer (A) by the melt polymerization method.

[0123] (Carbonate Ester Compound) Examples of the carbonate ester compound include diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds. Examples of the diaryl carbonate compound include a compound represented by the following general formula (41) and a compound represented by the following general formula (42).

[0124]

[0125] In the general formulas (41) and (42), Ar １ and Ar ２ Each of Ar represents an aryl group, and may be the same or different. ３ and Ar ４ each represents an aryl group, and may be the same or different; D １ represents the divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms or the divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0126] Examples of the dialkyl carbonate compound include a compound represented by the following general formula (43) and a compound represented by the following general formula (44).

[0127]

[0128] In general formulas (43) and (44), R ２１ and R ２２ Each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and may be the same or different. ２３ and R ２４ each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same or different from each other; D ２ represents the divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms or the divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0129] Examples of the alkylaryl carbonate compound include a compound represented by the following general formula (45) and a compound represented by the following general formula (46).

[0130]

[0131] In the general formulas (45) and (46), Ar ５ is an aryl group, R ２５ represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. ６ is an aryl group, R ２６ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms; D ３ represents the divalent linear aliphatic hydrocarbon group having 2 to 40 carbon atoms or the divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0132] Examples of diaryl carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, and bisphenol A bisphenyl carbonate. Examples of dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of alkyl aryl carbonate compounds include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. A preferred carbonate ester compound is diphenyl carbonate. One or more carbonate ester compounds can be used to produce the polycarbonate-polyorganosiloxane copolymer (A).

[0133] (Terminator) When producing the polycarbonate-polyorganosiloxane copolymer (A), a terminal terminator can be used as needed. As the terminal terminator, a known terminal terminator used in the production of polycarbonate resins may be used, and specific examples thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0134] (Branching Agent) A branching agent can also be used in producing the polycarbonate-polyorganosiloxane copolymer (A). Examples of branching agents include phloroglucin, trimellitic acid, 1,1,1-tris(4-hydroxyphenyl)ethane, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, and isatin bis(o-cresol).

[0135] Specifically, the polycarbonate-polyorganosiloxane copolymer (A) can be produced by melt polymerization, for example, according to the following procedure. A mixture of raw material monomers containing a diol monomer (a1), a polyorganosiloxane (a2), and a carbonate ester compound is subjected to a transesterification reaction. The mixture of raw material monomers may optionally contain a diol monomer (a3). The amount of the carbonate ester compound relative to the total amount of the diol monomers (a1) and (a3) ​​is preferably 0.9 to 1.2 times by mole, more preferably 0.95 to 1.05 times by mole. Under polymerization conditions, when the diol monomers (a1) and (a3) ​​are more volatile than the carbonate ester compound, it is preferable that the ratio of the amount of the carbonate ester compound relative to the total amount of the diol monomers (a1) and (a3) ​​be 1 or less. Under polymerization conditions, when the diol monomers (a1) and (a3) ​​are less volatile than the carbonate ester compound, it is preferable that the ratio of the amount of the carbonate ester compound relative to the total amount of the diol monomers (a1) and (a3) ​​be 1 or more. By adjusting the ratio of the amount of carbonate ester compound to the total amount of diol monomers (a1) and (a3) ​​within the above range, the number average molecular weight and weight average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer (A) can be increased. When a terminal terminator is used in the above transesterification reaction, it is preferable that the amount of terminal terminator is in the range of 0.05 to 10 mol% relative to the total amount of diol monomer (a1), polyorganosiloxane (a2), and, if necessary, polyorganosiloxane (a3). This ensures that the hydroxyl group terminals of the resulting polycarbonate-polyorganosiloxane copolymer (A) are sufficiently blocked, resulting in a polycarbonate resin with excellent heat resistance and water resistance. The amount of terminal terminator relative to the total amount of diol monomer (a1), polyorganosiloxane (a2), and, if necessary, polyorganosiloxane (a3) ​​is more preferably 1 to 6 mol%. The entire amount of the terminal terminator may be added to the reaction system in advance, or a portion may be added to the reaction system in advance, and the remainder may be added as the reaction proceeds.It is preferred that an antioxidant is simultaneously charged into a reactor together with the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound, and the transesterification reaction is carried out in the presence of the antioxidant.

[0136] The reaction temperature for carrying out the transesterification reaction is not particularly limited, and may be, for example, in the range of 100 to 260 ° C, preferably in the range of 100 to 250 ° C. Furthermore, a method in which the temperature is gradually increased from 150 ° C to 250 ° C as the reaction progresses is preferred, and a method in which the temperature is gradually increased from 170 ° C to 250 ° C is more preferred. If the temperature of the transesterification reaction is 100 ° C or higher, the reaction rate is sufficiently fast, while if it is 250 ° C or lower, many side reactions do not occur, and problems such as discoloration of the resulting polycarbonate-polyorganosiloxane copolymer (A) are unlikely to occur. The temperature in the final reactor is preferably 210 ° C or higher, more preferably 225 ° C or higher.

[0137] The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. There are no particular limitations as long as the reaction is carried out efficiently. For example, at the initial stage of the reaction, ５ ~5.07 x 10 ６ The pressure is then reduced to atmospheric pressure (normal pressure) or pressurized up to 1.33 to 1.33 × 10 Pa in the latter stage of the reaction. ３ The reaction time may be such that the reaction is continued until the target molecular weight is reached, and is, for example, 0.2 to 10 hours.

[0138] The above transesterification reaction is carried out, for example, in the absence of an inert solvent, but may be carried out, if necessary, in the presence of 1 to 150 parts by mass of an inert solvent per 100 parts by mass of the resulting polycarbonate resin. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; and tricyclo[5.2.1.0] ２，６] cycloalkanes such as decane, cyclooctane, and cyclodecane. If necessary, the reaction may be carried out in an inert gas atmosphere, and examples of the inert gas include argon, carbon dioxide, nitrous oxide, nitrogen, and other gases, chlorofluorohydrocarbons, alkanes such as ethane and propane, and alkenes such as ethylene and propylene.

[0139] In the melt polymerization method, it is preferable to use a basic catalyst as the catalyst. Examples of the basic catalyst include at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing an aryl group, and metal compounds. These compounds can be used alone or in combination. The basic catalyst is preferably at least one selected from the group consisting of inorganic salts (excluding organic acid salts and silicates), oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing an aryl group, with alkali metal hydroxides being more preferred. The basic catalysts can be used alone or in combination.

[0140] Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, etc. Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, barium diacetate, etc.

[0141] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having an alkyl or aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Further examples include bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0142] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0143] Specific examples of quaternary phosphonium salts containing an aryl group include tetra(aryl or alkyl)phosphonium hydroxides such as tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide; tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-t-butylphenyl)phosphonium diphenylphosphate, triphenylbutylphosphonium phenolate, and triphenylbutylphosphonium tetraphenylborate. The quaternary phosphonium salt containing an aryl group is preferably combined with a nitrogen-containing organic basic compound, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0144] The amount of the basic catalyst used is preferably 1 × 10 per mole of the diol monomer (a1) or the total mole of the diol monomers (a1) and (a3). －９ ~1 x 10 －２ mole, preferably 1 x 10 －８ ~1 x 10 －４ mole, more preferably 1 x 10 －７ ~1 x 10 －５ You can choose from a range of moles.

[0145] A catalyst deactivator may be added in the latter stage of the reaction. Known catalyst deactivators are effectively used as the catalyst deactivator. Examples of catalyst deactivators include sulfonic acid esters, ammonium salts of sulfonic acid, and phosphonium salts of sulfonic acid.

[0146] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the amount of catalyst deactivator used is preferably 0.5 to 50 mol, more preferably 1.0 to 30 mol, and even more preferably 5.0 to 15 mol, per mol of the catalyst. It is preferable to add the catalyst deactivator, complete the polymerization reaction, and then mix in the antioxidant.

[0147] The melt polymerization reaction may be carried out either continuously or batchwise. The reaction apparatus used for melt polymerization may be a vertical reaction apparatus equipped with an anchor-type impeller, a Maxblend impeller, or a helical ribbon impeller, or a horizontal reaction apparatus equipped with a paddle impeller, a lattice impeller, or a spectacle impeller. It may also be an extruder equipped with a screw. In the case of a continuous reaction, it is preferable to use an appropriate combination of such reaction apparatuses.

[0148] [Light-resistant agent] When the polycarbonate-based resin composition according to the present invention contains the polycarbonate-based resin (S) and a light-resistant agent, the polycarbonate-based resin composition and its molded article have the effect of exhibiting excellent impact resistance and excellent light resistance. Specific examples of the light-resistant agent include those generally known as ultraviolet absorbers, light stabilizers, and weather resistance agents.

