Polycarbonate-polyorganosiloxane copolymer, polycarbonate resin composition and molded body

Abstract

The present invention relates to: a polycarbonate-polyorganosiloxane copolymer which contains a polycarbonate block that contains a structural unit (A-1) represented by general formula (1) and a polyorganosiloxane block that contains a structural unit (A-2) represented by general formula (2), and which satisfies condition (I) and condition (II); a polycarbonate resin composition which contains this polycarbonate-polyorganosiloxane copolymer; and a molded body which is formed of this polycarbonate resin composition.

Description

Polycarbonate-polyorganosiloxane copolymer, polycarbonate resin composition, and molded article

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate resin composition, and a molded article.

[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 the electrical and electronic equipment field and the automotive field. In recent years, from the viewpoint of carbon neutrality, there has been a demand for the development of polycarbonate resins made from plant-derived monomers. Examples of technologies related to such polycarbonate resins include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes a polycarbonate copolymer containing structural units derived from a specific dihydroxy compound and structural units derived from an alicyclic dihydroxy compound, characterized in that the polycarbonate copolymer has an Abbe number of 50 or more and a 5% heat loss temperature of 340°C or more, with the aim of providing a polycarbonate copolymer containing structural units derived from plants, which has excellent mechanical strength, heat resistance, a small refractive index, a large Abbe number, a small birefringence, and excellent transparency.

[0004] Patent Document 2 describes a molded article that is obtained by molding using a resin composition containing a polycarbonate resin having structural units derived from a specific dihydroxy compound and structural units derived from other dihydroxy compounds, with the aim of providing a resin molded article that has excellent thin-wall moldability, impact resistance, surface hardness, and moist heat resistance, and that has low optical distortion, and that is characterized in that the proportion of the structural units derived from the specific dihydroxy compound in the polycarbonate resin accounts for 70 mol % or more of the structural units derived from all dihydroxy compounds that constitute the polycarbonate resin, and that the polycarbonate resin has a reduced viscosity of 0.45 dL / g or less and a thickness of 0.1 mm or more and 1 mm or less.

[0005] Patent Document 3 describes a civil engineering and construction material part made of polycarbonate containing a structural unit derived from a specific dihydroxy compound, with the aim of improving environmental and resource conservation to some extent and at the same time providing a material part having properties suitable for the civil engineering and construction field.

[0006] JP 2008-24919 A ​​JP 2014-198761 A JP 2009-144013 A

[0007] According to the investigations of the present inventors, it has become clear that, for example, the molded body of the polycarbonate copolymer described in Patent Document 1, the molded body described in Patent Document 2, and the civil engineering and construction material parts made of polycarbonate described in Patent Document 3 have excellent scratch resistance, but there is room for improvement in impact resistance.

[0008] The present invention has been made in view of the above circumstances, and provides a polycarbonate-polyorganosiloxane copolymer and a polycarbonate-based resin composition that can give molded articles having excellent impact resistance and scratch resistance.

[0009] The present inventors have found that a polycarbonate-polyorganosiloxane copolymer containing a specific structural unit and a polycarbonate-based resin composition containing the copolymer can provide a molded article having excellent impact resistance and scratch resistance.

[0010] That is, according to the present invention, there are provided the following polycarbonate-polyorganosiloxane copolymer, polycarbonate resin composition, and molded article.

[0011] [1] A polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2), and a polycarbonate-polyorganosiloxane copolymer that satisfies the following conditions (I) and (II): [In general formula (2), R １ and R ２each 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. a represents an integer from 2 to 500.] Condition (I): The Charpy impact strength of a rectangular molded piece obtained by molding the polycarbonate-polyorganosiloxane copolymer and having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm, which is post-processed to have a notch (r=0.25 mm±0.05 mm), is 15 kJ / m, as measured at a measurement temperature of 23°C in accordance with ISO 179-1:2010. ２ or more Condition (II): The pencil hardness of a molded product of the polycarbonate-polyorganosiloxane copolymer measured in accordance with JIS K 5600-5-4:1999 is HB or more. [2] The polycarbonate-polyorganosiloxane copolymer according to [1], wherein the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0% by mass or more and 25.0% by mass or less, and the content of the structural unit (A-1) represented by the general formula (1) is 73.0% by mass or more. [In general formula (XX), R １ and R ２ is R in the general formula (2). １ and R ２ [3] The polycarbonate-polyorganosiloxane copolymer according to [1], further comprising 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 １２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.] [4] The polycarbonate-polyorganosiloxane copolymer according to [3], wherein the structural unit (A-3) has at least one structure selected from the structures represented by the following general formulas (31) to (34): [In general formula (31), n ​​represents an integer of 2 to 18.] [5] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) has a structural unit (A-32) represented by general formula (32), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x, the total content of the structural units (A-1) and (A-32) in the polycarbonate blocks contained in the polycarbonate-polyorganosiloxane copolymer 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 structural unit represented by the following general formula (XX) satisfy the following condition (C2) or (D2): 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 general formula (XX), R １ and R ２ is R in the general formula (2). １ and R ２ [6] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) has a structural unit (A-31) represented by the general formula (31), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is defined as x, 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 following general formula (XX) satisfy the following condition (C1) or (D1): 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 general formula (XX), R １ and R ２ is R in the general formula (2).１ and R ２represents the same meaning as above.] [7] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) has a structural unit (A-32) represented by the general formula (32) and a structural unit (A-33) represented by the general formula (33), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x, the molar ratio of the total of the structural units (A-32) and (A-33) to the structural unit (A-1) ((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 structural unit represented by 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, (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, (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, (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, (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 general formula (XX), R １ and R ２ is R in the general formula (2). １ and R ２ [8] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [7], wherein a is an integer of 2 or more and 300 or less. [9] The R １ and R ２

[10] A polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [9], wherein R is a methyl group.