[0149] When the polycarbonate resin composition contains a light-resistant agent, the content of the light-resistant agent is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the polycarbonate resin composition, from the viewpoint of further improving light resistance; and from the viewpoint of the balance between impact resistance and scratch resistance of the polycarbonate resin composition and molded articles thereof, the content is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and even more preferably 1.0 part by mass or less. The polycarbonate resin composition according to the present invention can contain, as the light-resistant agent, one selected from ultraviolet absorbers and light-resistance stabilizers, either alone or in combination of two or more. As the light-resistance stabilizer, an amine-based light-resistance stabilizer is preferred, and a hindered amine-based light-resistance stabilizer is more preferred.

[0150] (UV absorber) Examples of UV absorbers include at least one selected from the group consisting of benzotriazole-based UV absorbers, benzoxazinone-based UV absorbers, salicylate-based UV absorbers, malonic acid ester-based UV absorbers, oxalyl alanide-based UV absorbers, triazine-based UV absorbers, benzophenone-based UV absorbers, and cyanoacrylate-based UV absorbers.These can be used alone or in combination of two or more.From the viewpoint of light resistance, the UV absorber preferably includes at least one selected from the group consisting of benzotriazole-based UV absorbers and benzoxazinone-based UV absorbers, more preferably at least one selected from the group consisting of benzotriazole-based UV absorbers and benzoxazinone-based UV absorbers, and even more preferably a benzotriazole-based UV absorber.

[0151] Examples of benzotriazole-based ultraviolet absorbers include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-4-octyloxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-tert-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t tert-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-[2-hydroxy-3-(3,4,5,6-tetra-hydrophthalimidomethyl)-5-methylphenyl]benzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], methyl-3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol (molecular weight approximately 300) condensate, and the like. Among these, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, or 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] is preferred, and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol] is more preferred. These can be used alone or in combination of two or more.

[0152] The benzoxazinone compound may be, for example, a compound represented by the following general formula (101).

[0153] [In general formula (101), R １０１R represents a residue obtained by removing s hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule. １０２ represents hydrogen, a halogen group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. s represents an integer of 2 or 3, and t represents an integer of 1 to 4.]

[0154] In general formula (101), R １０１ R is a residue obtained by removing s hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule, and examples of R include arylene groups such as a phenylene group, a biphenylene group, and a naphthylene group. １０２ In the formula (I), examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group; examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; and examples of the alkenyloxy group having 2 to 8 carbon atoms include an allyloxy group, a 2-propenyloxy group, a 2-butenyloxy group, and a 2-methyl-3-propenyloxy group.

[0155] Among the compounds represented by the general formula (101), 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) [p-phenylenebis(1,3-benzoxazin-4-one)] is preferred. 2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) is a compound represented by the following formula:

[0156]

[0157] Examples of salicylate-based UV absorbers include phenyl salicylate, p-tert-butylphenyl salilethate, and p-octylphenyl salilethate. Examples of malonic acid ester-based UV absorbers include benzylidenebisdiethylmalonate, 4-methoxyphenylmethylenedimethylester, and tetraethyl-2,2'-(1,4-phenylenedimethylidene)bismalonate. Examples of oxalyl alanide-based UV absorbers include oxalyl alanide compounds having a hydrocarbon group having 1 to 12 carbon atoms. Examples of triazine-based UV absorbers include 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine.

[0158] (Light resistance stabilizer) As the light resistance stabilizer, for example, an amine-based light resistance stabilizer is preferred. As the amine-based light resistance stabilizer, one having a structure in which nitrogen is part of a cyclic structure is preferred, and one having a piperidine structure is more preferred. The piperidine structure defined here may be any structure as long as it is a saturated 6-membered cyclic amine structure, and also includes one in which a part of the piperidine structure is substituted with a substituent. Examples of the substituent that the piperidine structure may have include alkyl groups having 4 or less carbon atoms, and particularly methyl groups are preferred. As the amine compound, further, a compound having multiple piperidine structures is preferred, and when multiple piperidine structures are present, a compound in which these piperidine structures are connected by an ester structure is preferred. In particular, a compound represented by the following formula is preferred.

[0159]

[0160] The total content of the polycarbonate resin (S) and the light-resistant agent in the polycarbonate resin composition according to the present invention is preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, from the viewpoint of further improving the balance between tensile properties and light resistance and from the viewpoint of the balance between impact resistance and scratch resistance, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin (S) and the light-resistant agent is not particularly limited, but is, for example, 100% by mass or less, from the viewpoint of obtaining a polycarbonate resin composition having desired properties.

[0161] The content of the light stabilizer in the polycarbonate-based resin composition is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and even more preferably 0.05 part by mass or more, relative to 100 parts by mass of the polycarbonate-based resin composition. From the viewpoint of the balance between the impact resistance and scratch resistance of the polycarbonate-based resin composition and a molded article thereof, the content is preferably 5 parts by mass or less, more preferably 1.0 part by mass or less, and even more preferably 0.5 part by mass or less.

[0162] [Acrylic Resin] When the polycarbonate-based resin composition according to the present invention contains the polycarbonate-based resin (S) and an acrylic resin, the polycarbonate-based resin composition and a molded article thereof have the effect of having excellent impact resistance and excellent scratch resistance.

[0163] When the polycarbonate-based resin composition contains an acrylic resin, the content of the acrylic resin is preferably 1.0 part by mass or more, more preferably 5.0 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the polycarbonate-based resin composition, from the viewpoint of further improving the balance between scratch resistance and scratch resistance. From the viewpoint of the balance between impact resistance and scratch resistance of the polycarbonate-based resin composition and molded articles thereof, the content is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, and even more preferably 45 parts by mass or less. The polycarbonate-based resin composition according to the present invention may contain, as the acrylic resin, one or a combination of two or more selected from (co)polymers of monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, and methacrylonitrile. The term "(co)polymer" refers to a homopolymer or copolymer.

[0164] Examples of acrylic acid esters and methacrylic acid esters (hereinafter collectively referred to as "(meth)acrylic acid esters") include methyl (meth)acrylate, benzyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, glycidyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and nonyl (meth)acrylate. Examples of suitable acrylates include carboxymethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, acrylic (meth)acrylate, 2-hydroxyethyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-(meth)acroyloxyethyl succinate, 2-(meth)acroyloxyethyl maleate, 2-(meth)acroyloxyethyl phthalate, and 2-(meth)acroyloxyethyl hexahydrophthalate. Note that "(meth)acroyl" means "acroyl" and "methacroyl".

[0165] The total content of the polycarbonate resin (S) and the acrylic resin in the polycarbonate resin composition according to the present invention is, from the viewpoint of further improving the balance of tensile properties, impact resistance, and scratch resistance, preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin (S) and the acrylic resin is not particularly limited, but from the viewpoint of obtaining a polycarbonate resin composition having desired properties, it is, for example, 100% by mass or less.

[0166] [Elastomer] When the polycarbonate resin composition according to the present invention contains the polycarbonate resin (S) and an elastomer, the polycarbonate resin composition and molded articles thereof can be expected to have excellent impact resistance and chemical resistance. Note that the elastomer does not contain the acrylic resin.

[0167] When the polycarbonate-based resin composition contains an elastomer, there is a possibility of improving chemical resistance. The content of the elastomer is preferably 0.1 part by mass or more, more preferably 1.0 part by mass or more, and even more preferably 3.0 parts by mass or more, per 100 parts by mass of the polycarbonate-based resin composition, and from the viewpoint of the balance between the impact resistance and scratch resistance of the polycarbonate-based resin composition and molded articles thereof, is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

[0168] The elastomer can be any resin other than the above-mentioned acrylic resin without any particular limitation, and examples thereof include rubbery graft polymers and rubbery graft polymer latexes. The rubbery graft polymer is preferably a rubbery graft polymer whose rubber portion has structural units derived from an acrylic ester, and more preferably a rubbery graft polymer whose rubber portion has structural units derived from an acrylic ester and structural units derived from butadiene. The polycarbonate resin composition according to the present invention can contain, as the elastomer, one selected from the rubbery graft polymers and rubbery graft polymer latexes, either alone or in combination of two or more.

[0169] Examples of structural units derived from acrylate esters that constitute the rubbery graft polymer include structural units derived from methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate, t-butyl acrylate, etc. The structural units derived from acrylate esters may contain one or more of these structural units.

[0170] Examples of the butadiene-derived structural units constituting the rubbery graft polymer include structural units derived from butadiene, isoprene, etc. The butadiene-derived structural units may contain one or more of these structural units.

[0171] The rubbery graft polymer latex is obtained by polymerizing a vinyl monomer in the presence of a rubber latex having structural units derived from an acrylate ester and structural units derived from butadiene. The structural units derived from an acrylate ester and structural units derived from butadiene of the rubber latex include the structural units derived from an acrylate ester and structural units derived from butadiene listed as the rubber portion of the rubbery graft polymer.

[0172] Examples of the vinyl monomer include monofunctional monomers such as acrylonitrile and (meth)acrylic acid esters, and polyfunctional monomers such as divinylbenzene, ethylene glycol dimethacrylate, butylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate. One or more types of vinyl monomers may be used.

[0173] The total content of the polycarbonate resin (S) and the elastomer in the polycarbonate resin composition according to the present invention is, from the viewpoint of further improving the balance between tensile properties, impact resistance, and scratch resistance, preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin (S) and the elastomer is not particularly limited, but from the viewpoint of obtaining a polycarbonate resin composition having desired properties, it is, for example, 100% by mass or less.

[0174] [Colorant] When the polycarbonate resin composition according to the present invention contains the polycarbonate resin (S) and a colorant, the polycarbonate resin composition and a molded article thereof have the effects of having excellent impact resistance and excellent design properties.

[0175]

[0032] When the polycarbonate-based resin composition contains a colorant, the content of the colorant is preferably 0.01 part by mass or more, more preferably 0.03 part by mass or more, and even more preferably 0.05 part by mass or more, relative to 100 parts by mass of the polycarbonate-based resin composition, from the viewpoint of further improving designability, and is preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.0 part by mass or less, and particularly preferably 0.5 parts by mass or less, from the viewpoint of the balance between impact resistance and scratch resistance of the polycarbonate-based resin composition and molded articles thereof. The polycarbonate-based resin composition according to the present invention can contain, as a colorant, one type selected from inorganic pigments, organic pigments, and organic dyes, either alone or in combination of two or more types.

[0176] Examples of inorganic pigments include carbon black; and oxide pigments such as titanium oxide, zinc white, red iron oxide, chromium oxide, iron black, titanium yellow, zinc-iron brown, copper-chromium black, and copper-iron black.

[0177] Examples of organic pigments and organic dyes include phthalocyanine-based dyes and pigments; condensed polycyclic dyes and pigments such as azo-based, thioindigo-based, perinone-based, perylene-based, quinacridone-based, dioxazine-based, isoindolinone-based, and quinophthalone-based; and anthraquinone-based, perinone-based, perylene-based, methine-based, quinoline-based, heterocyclic, and methyl-based dyes and pigments.

[0178] The total content of the polycarbonate resin (S) and colorant in the polycarbonate resin composition according to the present invention is preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, from the viewpoint of further improving the balance between tensile properties, impact resistance, scratch resistance, and designability, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin (S) and colorant is not particularly limited, but is, for example, 100% by mass or less, from the viewpoint of obtaining a polycarbonate resin composition having desired properties. [Glittering particles] When the polycarbonate-based resin composition according to the present invention contains the polycarbonate-based resin (S) and the glittering particles, the polycarbonate-based resin composition and molded articles thereof have excellent impact resistance and excellent design properties.

[0179] When the polycarbonate-based resin composition contains glittering particles, the content of the glittering particles is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polycarbonate-based resin composition, from the viewpoint of further improving designability, and is preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, from the viewpoint of the balance between the impact resistance and scratch resistance of the polycarbonate-based resin composition and molded articles thereof. The polycarbonate-based resin composition according to the present invention can contain, as glittering particles, one kind selected from metal particles and optical interference pigments, either alone or in combination of two or more kinds.

[0180] Examples of metal particles include silver flakes, nickel flakes, gold flakes, titanium flakes, and aluminum flakes, with silver flakes and aluminum flakes being preferred.

[0181] Optical interference pigments are inorganic particles (excluding metal particles) coated with a metal or metal oxide. Examples of inorganic particles (excluding metal particles) include glass flakes, mica, alumina flakes, silica flakes, and mica flakes, with glass flakes being preferred. Examples of metals that coat inorganic particles (excluding metal particles) include silver, nickel, gold, titanium, and aluminum, with silver being preferred. Examples of metal oxides that coat inorganic particles (excluding metal particles) include silver oxide, titanium oxide, iron oxide, and aluminum oxide, with titanium oxide being preferred. The inorganic particles (excluding metal particles), the metals that coat inorganic particles (excluding metal particles), and the metal oxides that coat inorganic particles (excluding metal particles) can each be used alone or in combination of two or more.

[0182] The average particle size of the glittering particles is preferably 20 μm or more and 100 μm or less. By making the average particle size of the glittering particles 20 μm or more, the design properties of the polycarbonate-based resin composition and its molded articles can be improved, and by making the average particle size of the glittering particles 100 μm or less, a decrease in the impact resistance of the polycarbonate-based resin composition and its molded articles can be suppressed.

[0183] The average thickness of the glittering particles is preferably 1 μm or more and 10 μm or less. By making the average thickness of the glittering particles 1 μm or more, excessive crushing of the glittering particles can be suppressed during the production process of the polycarbonate-based resin composition and its molded articles, and by making the average thickness of the glittering particles 10 μm or less, deterioration of the moldability of the polycarbonate-based resin composition can be suppressed.

[0184] [Inorganic Filler] When the polycarbonate-based resin composition according to the present invention contains the polycarbonate-based resin (S) and an inorganic filler, the polycarbonate-based resin composition and a molded article thereof exhibit the effects of having excellent impact resistance and excellent rigidity.

[0185] When the polycarbonate-based resin composition contains an inorganic filler, the inorganic filler is preferably contained in an amount of 0.1 parts by mass or more and 100 parts by mass or less per 100 parts by mass of the polycarbonate-based resin composition. When the content of the inorganic filler is 0.1 parts by mass or more, the balance between tensile properties and rigidity can be further improved. When the content of the inorganic filler is 100 parts by mass or less, for example, the moldability and impact resistance can be further improved. From the viewpoint of further improving the balance between tensile properties and rigidity, the content of the inorganic filler in the polycarbonate-based resin composition according to the present invention is more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, and even more preferably 4.0 parts by mass or more per 100 parts by mass of the polycarbonate-based resin composition. From the viewpoint of further improving the balance between moldability and impact resistance and scratch resistance, the content is more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less.

[0186] Examples of inorganic fillers include at least one selected from the group consisting of glass fillers (e.g., glass fiber, glass beads, glass flakes, glass powder, etc.), carbon fiber, dolomite, silica, diatomaceous earth, talc, clay, mica, asbestos, calcium silicate, montmorillonite, bentonite, graphite, etc. From the viewpoint of further improving the balance between tensile properties and rigidity, glass fillers, silica, and carbon fiber are preferred, and glass fiber is more preferred. The polycarbonate resin composition according to the present invention can contain the inorganic filler selected from glass fillers, silica, and carbon fiber alone or in combination of two or more.

[0187] Any talc commercially available as an additive for thermoplastic resins can be used. Talc is a hydrous magnesium silicate, and in addition to the main components silicic acid and magnesium oxide, it may contain trace amounts of aluminum oxide, calcium oxide, and iron oxide, or these may be included. The average particle size is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 50 μm or less, more preferably 20 μm or less. The aspect ratio is, for example, in the range of 2 to 20. These average particle size and aspect ratio are determined by comprehensively considering other components, such as flowability during molding and the impact resistance and rigidity required for the molded product. Talc that has been surface-treated with a fatty acid or pulverized in the presence of a fatty acid can also be used.

[0188] When glass fibers are blended as an inorganic filler in the polycarbonate resin composition according to the present invention, the rigidity of the molded article can be further improved. The glass fibers are preferably produced using alkali-containing glass, low-alkali glass, or alkali-free glass as the raw material, and the fiber form may be any of roving, milled fiber, chopped strand, etc. The cross section of the glass fiber may also be flat. The diameter of the glass fiber is preferably 3 μm or more and 30 μm or less, and the length is preferably 1 mm or more and 6 mm or less. When the diameter of the glass fiber is 3 μm or more, the rigidity of the polycarbonate resin composition can be further increased, and when it is 30 μm or less, the appearance of the molded article becomes good.