[11] A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [9].

[12] A molded article made of the polycarbonate-based resin composition according to

[10] .

[0012] According to the present invention, it is possible to provide a polycarbonate-polyorganosiloxane copolymer and a polycarbonate-based resin composition that can give molded articles that are excellent in impact resistance and scratch resistance.

[0013] The polycarbonate-polyorganosiloxane copolymer of the present invention, a polycarbonate-based resin composition containing the copolymer, and a molded article of the resin composition are described in detail below. In this specification, any definition considered preferable can be adopted at will, and a combination of preferred definitions is 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 can be selected and combined. When compounds and chemical structures described herein have multiple stereoisomers and structural isomers, all stereoisomers and structural isomers are included. However, unless otherwise specified, the term "XX to YY" is used interchangeably.

[0014] 1. Polycarbonate-Polyorganosiloxane Copolymer The polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2). The polycarbonate-polyorganosiloxane copolymer of the present invention can provide a molded article having excellent impact resistance and scratch resistance.

[0015]

[0016] In general formula (2), 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. a represents an integer of 2 to 500.

[0017] <Polycarbonate Block> The polycarbonate block is represented by the following general formula (X) and contains a structural unit (A-1) represented by general formula (1).

[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 polycarbonate block of the polycarbonate-polyorganosiloxane copolymer of the present invention 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-polyorganosiloxane copolymer contains the structural unit (A-3), the impact resistance of the molded article can be further improved.

[0022]

[0023] 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.

[0024] From the viewpoint of reducing the melt flow rate of the polycarbonate-polyorganosiloxane copolymer 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 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-polyorganosiloxane copolymer 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).

[0025] 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 an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. 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.

[0026] 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.

[0027] 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.

[0028]

[0029] In general formula (3a), R １０１ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0030] 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.

[0031]

[0032] 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.

[0033]

[0034] 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.

[0035]

[0036] 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.

[0037]

[0038] 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:

[0039]

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] From the viewpoint of further increasing the impact resistance of the molded article, 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), and even more preferably includes at least one selected from structural units (A-31) to (A-33).

[0046] In the general formula (31), n ​​represents an integer of 2 to 18, preferably 3 to 10, and more preferably 4 to 8.

[0047] 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.

[0048] From the viewpoint of obtaining a molded article having excellent scratch resistance and impact resistance, the polycarbonate block content in the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 65.0% by mass or more, more preferably 80.0% by mass or more, even more preferably 85.0% by mass or more, and is preferably 99.0% by mass or less, more preferably 97.0% by mass or less, even more preferably 95.0% by mass or less. The polycarbonate block content in the polycarbonate-polyorganosiloxane copolymer is preferably 65.0 to 99.0% by mass, more preferably 80.0 to 97.0% by mass, even more preferably 85.0 to 95.0% by mass.

[0049] From the viewpoint of further improving the scratch resistance of the molded article, the content of the structural unit (A-1) in the polycarbonate-polyorganosiloxane copolymer is preferably 45.0 mass% or more, more preferably 55.0 mass% or more, even more preferably 65.0 mass% or more, and preferably 99.0 mass% or less, more preferably 95.0 mass% or less, even more preferably 90.0 mass% or less. The content of the structural unit (A-1) in the polycarbonate-polyorganosiloxane copolymer is preferably 45.0 to 99.0 mass%, more preferably 55.0 to 95.0 mass%, even more preferably 65.0 to 90.0 mass%. When the polycarbonate-polyorganosiloxane copolymer contains the structural unit (A-3), the content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer is preferably 1.0 mass% or more, more preferably 5.0 mass% or more, even more preferably 10.0 mass% or more, and preferably 50.0 mass% or less, more preferably 40.0 mass% or less, even more preferably 35.0 mass% or less, from the viewpoint of further improving the impact resistance of the molded article. The content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer is preferably 1.0 to 50.0 mass%, more preferably 5.0 to 40.0 mass%, even more preferably 10.0 to 35.0 mass%.

[0050] From the viewpoint of improving the scratch resistance of a molded article, the content of the structural unit (A-1) in the polycarbonate block is preferably 60.0 mol% or more, more preferably 70.0 mol% or more, and preferably 100.0 mol% or less, more preferably 90.0 mol% or less, and even more preferably 80.0 mol% or less. From the viewpoint of improving the scratch resistance of a molded article, the content of the structural unit (A-1) in the polycarbonate block is preferably 60.0 to 100.0 mol%, more preferably 70.0 to 90.0 mol%, and even more preferably 70.0 to 80.0 mol%. When the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-1) in the polycarbonate block is preferably 50.0 mol% or more, more preferably 60.0 mol% or more, even more preferably 70.0 mol% or more, and preferably 99.0 mol% or less, more preferably 90.0 mol% or less, even more preferably 80.0 mol% or less, from the viewpoint of improving the scratch resistance of the molded article. When the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-1) in the polycarbonate block is preferably 50.0 to 99.0 mol%, more preferably 60.0 to 90.0 mol%, even more preferably 70.0 to 80.0 mol%. When the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-3) in the polycarbonate block is preferably 3.0 mol% or more, more preferably 5.0 mol% or more, even more preferably 8.0 mol% or more, and even more preferably 10.0 mol% or more from the viewpoint of improving the impact resistance of the molded article, and is preferably 50.0 mol% or less, more preferably 40.0 mol% or less, and even more preferably 30.0 mol% or less from the viewpoint of obtaining a molded article excellent in scratch resistance and impact resistance. When the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-3) in the polycarbonate block is preferably 3.0 to 50.0 mol%, more preferably 5.0 to 40.0 mol%, even more preferably 8.0 to 30.0 mol%, and even more preferably 10.0 to 30.0 mol%.The contents of the polycarbonate block, the structural unit (A-1), and the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer are calculated by nuclear magnetic resonance (NMR) measurement.

[0051] <Terminal Structure of Polycarbonate-Polyorganosiloxane Copolymer> In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention has an —OR Ｔ R Ｔ is Ar, which will be described later. １ , Ar ２ , Ar ３ , Ar ４ , 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. ＴThe 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.

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

[0053]

[0054] In general formula (2), 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. a represents an integer of 2 to 500.

[0055]

[0056] In general formula (XX), R １ and R ２ is R in the general formula (2). １ and R ２ It has the same meaning as:

[0057] In the formula, 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 ２Examples 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 ~R ４ 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 ~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 １ ~R ４ More preferably, all of are methyl groups.

[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. ６represents 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. ５ 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 ７represents 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 the formula, 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 R ２ 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 ４The 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 ８ Examples 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. １１１Examples 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 repeating structural units represented by general formula (XX) plus 1, and 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 still more preferably 20 to 50. The average value of a in the polycarbonate-polyorganosiloxane copolymer 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 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-polyorganosiloxane copolymer is preferably 2 to 300, more preferably 10 to 95, even more preferably 15 to 70, even more preferably 15 to 50, and even more preferably 20 to 50. When the average value of a in the polycarbonate-polyorganosiloxane copolymer is 10 to 95, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and is a highly transparent copolymer, which is preferable. Furthermore, when the average value of a in the polycarbonate-polyorganosiloxane copolymer is 15 to 50, the molded article obtained from the polycarbonate-polyorganosiloxane copolymer has improved mechanical properties such as surface hardness, tensile strength, and tensile elongation, and a good molded appearance is obtained, which is preferable. The average value of a in the polycarbonate-polyorganosiloxane copolymer 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-polyorganosiloxane copolymer 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-polyorganosiloxane copolymer 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. When the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 10 or more, the impact resistance and scratch resistance of the obtained molded body can be further improved, which is more preferable. When the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 100 or less, the decrease in handleability due to an increase in the viscosity or melting point of the polyorganosiloxane can be suppressed, which is more preferable. When the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 50 or less, the physical property improving effect due to the polycarbonate-polyorganosiloxane copolymer containing polyorganosiloxane blocks is further improved, which is even more preferable.The average value b2 in the polycarbonate-polyorganosiloxane copolymer 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 R ６ 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 improve impact resistance.

[0078] The content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer of the present invention is, from the viewpoint of improving the impact resistance of the molded article, 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 5.0% by mass or more, and preferably 25.0% by mass or less, more preferably 20.0% by mass or less, even more preferably 15.0% by mass or less, still more preferably 7.5% by mass or less. The content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0 to 25.0% by mass, more preferably 3.0 to 20.0% by mass, even more preferably 4.0 to 15.0% by mass, still more preferably 5.0 to 7.5% by mass.

[0079] When the content of the structural unit represented by the general formula (XX) is within the above range, from the viewpoint of further improving the scratch resistance and impact resistance of the molded article, the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-polyorganosiloxane copolymer is preferably 73.0% by mass or more, more preferably 76.0% by mass or more, even more preferably 78.0% by mass or more, and preferably 96.0% by mass or less, more preferably 92.0% by mass or less, even more preferably 88.0% by mass or less. In this case, the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-polyorganosiloxane copolymer is preferably 73.0 to 96.0% by mass, more preferably 76.0 to 92.0% by mass, even more preferably 78.0 to 88.0% by mass.

[0080] In this specification, the term "content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer" refers to the content of the structural unit (A-1), the structural unit represented by general formula (XX), the structural unit represented by the following general formula (Y), -ORＴ and, if necessary, the structural unit (A-3).

[0081]

[0082] In general formula (Y), R Ｙ is R ７ or R ８ It is. Ｙ is R ８ If z ０ haz ２ and R Ｙ is R ７ If z ０ haz １ It is. ７ , R ８ , z １ , and z ２ represents the same meaning as above.