[0189] The fiber length of the glass fiber is, for example, 0.01 mm to 8 mm, preferably 0.1 mm to 6 mm. The fiber diameter is, for example, approximately 0.1 μm to 30 μm, preferably 0.5 μm to 25 μm. These glass fibers may be used alone or in combination. To enhance their affinity with resins, glass fibers may be surface-treated with a silane coupling agent such as an aminosilane, epoxysilane, vinylsilane, or methacrylsilane, a chromium complex compound, or a boron compound, or may be further subjected to a sizing treatment using a sizing agent. Suitable examples of such glass fibers include MA-409C (average fiber diameter: 13 μm) and TA-409C (average fiber diameter: 23 μm) manufactured by Asahi Fiberglass Co., Ltd., and T-511 (average fiber diameter: 12-14 μm) manufactured by Nippon Electric Glass Co., Ltd.

[0190] When the polycarbonate-based resin composition according to the present invention contains talc as an inorganic filler, the content of the inorganic filler is, from the viewpoint of further improving the balance between tensile properties and rigidity and from the viewpoint of improving dimensional stability, preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, and still more preferably 4.0 parts by mass or more, relative to 100 parts by mass of the polycarbonate-based resin composition; and, from the viewpoint of further improving the balance between moldability and impact resistance and scratch resistance, preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and still more preferably 8.0 parts by mass or less.

[0191] When the polycarbonate-based resin composition according to the present invention contains glass fiber as an inorganic filler, the content of the inorganic filler is, from the viewpoint of further improving the balance between tensile properties and rigidity and from the viewpoint of improving dimensional stability, preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, even more preferably 4.0 parts by mass or more, even more preferably 6.0 parts by mass or more, and still more preferably 8.0 parts by mass or more, relative to 100 parts by mass of the polycarbonate-based resin composition; and from the viewpoint of further improving moldability and impact resistance and from the viewpoint of further improving appearance, it is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less.

[0192] The total content of the polycarbonate resin composition and inorganic filler in the polycarbonate resin composition according to the present invention is, from the viewpoint of further improving the balance between tensile properties and rigidity, preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin composition and inorganic filler is not particularly limited, but from the viewpoint of obtaining a resin composition having desired properties, it is, for example, 100% by mass or less.

[0193] [Flame Retardant] When the polycarbonate resin composition according to the present invention contains the polycarbonate resin (S) and a flame retardant, the polycarbonate resin composition and a molded article thereof exhibit the effects of having excellent impact resistance and excellent flame retardancy.

[0194] Examples of the flame retardant include at least one selected from the group consisting of phosphorus-based flame retardants, halogen-based flame retardants, and metal salt-based flame retardants. From the viewpoint of further improving flame retardancy, at least one selected from the group consisting of phosphorus-based flame retardants and metal salt-based flame retardants is preferred.

[0195] Examples of phosphorus-based flame retardants include red phosphorus and phosphate ester-based flame retardants. Phosphate ester-based flame retardants are preferably halogen-free, and examples include phosphate ester monomers, oligomers, polymers, and mixtures thereof. Examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri(2-ethylhexyl)phosphate, diisopropylphenyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, and the like, as well as substitution products and condensates thereof. Among these, condensed phosphate ester-based flame retardants are preferred.

[0196] Commercially available phosphate ester compounds that can be used as phosphate ester flame retardants include, for example, TPP (triphenyl phosphate), TXP (trixylenyl phosphate), CR733S (resorcinol bis(diphenyl phosphate)), CR741 (bisphenol A bis(diphenyl phosphate)), PX200 (1,3-phenylene-tetrakis(2,6-dimethylphenyl)phosphate), PX201L (1,4-phenylene-tetrakis(2,6-dimethylphenyl)phosphate), and PX202 (4,4'-biphenylene-tetrakis)2,6-dimethylphenyl)phosphate, all manufactured by Daihachi Chemical Industry Co., Ltd. The phosphate ester flame retardants are obtained by reacting dihydric phenols or monohydric phenols represented by Ar-OH (Ar represents an aryl group) with phosphorus oxychloride. These phosphate ester flame retardants may be used alone or in combination. As the phosphate ester flame retardant, 1,3-phenylene-tetrakis(2,6-dimethylphenyl)phosphate is preferred.

[0197] When the polycarbonate-based resin composition according to the present invention contains a phosphorus-based flame retardant as a flame retardant, the content of the flame retardant is, from the viewpoint of further improving flame retardancy, preferably 1.0 part by mass or more, more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, even more preferably 5.0 parts by mass or more, and still more preferably 7.0 parts by mass or more, per 100 parts by mass of the polycarbonate-based resin composition; and, from the viewpoint of the balance between impact resistance and scratch resistance of the polycarbonate-based resin composition and a molded article thereof, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and still more preferably 12 parts by mass or less.

[0198] Examples of halogen-based flame retardants include tetrabromobisphenol A (TBA), halogenated polycarbonate, copolymers of halogenated polycarbonate, oligomers thereof (TBA carbonate oligomer), decabromodiphenyl ether, TBA epoxy oligomer, halogenated polystyrene, and halogenated polyolefin. The halogen-based flame retardants can be used alone or in combination of two or more.

[0199] Examples of metal salt flame retardants include organic alkali metal salts and organic alkaline earth metal salts.The metal salt flame retardant preferably includes at least one selected from organic alkali metal salts and organic alkaline earth metal salts, and more preferably at least one selected from organic alkali metal salts and organic alkaline earth metal salts.The organic sulfonate salts of the alkali metal or alkaline earth metal (hereinafter, both may be collectively referred to as "alkali (earth) metal") include metal salts of fluorine-substituted alkylsulfonic acid, such as metal salts of perfluoroalkanesulfonic acid and alkali metal or alkaline earth metal, and metal salts of aromatic sulfonic acid and alkali metal or alkaline earth metal.

[0200] Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkali metals are more preferred. Among these alkali metals, potassium and sodium are preferred, with potassium being more preferred, from the viewpoints of flame retardancy and thermal stability. Potassium salts can also be used in combination with alkali metal sulfonates made from other alkali metals.

[0201] Examples of alkali metal perfluoroalkanesulfonates include potassium perfluorobutanesulfonate, potassium trifluoromethanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more. Here, the number of carbon atoms in the perfluoroalkyl group is preferably 1 to 18, more preferably 1 to 10, and even more preferably 1 to 8. Among these, potassium perfluorobutanesulfonate is preferred.

[0202] Examples of aromatic sulfonic acid alkali (earth) metal salts include disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, potassium benzenesulfonate, sodium benzenesulfonate, sodium p-toluenesulfonate, and strontium benzenesulfonate. , magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, benzof Examples of suitable aromatic sulfonic acid salts include dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, formalin condensates of sodium naphthalenesulfonate, and formalin condensates of sodium anthracenesulfonate, with potassium diphenylsulfone-3-sulfonate being preferred. Of these alkali (earth) metal salts of aromatic sulfonates, sodium and potassium salts are preferred.

[0203] These metal salt flame retardants may be used alone or in combination of two or more. When the polycarbonate resin composition according to the present invention contains a metal salt flame retardant as a flame retardant, the content of the flame retardant is, from the viewpoint of further improving flame retardancy, preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, even more preferably 0.03 part by mass or more, and still more preferably 0.04 part by mass or more, relative to 100 parts by mass of the polycarbonate resin composition, from the viewpoint of the balance between impact resistance and scratch resistance of the polycarbonate resin composition and a molded article thereof, preferably 1.0 part by mass or less, more preferably 0.8 part by mass or less, even more preferably 0.6 part by mass or less, and still more preferably 0.4 part by mass or less.

[0204] The total content of the polycarbonate resin composition and the flame retardant in the polycarbonate resin composition according to the present invention is, from the viewpoint of further improving the balance between tensile properties and flame retardancy, preferably 50% by mass or more, 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, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, when the entire polycarbonate resin composition is taken as 100% by mass. The upper limit of the total content of the polycarbonate resin composition and the flame retardant is not particularly limited, but from the viewpoint of obtaining a resin composition having desired properties, it is, for example, 100% by mass or less.

[0205] When the polycarbonate-based resin composition according to the present invention contains at least two or more components selected from the group consisting of a light stabilizer, a glittering particle, a colorant, an inorganic filler, an elastomer, and a flame retardant, the polycarbonate-based resin composition can exhibit the respective effects derived from each component.

[0206] The content of the polycarbonate-based resin (S) in the polycarbonate-based resin composition according to the present invention varies depending on whether the polycarbonate-based resin composition contains an ultraviolet absorber, a flame retardant, a polystyrene-based resin, a polyester-based resin, or an inorganic filler, but is preferably 60% by mass or more, more preferably 65% ​​by mass or more, even more preferably 70% by mass or more, still more preferably 85% by mass or more, particularly preferably 95% by mass or more, and most preferably 99.0% by mass or more, and is preferably 99.99% by mass or less, more preferably 99.97% by mass or less, and even more preferably 99.96% by mass or less.