[0083] From the viewpoint of improving the impact resistance of the molded article, the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0% by mass or more, more preferably 4.0% by mass or more, even more preferably 9.0% by mass or more, and preferably 25.0% by mass or less, more preferably 16.0% by mass or less, even more preferably 13.0% by mass or less. The content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0 to 25.0% by mass, more preferably 4.0 to 16.0% by mass, even more preferably 9.0 to 13.0% by mass.

[0084] In this specification, the "content of polyorganosiloxane blocks in the polycarbonate-polyorganosiloxane copolymer" 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 ＴThe content of the polyorganosiloxane block and the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is calculated by nuclear magnetic resonance (NMR) measurement.

[0085] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention 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), wherein 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 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. In condition (D1), A-31 / A-1 is preferably 25.0 / 75.0 or less, more preferably 17.0 / 83.0 or less. In the condition (D1), the ratio A-31 / A-1 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 still more preferably 100.0 mol%.

[0086] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention comprises 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 is 90.0 mol% or more, and the molar ratio of the structural unit (A-32) to the structural unit (A-1) (A-32 / 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%.

[0087] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention 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%.

[0088] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention 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), and The polycarbonate-polyorganosiloxane copolymer (S-4) may be such that the molar ratio of the total of the structural units (A-32) and (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%.

[0089] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention 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), and The polycarbonate-polyorganosiloxane copolymer (S-5) may be such that the molar ratio of the total of the structural units (A-31) and (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 condition (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%.

[0090] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention 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), and The polycarbonate-polyorganosiloxane copolymer (S-6) may be such that the molar ratio of the total of the structural units (A-31) and (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%.

[0091] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), and may be a polycarbonate-polyorganosiloxane copolymer (S-7) that satisfies at least one condition selected from the following conditions (E1) to (E5): Condition (E1): The polystyrene-equivalent weight average molecular weight of the polycarbonate-polyorganosiloxane copolymer is 27,000 or more. Condition (E2): The melt flow rate (MFR) of the polycarbonate-polyorganosiloxane copolymer, measured in accordance with JIS K 7210 at 230°C and a load of 2.13 kg, is 25 g / 10 min or less. Condition (E3): The tensile modulus of the polycarbonate-polyorganosiloxane copolymer, measured in accordance with ISO 527-1,2:2012 at 1 mm / min using a JIS K7139 dumbbell tensile test piece Type A1 injection molded at a cylinder temperature of 200 to 270°C and a mold temperature of 80°C, is 2500 MPa or more. Condition (E4): The JIS K7139 dumbbell tensile test piece, measured in accordance with ISO 527-1,2:2012 at a cylinder temperature of 200 to 270°C and a mold temperature of 80°C. The tensile strength (yield) of the polycarbonate-polyorganosiloxane copolymer measured in accordance with ISO 527-1,2:2012 using Type A1 is 65 MPa or more. Condition (E5): In accordance with JIS K 7121, the sample is held at 50°C for 1 minute, then heated to 200°C, held at 200°C for 5 minutes, cooled to 50°C, held at 50°C for 5 minutes, and then heated from 50°C to 200°C at a rate of 20°C / min. The midpoint glass transition temperature is 115°C or more.

[0092] 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.

[0093] The polycarbonate-polyorganosiloxane copolymer (S-7) preferably satisfies at least two conditions selected from the conditions (E1) to (E5), more preferably satisfies at least three conditions selected from the conditions (E1) to (E5), even more preferably satisfies at least four conditions selected from the conditions (E1) to (E5), and most preferably satisfies all of the conditions (E1) to (E5). The weight-average molecular weight in the condition (E1) is preferably 32,000 or more. The melt flow rate in the condition (E2) is preferably 15 g / 10 min or less. The tensile modulus in the condition (E3) is preferably 2600 MPa or more. The tensile strength (yield) in the condition (E4) is preferably 70 MPa or more. The glass transition temperature in the condition (E5) is preferably 120°C or more.

[0094] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block containing the structural unit (A-1) represented by the general formula (1) and a polyorganosiloxane block containing the structure (A-2) represented by the general formula (2), and may be a polycarbonate-polyorganosiloxane copolymer (S-8) having a content of the structural unit represented by the general formula (XX) of 2.0% by mass or more and 25.0% by mass or less. The content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (S-8) is preferably 4.0% by mass or more, more preferably 6.0% by mass or more, even more preferably 8.0% by mass or more, and preferably 20.0% by mass or less, more preferably 15.0% by mass or less, even more preferably 13.0% by mass or less. The content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (S-8) is preferably 4.0 to 20.0 mass%, more preferably 6.0 to 15.0 mass%, and even more preferably 8.0 to 13.0 mass%.

[0095] The polycarbonate-polyorganosiloxane copolymer in the present invention is preferably the polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5), (S-6), (S-7), or (S-8), more preferably the polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), or (S-7), and even more preferably (S-2), (S-4), or (S-7).

[0096] From the viewpoint of improving scratch resistance and impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, even more preferably 11,500 or more, and 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 is preferably 5,000 to 30,000, more preferably 8,000 to 25,000, even more preferably 10,000 to 20,000, even more preferably 11,500 to 15,000. In particular, from the viewpoint of further improving scratch resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 11,500 or more.