[0207] The polycarbonate resin composition according to the present invention may contain additives such as a hydrolysis stabilizer, an antioxidant, and resins other than those mentioned above, in addition to the polycarbonate resin (S), a light stabilizer, glittering particles, a colorant, an inorganic filler, an elastomer, a flame retardant, and an acrylic resin.

[0208] For example, the polycarbonate resin composition may contain an antioxidant from the viewpoint of preventing oxidative degradation during melting and preventing coloration due to oxidative degradation. The content of the antioxidant is preferably 0.001 to 0.5 parts by mass, more preferably 0.01 to 0.3 parts by mass, and even more preferably 0.02 to 0.2 parts by mass, per 100 parts by mass of the polycarbonate resin composition. When the content of the antioxidant is within the above range, a sufficient antioxidant effect can be obtained and mold contamination during molding can be suppressed.

[0209] <Antioxidant> The polycarbonate resin composition according to the present invention may contain an antioxidant as appropriate, provided that the object of the present invention is not impaired. The antioxidant can suppress decomposition of the resin during production or molding of the polycarbonate resin composition. Known antioxidants can be used, and preferably at least one selected from phosphorus-based antioxidants and phenol-based antioxidants can be used. From the viewpoint of suppressing oxidative degradation of molded articles containing the polycarbonate resin composition during high-temperature molding, the phosphorus-based antioxidant is more preferably a phosphorus-based antioxidant having an aryl group, and more preferably a compound represented by the following general formula (102):

[0210]

[0211] In general formula (102), R Ｃ２１ ~R Ｃ２５ are hydrogen atoms, alkyl groups having 1 to 12 carbon atoms, or aryl groups having 6 to 14 carbon atoms, and may be the same or different. However, from the viewpoint of the effect as an antioxidant, R Ｃ２１ ~R Ｃ２５ cannot all be hydrogen atoms, and R Ｃ２１ ~R Ｃ２５ At least two of R are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms. Ｃ２１ ~R Ｃ２５ and R are preferably a compound in which any two of them are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms, and the remaining are hydrogen atoms. Ｃ２１ ~R Ｃ２５ Among compounds in which any two of the above are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms, and the remaining are hydrogen atoms, R Ｃ２１ or R Ｃ２５ At least one of the above is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.

[0212] Examples of alkyl groups having from 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, etc. Among these, from the viewpoint of imparting long-term moist heat resistance and long-term heat resistance, one or more selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, and various octyl groups is preferred, one or more selected from the group consisting of methyl, ethyl, isopropyl, and tert-butyl groups is more preferred, and tert-butyl groups is even more preferred.

[0213] Examples of the aryl group having 6 to 14 carbon atoms include a phenyl group, a tolyl group, and a xylyl group. Among these, from the viewpoint of being less susceptible to thermal decomposition and having an excellent effect of improving long-term moist heat resistance and long-term heat resistance, R Ｃ２１ ~R Ｃ２５ is more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, even more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, and even more preferably a hydrogen atom or a tert-butyl group.

[0214] Particularly preferably, R Ｃ２１ and R Ｃ２３ is a tert-butyl group, and R Ｃ２２ , R Ｃ２４ and R Ｃ２５ is a hydrogen atom.

[0215] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, diphenyl isooctyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithio phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 4,4' -isopropylidenediphenol dodecyl phosphite, 4,4'-isopropylidenediphenol tridecyl phosphite, 4,4'-isopropylidenediphenol tetradecyl phosphite, 4,4'-isopropylidenediphenol pentadecyl phosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyl)ditridecyl phosphite, 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-di-tridecyl phosphite-5-tert-butylphenyl)butane, 3,4,5,6-dibenzo-1,Examples of such phosphine include 2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite.

[0216] Specific examples of phosphorus-based antioxidants include "Irgafos168" (trademark, manufactured by BASF Japan Ltd.), "Irgafos12" (trademark, manufactured by BASF Japan Ltd.), "Irgafos38" (trademark, manufactured by BASF Japan Ltd.), "ADKSTAB 329K" (trademark, manufactured by ADEKA Corporation), "ADKSTAB PEP-36" (trademark, manufactured by ADEKA Corporation), "ADKSTAB PEP-8" (trademark, manufactured by ADEKA Corporation), "Sandstab P-EPQ" (trademark, manufactured by Clariant), "Weston 618" (trademark, manufactured by GE), "Weston 619G" (trademark, manufactured by GE), and "Weston 624" (trademark, manufactured by GE), and "Doverphos Examples of commercially available products include "S-9228PC" (manufactured by Dover Chemical Co.).

[0217] The phenolic antioxidant is preferably a hindered phenol. Specific examples of the phenolic antioxidant include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5.5)undecane, and the like.

[0218] Specific examples of the phenolic antioxidant include commercially available products such as "Irganox 1010" (BASF Japan Ltd., trademark), "Irganox 1076" (BASF Japan Ltd., trademark), "Irganox 1330" (BASF Japan Ltd., trademark), "Irganox 3114" (BASF Japan Ltd., trademark), "Irganox 3125" (BASF Japan Ltd., trademark), "BHT" (Takeda Pharmaceutical Co., Ltd., trademark), "Cyanox 1790" (Cyanamide Co., Ltd., trademark), and "Sumilizer GA-80" (Sumitomo Chemical Co., Ltd., trademark).

[0219] The antioxidant may be used alone or in combination of two or more. The content of the antioxidant in the polycarbonate resin composition according to the present invention is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, even more preferably 0.04 part by mass or more, still more preferably 0.08 part by mass or more, and is preferably 1.0 part by mass or less, more preferably 0.50 part by mass or less, even more preferably 0.25 part by mass or less, and still more preferably 0.15 part by mass or less, per 100 parts by mass of the polycarbonate resin composition. When multiple antioxidants are used, the total amount falls within the above range.

[0220] From the viewpoint of achieving both excellent scratch resistance and impact resistance, one embodiment of the polycarbonate-based resin composition of the present invention is a polycarbonate-based resin composition comprising a polycarbonate-based resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin, wherein the polycarbonate-polyorganosiloxane copolymer (A) can be the polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5), or (S-6).

[0221] From the viewpoint of achieving both excellent scratch resistance and impact resistance, a preferred embodiment of the polycarbonate resin composition of the present invention is a polycarbonate resin composition comprising a polycarbonate resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin, wherein the polycarbonate-polyorganosiloxane copolymer (A) can be the polycarbonate-polyorganosiloxane copolymer (S-1) or (S-2).

[0222] From the viewpoint of achieving both excellent scratch resistance and impact resistance, a more preferred embodiment of the polycarbonate-based resin composition of the present invention is a polycarbonate-based resin composition comprising a polycarbonate-based resin (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin, wherein the polycarbonate-polyorganosiloxane copolymer (A) may be the polycarbonate-polyorganosiloxane copolymer (S-2).

[0223] The method for producing the polycarbonate-based resin composition of the present invention is not particularly limited as long as it includes a step of mixing the polycarbonate-based resin (S) with at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin. For example, the polycarbonate-based resin composition can be produced by mixing the polycarbonate-based resin (S) with at least one selected from the group consisting of a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, and an acrylic resin using a mixer or the like, followed by melt-kneading. The melt-kneading can be carried out by a commonly used method, such as a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, or a multi-screw extruder. The heating temperature during melt-kneading is appropriately selected, for example, from the range of 150°C to 300°C, preferably from about 220°C to 300°C.

[0224] From the viewpoint of improving the impact resistance of the resulting molded article, the Charpy impact strength of a rectangular molded piece having a length of 80 mm, a width of 10 mm and a thickness of 4 mm obtained by molding the polycarbonate resin composition according to the present invention and having a notch (r=0.25 mm±0.05 mm) imparted thereto by post-processing is preferably 5 kJ / m ２ More preferably, 10 kJ / m ２ More preferably, 15 kJ / m ２From the viewpoint of further improving the impact resistance of the molded article of the obtained polycarbonate-based resin composition, the higher the Charpy impact strength, the better, so the upper limit is not particularly limited, but from the viewpoint of improving the tensile properties, it is preferably 110 kJ / m ２ Less than or equal to 95 kJ / m ２ More preferably, 85 kJ / m or less ２ The Charpy impact strength of a molded article of a polycarbonate-based resin composition can be increased by increasing the ratio of polyorganosiloxane blocks, and the higher the ratio of polyorganosiloxane units (A-2), the higher the Charpy impact strength of a molded article of a polycarbonate-based resin composition according to the present invention. Charpy impact strength can be measured in accordance with ISO-179-1:2010, specifically, by the method described in the Examples below. The molding conditions for the molded piece are a cylinder temperature of 200 to 270°C and a mold temperature of 80 to 120°C, and the cylinder temperature and mold can be appropriately set depending on the glass transition temperature of the polycarbonate-based resin composition used. Specifically, a molded piece can be obtained by the method described in the Examples below.

[0225] The deflection temperature under load of a molded article of the polycarbonate resin composition according to the present invention is preferably 112°C or higher, more preferably 115°C or higher, from the viewpoint of improving the heat resistance of the resulting molded article. From the viewpoint of further improving the heat resistance of the resulting molded article, the higher the deflection temperature under load, the better. Therefore, the upper limit is not particularly limited, but from the viewpoint of improving moldability, the deflection temperature under load is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 135°C or lower. The deflection temperature under load of a molded article of the polycarbonate resin composition can be increased by increasing the proportion of structures having a rigid skeleton. The higher the proportion of the structural unit (A-1) represented by general formula (1), the higher the deflection temperature under load of a molded article of the polycarbonate resin composition according to the present invention. The deflection temperature under load can be measured in accordance with Method A of ISO 527-1, 2 (2020), and specifically, it can be measured by the method described in the Examples described below.

[0226] The scratch hardness (pencil method) of a molded article of the polycarbonate-based resin composition according to the present invention is HB or higher, preferably F or higher, from the viewpoint of improving the scratch resistance of the resulting molded article. From the viewpoint of further improving the scratch resistance of the resulting molded article, the harder the scratch hardness, the better, so the upper limit is not particularly limited. The scratch hardness of a molded article of the polycarbonate-based resin composition can be increased by increasing the proportion of structures having a rigid skeleton, and the higher the proportion of the structural unit (A-1) represented by general formula (1), the higher the scratch hardness of a molded article of the polycarbonate-based resin composition according to the present invention. The scratch hardness can be measured in accordance with JIS K 5600-5-4:1999, specifically, by the method described in the Examples below.

[0227] The tensile modulus of the polycarbonate-based resin composition according to the present invention, measured in accordance with ISO 527-1,2:2012 using a JIS K7139 dumbbell tensile test piece Type A1, is preferably 2,400 MPa or more, more preferably 2,500 MPa or more, even more preferably 2,600 MPa or more, and even more preferably 2,700 MPa or more, from the viewpoint of improving the mechanical strength of the resulting molded article. From the viewpoint of further improving the impact resistance of the resulting molded article, the tensile modulus is preferably 10,000 MPa or less, more preferably 5,000 MPa or less, and even more preferably 3,500 MPa or less. The tensile modulus of a molded article of the polycarbonate-based resin composition can be increased by increasing the proportion of structures having a rigid skeleton. The tensile modulus of a molded article of the polycarbonate-based resin composition according to the present invention increases with an increase in the proportion of the structural unit (A-1) represented by general formula (1) in the polycarbonate-based resin (S). The tensile modulus can be a value measured at a tension speed of 1 mm / min and a measurement temperature of 23° C. The molding conditions for the molded piece are a cylinder temperature of 200 to 270° C. and a mold temperature of 80 to 120° C. The cylinder temperature and mold temperature can be set appropriately depending on the glass transition temperature of the polycarbonate resin composition used.

[0228] The tensile strength (yield) measured in accordance with ISO 527-1,2:2012 using a JIS K7139 dumbbell tensile test piece Type A1 obtained by molding the polycarbonate resin composition of the present invention is preferably 45 MPa or more, more preferably 50 MPa or more, and even more preferably 55 MPa or more, from the viewpoint of improving the mechanical strength of the resulting molded article. From the viewpoint of further improving the impact resistance of the resulting molded article, it is preferably 200 MPa or less, more preferably 150 MPa or less, even more preferably 100 MPa or less, and even more preferably 80 MPa or less. The tensile strength (yield) can be a value measured under conditions of a pulling rate of 50 mm / min and a measurement temperature of 23°C. The molding conditions for the molded piece are a cylinder temperature of 200 to 270°C, a mold temperature of 80°C, and a cycle time of 60 seconds. The cylinder temperature can be appropriately set depending on the glass transition temperature of the polycarbonate resin composition used.

[0229] The glass transition temperature of the polycarbonate resin composition according to the present invention is preferably 115°C or higher, more preferably 120°C or higher, even more preferably 130°C or higher, and even more preferably 140°C or higher, from the viewpoint of further improving the heat resistance of the resulting molded article. Since a higher glass transition temperature is preferable, the upper limit is not particularly limited, but from the viewpoint of improving processability, it is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. The glass transition temperature of the polycarbonate resin composition can be increased by increasing the proportion of structures having a rigid skeleton, and the higher the proportion of the structural unit (A-1) represented by general formula (1) in the polycarbonate resin (S), the higher the glass transition temperature of the polycarbonate resin composition according to the present invention.

[0230] 2. Molded Articles The molded article according to the present invention contains the polycarbonate resin composition. The molded article can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like, using a melt-kneaded product of the polycarbonate resin composition or pellets obtained through melt-kneading as a raw material. It is particularly preferred to produce the molded article by injection molding or injection compression molding using the obtained pellets.

[0231] The thickness of the molded article can be set arbitrarily depending on the application, and when transparency of the molded article is particularly required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. If the thickness of the molded article is 0.2 mm or more, warping does not occur and good mechanical strength is obtained.

[0232] The molded article may be coated with a hard coat film, an anti-fogging film, an antistatic film, or an anti-reflection film as needed, or may be coated with a composite of two or more types of film. Among these, a hard coat film is preferred because it has good light resistance and can prevent wear of the molded article surface over time. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic hard coat agents can be used.

[0233] The polycarbonate resin composition according to the present invention can be suitably used for impact-resistant applications, since the molded articles thereof have an excellent balance between impact resistance and scratch resistance. Examples of impact-resistant applications include structures whose outer surfaces are formed from the polycarbonate resin composition, and more specifically, plastic windows, touch panels, interior and exterior products, vehicle interior and exterior parts, housings, electrical appliance parts, building materials, and office automation equipment parts. The polycarbonate resin composition according to the present invention can be suitably used for producing the above-mentioned articles.

[0234] Molded articles made from the polycarbonate resin composition according to the present invention can be suitably used, for example, for: 1) automobile parts such as sunroofs, door visors, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms, and gratings; 3) windows for railway cars and ships; 4) electrical equipment parts such as various parts, outer panels, and housings for televisions, radio cassette players, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, cash registers, copiers, printers, and facsimiles; 5) precision equipment parts such as cases and covers for precision equipment such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as vinyl greenhouses and greenhouses; and 7) furniture parts such as lighting covers, blinds, and interior fixtures.

[0235] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. In these examples, polycarbonate-polyorganosiloxane copolymer will sometimes be abbreviated as PC-POS copolymer, and polydimethylsiloxane will sometimes be abbreviated as PDMS.

[0236] 1. Evaluation of Polycarbonate-Polyorganosiloxane Copolymer (A) The pellets containing PC-POS copolymer (A) produced in the following Production Examples were evaluated as follows: (1) １ H-NMR measurement under the following conditions １ Based on the integrated values ​​of peaks derived from the following specific structures obtained by H-NMR measurement, the contents of the structural unit represented by general formula (XX), the structural unit (A-1), the structural unit (A-31), and the structural unit (A-32), the molar fractions of the structural unit (A-1), the structural unit (A-31), and the structural unit (A-32) relative to the total amount of the structural unit represented by general formula (X) contained in the PC-POS copolymer, -OR ＴThe content of the terminal structure represented by the formula (1), the average value of a in the PC-POS copolymer (A), and the average value b2 when b and b1 in the PC-POS copolymer (A) are combined were calculated. (Measurement conditions) NMR apparatus: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: TH5 compatible with 5φ NMR sample tube Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Flip angle: 45° Number of accumulations: 256 NMR sample tube: 5φ Sample amount: 30 to 40 mg Sample pretreatment: Dry at 100°C for 6 hours (if structural unit A-32 is included) Solvent: deuterated chloroform Measurement temperature: room temperature Chemical shift correction: The peak derived from chloroform protons in deuterated chloroform was set to 7.26 ppm as the reference A: Peak integral value in the range of δ 7.30 to 7.43 (Note that peaks derived from chloroform protons in deuterated chloroform also appear in this range, but since the sample concentration was sufficient, this does not affect the structural assignment.) B: Peak integral value in the range of δ -0.20 to 0.30 C: Peak integral value in the range of δ 3.30 to 3.75 D: Peak integral value in the range of δ 4.75 to 5.30 E: Peak integral value in the range of δ 0.75 to 1.98 F: Peak integral value in the range of δ 1.98 to 2.70 G: Peak integral value in the range of δ 0.40 to 0.55 H: Peak integral value in the range of δ 1.30 to 1.50 aa = A / 2 bb = B / 6 cc = C / 4 dd = D / 3 ee = (E - F / 6 x 8 - G) / 10 kk = G / 2 ll = H / 4