[0097] The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer is preferably 20,000 or more, more preferably 25,000 or more, even more preferably 30,000 or more, even more preferably 33,000 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 is preferably 20,000 to 60,000, more preferably 25,000 to 50,000, even more preferably 30,000 to 45,000, even more preferably 33,000 to 43,000. In particular, from the viewpoint of further improving scratch resistance, the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer is preferably 30,000 or more, more preferably 31,000 or more, and even more preferably 33,000 or more. The reason why scratch resistance is improved by adjusting the number average molecular weight and weight average molecular weight within the above ranges is not clear, but is presumed as follows: When the number average molecular weight and weight average molecular weight are above a certain level, the entanglement and interaction between polymer chains is strengthened, improving the rigidity of the entire resin, and therefore improving scratch 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 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] <Method for Producing Polycarbonate-Polyorganosiloxane Copolymer> The polycarbonate-polyorganosiloxane copolymer 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.

[0100] <<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):

[0101]

[0102]

[0103] <<Diol Monomer (a3)>> When the polycarbonate-polyorganosiloxane copolymer 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 the structures represented by general formulas (3a) and (4a).

[0104] In general formulas (3a) and (4a), R １１ and R １２ The diol monomer (a1) is not included in the diol monomer (a3).

[0105] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably contains a polyorganosiloxane structure represented by the following general formula (21a).

[0106] 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.

[0107] The polyorganosiloxane (a2) preferably contains a polyorganosiloxane represented by the following general formula (22a):

[0108] 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.

[0109] The polyorganosiloxane (a2) preferably contains at least one of the polyorganosiloxanes represented by the following general formulas (23a) to (26a).

[0110]

[0111] 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.

[0112] 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.

[0113] Polycarbonate-polyorganosiloxane copolymers 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. A polycarbonate-polyorganosiloxane copolymer can be produced by reacting raw material monomers, polyorganosiloxane (a2), diol monomer (a1), and a carbonate ester compound described below, preferably in the presence of a basic catalyst, using a melt polymerization method. Diol monomer (a3) ​​may also be used as the raw material monomer, if necessary. Furthermore, a terminal terminator may also be added to carry out the polymerization reaction. Since melt polymerization does not require solvents such as methylene chloride, which are required in interfacial polymerization, it is environmentally and economically advantageous. Additionally, since it does not use the highly toxic phosgene used in interfacial polymerization, it is advantageous from a production standpoint. Therefore, polycarbonate-polyorganosiloxane copolymers are preferably produced by melt polymerization.

[0114] (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).

[0115]

[0116] 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.

[0117] 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).

[0118]

[0119] 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; 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.

[0120] Examples of the alkyl aryl carbonate compound include a compound represented by the following general formula (45) and a compound represented by the following general formula (46).

[0121]

[0122] 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.

[0123] 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.

[0124] (Terminator) When producing a polycarbonate-polyorganosiloxane copolymer, 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.

[0125] (Branching Agent) A branching agent can also be used when producing the polycarbonate-polyorganosiloxane copolymer. 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).

[0126] Specifically, a polycarbonate-polyorganosiloxane copolymer can be produced by melt polymerization, for example, by the following procedure. A mixture of raw material monomers containing diol monomer (a1), polyorganosiloxane (a2), and a carbonate ester compound is subjected to a transesterification reaction. The mixture of raw material monomers may optionally contain diol monomer (a3). The amount of the carbonate ester compound relative to the total amount of 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 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 diol monomers (a1) and (a3) ​​be 1 or less. Under polymerization conditions, when 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 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 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), because this sufficiently caps the hydroxyl group terminals of the resulting polycarbonate-polyorganosiloxane copolymer, 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.

[0127] The reaction temperature for carrying out the transesterification reaction is not particularly limited, and may be, for example, in the range of 100 to 330 ° C, preferably 150 to 300 ° C, and more preferably 170 to 240 ° C. Furthermore, a method in which the temperature is gradually increased from 150 ° C to 300 ° C as the reaction progresses is preferred, and a method in which the temperature is gradually increased from 170 ° C to 240 ° 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 330 ° C or lower, side reactions do not occur frequently, and problems such as discoloration of the resulting polycarbonate-polyorganosiloxane copolymer are unlikely to occur. The temperature in the final reactor is preferably 210 ° C or higher, more preferably 225 ° C or higher.

[0128] 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. ４ 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.

[0129] 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.

[0130] 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 organic acid salts, inorganic salts, 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.

[0131] 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.

[0132] 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.

[0133] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] The Charpy impact strength of a rectangular molded piece obtained by molding the polycarbonate-polyorganosiloxane copolymer of the present invention, having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm, and having a notch (r=0.25 mm±0.05 mm) imparted thereto by post-processing, is set to 15 kJ / m. ２ or more, preferably 18 kJ / m ２ More preferably, 30 kJ / m ２ More preferably, 40 kJ / m ２ From the viewpoint of further improving the impact resistance of the obtained molded article, 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 ２The Charpy impact strength of the polycarbonate-polyorganosiloxane copolymer 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 the polycarbonate-polyorganosiloxane copolymer of the present invention. The method for adjusting the Charpy impact strength of a molded article of the polycarbonate-polyorganosiloxane copolymer to fall within the above range is not particularly limited, but includes, for example, a method using the polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5), or (S-6). The Charpy impact strength can be measured in accordance with ISO-179-1:2010 at a measurement temperature of 23°C, and specifically, can be measured by the method described in the Examples below. The molding conditions for the above molded pieces 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 set appropriately depending on the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer used. Specifically, molded pieces can be obtained by the method described in the examples below.

[0140] The scratch hardness (pencil method) of a molded article of the polycarbonate-polyorganosiloxane copolymer 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 the polycarbonate-polyorganosiloxane copolymer 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 the polycarbonate-polyorganosiloxane copolymer of the present invention. The method for adjusting the scratch hardness of the polycarbonate-polyorganosiloxane copolymer molded article to the above range is not particularly limited, but for example, there is a method using the polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5), or (S-6). The scratch hardness can be measured in accordance with JIS K 5600-5-4:1999, and specifically, it can be measured by the method described in the examples below.

[0141] From the viewpoint of obtaining a molded article having excellent transparency, the total light transmittance for visible light of a 1.0 mm thick flat plate obtained by molding the polycarbonate-polyorganosiloxane copolymer according to the present invention is preferably 60% or more, more preferably 70% or more, even more preferably 80% or more, even more preferably 85% or more, and even more preferably 90% or more. The total light transmittance can be measured in accordance with ISO 13468-1:1996.

[0142] The melt flow rate (MFR) of the polycarbonate-polyorganosiloxane copolymer according to the present invention is preferably 1.0 g / 10 min or more, more preferably 2.5 g / 10 min or more, and even more preferably 3.0 g / 10 min or more, from the viewpoint of fluidity. From the viewpoint of improving scratch resistance, it is preferably 25.0 g / 10 min or less, more preferably 20.0 g / 10 min or less, and even more preferably 15.0 g / 10 min or less. The higher the MFR, the better the fluidity. MFR is measured by the measurement method specified in ISO 1133:1997, and specifically, it can be measured by the method described in the Examples below. The reason why scratch resistance is improved by adjusting the melt flow rate within the above range is unclear, but is presumed to be as follows. When the melt flow rate is within the above range, the resin pressure during molding increases, and high pressure is applied to the surface of the molded article. This is thought to result in a denser polymer on the surface of the molded article, resulting in increased surface hardness.

[0143] The tensile modulus of elasticity obtained by molding the polycarbonate resin composition according to the present invention, as measured in accordance with ISO 527-1,2:2012 using a JIS K7139 dumbbell tensile test piece Type A1, is preferably 2400 MPa or more, more preferably 2500 MPa or more, even more preferably 2600 MPa or more, and even more preferably 2700 MPa or more, from the viewpoint of further improving the mechanical strength and scratch resistance of the resulting molded article. Since a higher tensile modulus is preferable from the viewpoint of further improving the scratch resistance of the resulting molded article, the upper limit is not particularly limited, but from the viewpoint of improving impact resistance, it is preferably 10,000 MPa or less, more preferably 5,000 MPa or less, and even more preferably 3,500 MPa or less. The reason why scratch resistance is improved by adjusting the tensile modulus within the above range is not clear, but is presumed to be as follows. When the tensile modulus is within the above range, it is believed that the rigidity of the resin surface is also increased, and when the resin surface is subjected to external pressure or displacement, the resulting deformation is reduced, thereby improving scratch resistance. The tensile modulus of the polycarbonate-polyorganosiloxane copolymer 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 tensile modulus of the polycarbonate-polyorganosiloxane copolymer of the present invention. The tensile modulus can be measured under conditions of a pulling rate of 1 mm / min and a measurement temperature of 23°C, and specifically, can be measured by the method described in the Examples below. The molding conditions for the above 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-polyorganosiloxane copolymer used. Specifically, molded pieces can be obtained by the method described in the Examples below.

[0144] 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 according to 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 further improving the mechanical strength and scratch resistance of the resulting molded article. Since a higher tensile strength (yield) is preferable from the viewpoint of further improving the mechanical strength and scratch resistance of the resulting molded article, the upper limit is not particularly limited, but from the viewpoint of improving impact resistance, 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 reason why scratch resistance is improved by adjusting the tensile strength (yield) within the above range is not clear, but is presumed to be as follows. When the tensile strength (yield) is within the above range, it is thought that when the resin surface is subjected to pressure or displacement, the resin surface deforms, requiring greater pressure or displacement. Therefore, it is believed that scratch resistance is improved when the tensile strength (yield) is within the above range. The tensile strength (yield) can be measured under conditions of a pulling rate of 50 mm / min and a measurement temperature of 23°C, and specifically, can be measured by the method described in the Examples below. The molding conditions for the above 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 set appropriately depending on the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer used.