[0237] Pellets containing PC-POS copolymer (A) produced in Production Examples 1-1 to 1-4 and 2-1 to 2-2 T １ = aaa １ +bb １ +cc １ +dd １ +ee １ TX １ =dd １ +ee １ f １ = aa １ / T １ x 100g １ =bb １ / T １ x 100 h１ =cc １ / T １ ×100 i １ =dd １ / T １ x 100 j １ =ee １ / T １ x100 TW １ = f １ x 93+g １ ×74.1+h １ ×44+i １ ×172+j １ × 170 Content (mass%) of structural unit (A-1): i １ ×172 / TW １ x 100 Content (mass%) of structural unit (A-32): j １ x170 / TW １ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f １ ×93 / TW １ × 100 Polycarbonate block content (mass%): (i １ x 172 + j １ ×170) / TW １ × 100 Content (mass%) of the structural unit represented by general formula (XX): g １ ×74.1 / TW １ × 100 Polyorganosiloxane block content (mass%): (g １ ×74.1+h １ ×44) / TW １ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: dd １ / TX １ × 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: ee １ / TX １ × 100 Average value of a in PC-POS copolymer (A): bb １ / (kk １ / 2) Average value b2 in PC-POS copolymer (A): cc １ / kk １

[0238] Pellets containing PC-POS copolymer (A) produced in Production Examples 3-1 to 3-3 T ３ = aa ３ +bb ３ +cc ３ +dd ３ +ll ３ TX ３ =dd ３ +ll ３ f ３ = aa ３ / T ３ x 100g ３ =bb ３ / T ３ x 100 h ３ =cc ３ / T ３ ×100 i ３ =dd ３ / T ３ x 100 j ３ =ll ３ / T ３ x100 TW ３ = f ３ x 93+g ３ ×74.1+h ３ ×44+i ３ x 172 + j ３ × 144 Content (mass%) of structural unit (A-1): i ３ ×172 / TW ３ x 100 Content (mass%) of structural unit (A-31): j ３ x144 / TW ３ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f ３ ×93 / TW ３ × 100 Polycarbonate block content (mass%): (i ３ x 172 + j ３ ×144) / TW ３ × 100 Content (mass%) of the structural unit represented by general formula (XX): g ３ ×74.1 / TW ３ × 100 Polyorganosiloxane block content (mass%): (g ３ ×74.1+h ３ ×44) / TW ３× 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: dd ３ / TX ３ × 100 Molar fraction of the structural unit (A-31) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: 11 ３ / TX ３ × 100 Average value of a in PC-POS copolymer (A): bb ３ / (kk ３ / 2) Average value b2 in PC-POS copolymer (A): cc ３ / kk ３

[0239] 2. Evaluation of Polycarbonate Resin Compositions The polycarbonate resin compositions produced in the following examples and comparative examples were evaluated as follows: (1) １ H-NMR measurement under the following measurement conditions １ Based on the integral values ​​of the peaks derived from the following specific structure obtained by H-NMR measurement, the contents of the structural unit represented by general formula (XX), the structural unit (A-1), and the structural unit (A-32), and the molar fractions of the structural unit (A-1) and the structural unit (A-32) relative to the total amount of the structural unit represented by general formula (X) contained in the PC-POS copolymer were calculated. (Measurement conditions) NMR apparatus: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: TH5 compatible with 5φ NMR sample tube Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Flip angle: 45° Number of accumulations: 256 NMR sample tube: 5φ Sample amount: 30 to 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature Chemical shift correction: the peak derived from the proton of chloroform in deuterated chloroform was set as the reference at 7.26 ppm. ２ : Peak integral value in the range of δ-0.20 to 0.30 B ２ : Peak integral value in the range of δ 4.75 to 5.30 C ２ : Peak integral value in the range of δ 0.75 to 1.98 D ２ : Peak integral value in the range of δ 0.40 to 0.55 E ２: Peak integral value in the range of δ 2.23 to 2.28 aa ２ = A ２ / 6 bb ２ = (B ２ -E ２ / 2) / 3 cc ２ = (C ２ -E ２ x11-D ２ ) / 10 dd ２ =D ２ / 2 Pellets containing the polycarbonate resin compositions produced in Example 1 and Comparative Example 1 T ２ = aa ２ +bb ２ +cc ２ TX ２ =bb ２ +cc ２ f ２ = aa ２ / T １ x 100g ２ =bb ２ / T １ x 100 h ２ =cc ２ / T １ x100 TW ２ = f ２ ×74.1+g ２ x 172 + h ２ × 170 Content (mass%) of structural unit (A-1): g ２ ×172 / TW ２ × 100 Content (mass%) of structural unit (A-32): h ２ x170 / TW ２ × 100 Polycarbonate block content (mass%): (g ２ x 172 + h ２ ×170) / TW ２ x 100 Content (mass%) of the structural unit represented by general formula (XX): f ２ ×74.1 / TW ２ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: bb ２ / TX ２× 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by general formula (X) contained in the PC-POS copolymer: cc ２ / TX ２ ×100

[0240] (2) Charpy Impact Strength The polycarbonate resin compositions produced in the following Examples 1 and 2, and Comparative Examples 1 and 2, were injection molded using an injection molding machine (DSM Xplore: 10cc Injection Molding Machine) at a cylinder temperature of 250 ° C., a mold temperature of 120 ° C., and rectangular test pieces measuring 80 mm in length, 10 mm in width, and 4 mm in thickness. Furthermore, using test pieces to which a notch (r = 0.25 mm ± 0.05 mm) had been added by post-processing, the Charpy impact strength was measured at -20 ° C., -10 ° C., and room temperature using a Charpy impact tester (Charpy Impact Tester, Model 611, manufactured by Toyo Seiki Seisakusho, Ltd.) in accordance with ISO 179-1:2010. The higher the Charpy impact strength, the better the impact resistance.

[0241] (3) Deflection Temperature Under Load The polycarbonate resin compositions produced in the following Examples 1 and 2 and Comparative Examples 1 and 2 were used in an injection molding machine (DSM Xplore: 10 cc Injection Molding Machine) at a cylinder temperature of 250 ° C., a mold temperature of 120 ° C., and strip-shaped test pieces measuring 80 mm in length, 10 mm in width, and 4 mm in thickness were prepared. The deflection temperature under load (load 1.8 MPa) was measured using the obtained strip test pieces in accordance with ISO 75-1,2:2020. A higher deflection temperature under load indicates better heat resistance.

[0242] (4) Scratch Hardness Using the same test pieces as those used to measure Charpy impact strength, which were obtained from pellets containing the polycarbonate resin compositions produced in the following Examples and Comparative Examples, the scratch hardness was measured in accordance with JIS K 5600-5-4:1999 at a load of 750 g and a measurement temperature of 23°C.

[0243] (5) Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw) The number average molecular weight (Mn) and weight average molecular weight (Mw) of pellets containing polycarbonate-polyorganosiloxane copolymers (PC-POS1 and PC-POS2) produced in the following Production Examples were calculated by gel permeation chromatography (GPC) measurement under the following conditions: Test equipment: Waters Acquity e2695 APC Column: TOSOH TSK-GEL SuperAWM-H x 2 Solvent: dimethylformamide (DMF) containing 10 mM lithium bromide Column temperature: 40 ° C. Flow rate: 0.6 mL / min Detector: RI Injection concentration: 0.1 w / v % Injection volume: 20 μL To prepare the calibration curve, the following standard polystyrene manufactured by Tosoh Corporation was used, and a cubic equation obtained by approximation using the least squares method was used. Standard polystyrene: F-450, F-288, F128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 The number average molecular weight (Mn) and weight average molecular weight (Mw) of pellets containing polycarbonate-polyorganosiloxane copolymers (PC-POS1 and PC-POS2) produced in the following Production Examples were measured as follows. 10 mg of the pellets were taken, and 10 mL of dimethylformamide containing 10 mM lithium bromide was added to completely dissolve the pellets. The resulting solution was filtered through a membrane filter, and GPC measurement was performed.