[0145] The glass transition temperature of the polycarbonate-polyorganosiloxane copolymer 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 scratch 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 160°C or lower. The reason why scratch resistance is improved by adjusting the glass transition temperature within the above range is not clear, but is presumed as follows. When the glass transition temperature is within the above range, it is thought that the molecular mobility of the resin surface at the use temperature or test temperature is low, or the intermolecular interaction is high. In such a state, the flexibility of the resin surface tends to be low and the rigidity tends to be increased, and as a result, deformation when the resin surface is subjected to pressure or displacement is suppressed, and scratch resistance is thought to be improved. The glass transition temperature of the polycarbonate-polyorganosiloxane copolymer can be increased by increasing the proportion of the structure having a rigid skeleton, and the higher the proportion of the structural unit (A-1) represented by general formula (1), the higher the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer of the present invention. Specifically, the glass transition temperature can be measured by the method described in the Examples below.

[0146] 2. Polycarbonate Resin Composition The polycarbonate resin composition of the present invention (hereinafter sometimes referred to as the "resin composition") may consist solely of the polycarbonate-polyorganosiloxane copolymer, or may contain a polycarbonate resin (P) other than the polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes referred to as the "polycarbonate resin (P)"). From the viewpoint of improving the impact resistance, tensile properties, and chemical resistance of the molded article, the content of the polycarbonate-polyorganosiloxane copolymer in the polycarbonate resin composition 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. The upper limit of the content of the polycarbonate-polyorganosiloxane copolymer in the polycarbonate resin composition is not particularly limited, but from the viewpoint of obtaining a resin composition having desired properties, it is, for example, 100 mass % or less.

[0147] From the viewpoint of improving the impact resistance of a molded article, the content of the structural unit represented by general formula (XX) in the polycarbonate resin composition is preferably 2% by mass or more, more preferably 3% by mass or more, even more preferably 4% by mass or more, and is preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less.

[0148] The number average molecular weight (Mn) of the polycarbonate resin composition 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 composition is a weighted average of the number average molecular weights (Mn) of the copolymers or resins contained in the resin composition, 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 number average molecular weight (Mw) of the polycarbonate resin composition is preferably 20,000 or more, more preferably 25,000 or more, even more preferably 30,000 or more, even more preferably 33,000 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.

[0149] <Polycarbonate-based resin (P)> The polycarbonate-based resin (P) is not particularly limited, and various known polycarbonate-based resins can be used. The polycarbonate-based resin (P) is preferably a polycarbonate-based resin that does not contain a polyorganosiloxane unit (A-2) containing a structural unit represented by the general formula (2) above, but contains a polycarbonate block (A-1) containing a structural unit represented by the general formula (1) above and / or at least one structural unit (A-3) selected from structures represented by general formulas (3) and (4). Examples of the structural unit (A-1) and structural unit (A-3) contained in the polycarbonate-based resin (P) include the same as the structural unit (A-1) and structural unit (A-3) contained in the polycarbonate-polyorganosiloxane copolymer. The preferred embodiments are also the same. The polycarbonate-based resin (P) preferably contains the structural unit (A-1) and the structural unit (A-3) as main components. The polycarbonate-based resin (P) preferably contains the structural unit (A-1) and the structural unit (A-3) in a total amount of 50 mass% or more, more preferably 80 mass% or more, even more preferably 90 mass% or more, and even more preferably 98 mass% or more, based on the total structure of the polycarbonate-based resin (P). The number average molecular weight (Mn) of the polycarbonate-based resin (P) 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 preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, and even more preferably 15,000 or less.

[0150] <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 a molded article 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 (51):

[0151]

[0152] In formula (2), 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.

[0153] 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.

[0154] 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.

[0155] Particularly preferably, R Ｃ２１ and R Ｃ２３ is a tert-butyl group, and R Ｃ２２ , R Ｃ２４ and R Ｃ２５ is a hydrogen atom.

[0156] 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.

[0157] 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.).

[0158] 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.

[0159] 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).

[0160] 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.

[0161] 3. Molded Article The molded article of 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. In particular, it is preferable to produce the molded article by injection molding or injection compression molding using the obtained pellets.

[0162] 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, no warping occurs and good mechanical strength is obtained. Furthermore, if the thickness of the molded article is 4.0 mm or less, high transparency is obtained.

[0163] 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 preferably formed because it has good weather 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.

[0164] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In these examples, polydimethylsiloxane may be abbreviated as PDMS.

[0165] 1. Preparation of Terminally Modified Polyorganosiloxane Preparation Example 1: Preparation of PDMS-1 In a nitrogen atmosphere, To 100 g of an α,ω-dihydrogenorganopolysiloxane having an average chain length of 25 in the polyorganosiloxane structure represented by the following formula: A two-fold molar amount (78.1 g) of one-terminal allyl-modified polyethylene glycol having an average repeating unit number of oxyethylene units of 15 was added relative to the polyorganosiloxane. 455 g of isopropyl alcohol (2.5 parts relative to the total mass of the α,ω-dihydrogenorganopolysiloxane and one-terminal allyl-modified polyethylene glycol) was added thereto, and the mixture temperature was controlled to 80 ° C. and stirred for 10 minutes or more. Next, a toluene solution of a platinum vinylsiloxane complex (platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added as a hydrosilylation catalyst in an amount such that the mass of platinum atoms was 5 ppm by mass relative to the siloxane in the polyorganosiloxane, and the mixture was stirred for 10 hours. The isopropyl alcohol, toluene, and platinum catalyst were removed from the resulting mixture to obtain polyether-modified polyorganosiloxane PDMS-1. The structure of the resulting PDMS-1 is shown below.