[0244] The differential molecular weight distribution curve can be obtained in the following manner. First, the time curve (elution curve) of the intensity distribution detected by the RI detector is used to obtain a molecular weight distribution curve versus the logarithmic value of the molecular weight (log(M)) using a calibration curve. Next, an integrated molecular weight distribution curve versus log(M) is obtained when the total area of ​​the distribution curve is taken as 100%, and then this integrated molecular weight distribution curve is differentiated by log(M) to obtain a differential molecular weight distribution curve versus log(M). The number average molecular weight (Mn) and weight average molecular weight (Mw) are defined by the number of molecules (Ni) of the molecular weight (Mi) at each elution position on the obtained differential molecular weight distribution curve, using the following equation: Mn = Σ(Ni·Mi) ２ ) / Σ(Ni・Mi) Mw=Σ(Ni・Mi ２) / Σ(Ni·Mi) Note that a series of operations for obtaining the differential molecular weight distribution curve, number average molecular weight (Mn) and weight average molecular weight (Mw) can usually be performed using analysis software built into the GPC measurement device.

[0245] (6) Viscosity Average Molecular Weight (Mv) The viscosity average molecular weight (Mv) was calculated by measuring the viscosity of a methylene chloride solution at 20°C using an Ubbelohde viscometer, determining the intrinsic viscosity [η] from the viscosity, and then using the following formula (Schnell formula):

[0246] 2. Production of Polycarbonate-Polyorganosiloxane (PC-POS) Copolymer Production Example 1-1: Production of PC-POS1-1 Polycarbonate-polyorganosiloxane PC-POS1-1 was produced by the following method, and the resulting pellets containing PC-POS1-1 were evaluated by the methods described above. The results are shown in Table 1. A 10 L stainless steel reactor equipped with a stirrer, a trap for capturing distilled phenol, and a pressure reducing device was charged with the diol monomer shown in Table 1, diphenyl carbonate (2,500.0 g / 11.7 mol) having the molar fraction shown in Table 1 when the total amount of the diol monomer is 100, and polyether-modified polyorganosiloxane PDMS-1 (KF-6123, manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the formula below in the amount shown in Table 1, which corresponds to the mass of the resulting PC-POS1-1 (theoretical value), and these were completely melted at a temperature of 100°C inside the reactor, and the inside of the reactor was purged with nitrogen.

[0247] Polymerization was initiated by adding 0.59 mL of 0.01 N sodium hydroxide, and the temperature in the reactor was raised to 190 ° C. over a period of about 50 to 100 minutes. The pressure in the reactor was reduced to 150 mmHg, and these conditions were maintained until the amount of phenol distilled reached 1.6 L. Next, the pressure in the reactor was reduced to 10 mmHg, and these conditions were maintained until 2.0 L of phenol was distilled. Next, the temperature in the reactor was raised to 220 ° C. over a period of about 15 minutes, and after maintaining this for about 10 minutes, the temperature in the reactor was raised to the final polymerization temperature shown in Table 1 over a period of about 10 minutes. Thereafter, the pressure in the reactor was reduced to 1 mmHg or less, and the reaction was continued until a predetermined stirring torque was reached. Nitrogen was then introduced to raise the pressure to atmospheric pressure, and Irganox 1010 and Irgafos 168 were each added so that their contents in the resulting polymer were 1,000 ppm, followed by stirring for 10 minutes or more. Thereafter, high-pressure nitrogen was introduced into the reactor, extruding resin strands from the bottom of the reactor. The resulting strands were cut with a pelletizer to obtain pellets containing PC-POS1-1, which is the polycarbonate-polyorganosiloxane copolymer (A). The resulting pellets containing PC-POS1-1 were evaluated by the methods described above. The results are shown in Table 1. Note that, under Production Condition 1, the "mass (theoretical value) of the resulting PC-POS1-1" refers to the sum of the charged mass of all diol monomers, the charged mass of diphenyl carbonate, and the charged mass of PDMS-1, minus the mass (theoretical value) of phenol produced from the charged diphenyl carbonate.

[0248] Production Examples 1-2 to 3-3: Production of PC-POS 1-2 to 3-3 Pellets containing PC-POS 1-2 to 3-3 were obtained in the same manner as in Production Example 1-1, except that the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature were changed as shown in Tables 1 to 3. The obtained pellets containing PC-POS 1-2 to 3-3 were evaluated by the methods described above. The results are shown in Tables 1 to 3. In the tables, "(A-31) to (A-34)" refer to (A-31), (A-32), (A-33), and (A-34).

[0249]

[0250]

[0251]

[0252] Examples 1-1 to 3-7 and Comparative Examples 1-1 to 3-4 As shown in Tables 4 to 8, PC-POS 1-1 to PC-POS 3-3 were mixed with a light stabilizer (ADEKA CORPORATION's "ADEKA STAB LA-77Y" and Chemipro Chemical Co., Ltd.'s "KEMISORB79"), glittering particles (Nippon Glass Co., Ltd.'s "MC5090PS" and Nippon Boshoku Kogyo Co., Ltd.'s "ASTROSHINE NJ-80"), colorants (LANXESS's "Macrolex Violet 3R" 10% by mass, LANXESS's "Macrolex Green 5B" 50% by mass, LANXESS's "Macrolex Blue RR" 10% by mass, and Arimoto Chemical Industry's "Diaresin Red" The resulting mixture was mixed with a black mixed colorant obtained by mixing 30% by mass of "A" or an elastomer ("KANE ACE M-590" manufactured by Kaneka Corporation), and the mixture was supplied to a small tabletop kneader (Micro 15 cc Twin Screw Compounder manufactured by DSM Xplore), and melt-kneaded at a barrel temperature of 250°C and a screw rotation speed of 50 rpm. The molten resin was then supplied to a tabletop injection molding machine (Micro 10 cc Injection Molding Machine manufactured by DSM Xplore), and molded at a cylinder temperature of 250°C and a mold temperature of 100°C. The Positive Charpy impact strength, deflection temperature under load, and scratch hardness were evaluated by the methods described above. However, since PC-POS 3-3 has a low glass transition point, in the comparative examples using this material, the barrel temperature was set to 210° C., the cylinder temperature was set to 210° C., and the mold temperature was set to 70° C. The results are shown in Tables 4 to 8.

[0253]

[0254]

[0255]

[0256]

[0257]

[0258] As shown in Tables 4 to 8, the polycarbonate resin compositions of the Examples were found to have an excellent balance between impact resistance and scratch resistance compared to the polycarbonate resin compositions of the Comparative Examples which contained the corresponding light stabilizer, glittering particles, colorant, or elastomer.

Claims

1. A polycarbonate-based resin composition (S) containing a polycarbonate-polyorganosiloxane copolymer (A), and at least one selected from the group consisting of a light-resistant agent, an elastomer, a colorant, a glittering particle, an inorganic filler, a flame retardant, and an acrylic resin, wherein the polycarbonate-based resin (S) contains a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a repeating structure (A-2) of the structure represented by the following general formula (XX), the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-based resin (S) is 78.0% by mass or more, and the content of the structural unit represented by the following general formula (XX) in the polycarbonate-based resin (S) is 2.0% by mass or more and 25.0% by mass or less. [In general formula (XX), R １ and R ２ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. ] 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin (S) further contains at least one structural unit (A-3) selected from the structures represented by the following general formulas (3) and (4). [In general formulas (3) and (4), R １１ represents a divalent linear or branched aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and R １２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms. ] 3. The polycarbonate resin composition according to claim 2, wherein the structural unit (A-3) has at least one selected from the structural units (A-31) to (A-34) represented by the following general formulas (31) to (34). [In general formula (31), n represents an integer of 2 to 18.] 4. The said R １ and R ２ The polycarbonate resin composition according to any one of claims 1 to 3, wherein is a methyl group.

5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the light stabilizer contains at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers, benzoxazinone-based ultraviolet absorbers, salicylate-based ultraviolet absorbers, malonic ester-based ultraviolet absorbers, oxalylalanide-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, cyanoacrylate-based ultraviolet absorbers, and amine-based light stabilizers.

6. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the elastomer contains at least one selected from the group consisting of rubbery graft polymers and rubbery graft polymer latexes.

7. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the colorant contains at least one selected from the group consisting of inorganic pigments, organic pigments, and organic dyes.

8. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the glitter particles contain at least one selected from the group consisting of particles obtained by coating at least one selected from the group consisting of metal particles and interference pigments with a metal or a metal oxide.

9. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the inorganic filler contains at least one selected from glass fillers, silica, and carbon fibers.

10. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the flame retardant contains at least one selected from the group consisting of phosphorus-based flame retardants and metal salt-based flame retardants.

11. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the acrylic resin contains at least one selected from the group consisting of (co)polymers of monomers selected from the group consisting of acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, acrylonitrile, and methacrylonitrile.

12. A molded article of the polycarbonate resin composition according to any one of claims 1 to 11.

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