[0166]

[0167] <Method for measuring the average chain length of polyorganosiloxane and the average number of oxyethylene repeating units of polyethylene glycol> The average chain length of polyorganosiloxane was calculated from the integral ratio of methyl groups of polydimethylsiloxane by NMR measurement. The average number of repeating units of polyethylene glycol was calculated from the integral ratio of dimethylene groups of polyethylene glycol by NMR measurement. １H-NMR measurement conditions NMR device: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: 50TH5AT / FG2 Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5φ Sample amount: 30 to 40 mg Solvent: deuterated chloroform Measurement temperature: 23°C Number of accumulations: 256 Chemical shift correction: Protons derived from chloroform in deuterated chloroform ( １ H) peak was set to the reference of 7.26 ppm.

[0168] 2. Evaluation of Polycarbonate-Polyorganosiloxane Copolymer The following evaluations were carried out on the pellets containing the polycarbonate-polyorganosiloxane copolymer produced in the following Examples and Comparative Examples, and the pellets containing polycarbonate produced in the Comparative Examples. (1) １ H-NMR measurement under the following measurement 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), the structural unit (A-32), and the structural unit (A-33), the molar fractions of the structural units (A-1), (A-31), (A-32), and (A-33) relative to the total amount of the structural unit represented by 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 polycarbonate-polyorganosiloxane copolymer, and the average value b2 when b and b1 in the polycarbonate-polyorganosiloxane copolymer were 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 Pulse width: 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: peak derived from chloroform protons in deuterated chloroform set as standard at 7.26 ppm 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 the sample concentration is sufficient so 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 1.30 to 1.50 (Note that peaks derived from water protons in deuterated chloroform also appear in this range, but the sample concentration is sufficient so that this does not affect the structural assignment.) F: Peak integral value in the range of δ 0.75 to 1.98 G: Peak integral value in the range of δ 1.98 to 2.70 H: Peak integral value in the range of δ 0.40 to 0.55 aa = A / 2 bb = B / 6 cc = C / 4 dd = D / 3 ee = (F-G / 6 × 8 - H) / 10 kk = E / 4 11 = G / 6 oo = H / 2 Pellets containing the polycarbonate-polyorganosiloxane copolymer produced in Example 1 T １ =dd TX １ =dd f １ = aa / T １ x 100g １ = bb / T １ x 100 h １ = cc / T １ ×100 i １ = dd / T １ x100 TW １ = f １x 93+g １ ×74.1+h １ ×44+i １ × 172 Content (mass%) of structural unit (A-1): i １ ×172 / 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 ×172) / 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 formula (X) contained in the PC-POS copolymer: dd / TX １ ×100 Average value of a in the polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2) Average value b2 in the polycarbonate-polyorganosiloxane copolymer: cc / oo Pellets containing the polycarbonate-polyorganosiloxane copolymers produced in Examples 2 to 6 and Comparative Example 1 T ２ =aa+bb+cc+dd+kk TX ２ =dd+kkf ２ = aa / T ２ x 100g ２ = bb / T ２ x 100 h ２ = cc / T ２ ×100 i ２ = dd / T ２ ×100 n ２ = kk / T ２ x100 TW ２ = f ２ x 93+g ２ ×74.1+h ２ ×44+i ２ ×172+n ２ × 144 Content (mass%) of structural unit (A-1): i２ ×172 / TW ２ × 100 Content (mass%) of structural unit (A-31): n ２ x144 / TW ２ ×100 -OR Ｔ The content of the terminal structure represented by: f ２ ×93 / TW ２ × 100 Polycarbonate block content (mass%): (i ２ ×172+n ２ ×144) / TW ２ × 100 Content (mass%) of the structural unit represented by general formula (XX): g ２ ×74.1 / TW ２ × 100 Polyorganosiloxane block content (mass%): (g ２ ×74.1+h ２ ×44) / TW ３ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: dd / TX ２ × 100 Molar fraction of the structural unit (A-31) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: kk / TX ２ ×100 Average value of a in the polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2) Pellets containing the polycarbonate-polyorganosiloxane copolymers produced in Examples 7 to 15 and Comparative Examples 2 to 4 T ３ =aa+bb+cc+dd+ee TX ３ =dd+ee f ３ = aa / T ３ x 100g ３ = bb / T ３ x 100 h ３ = cc / T ３ ×100 i ３ = dd / T ３ x 100 j ３ = ee / T ３ x100 TW ３ = f ３ x 93+g ３ ×74.1+h ３ ×44+i ３ x 172 + j ３× 170 Content (mass%) of structural unit (A-1): i ３ ×172 / TW ３ x 100 Content (mass%) of structural unit (A-32): j ３ x170 / 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 ×170) / TW １ × 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 formula (X) contained in the PC-POS copolymer: dd / TX ３ × 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: ee / TX ３ ×100 Average value of a in the polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2) Average value b2 in the polycarbonate-polyorganosiloxane copolymer: cc / oo Pellets containing polycarbonate-polyorganosiloxane copolymers produced in Examples 16 to 20 and Comparative Examples 6 and 7 T ４ =aa+bb+cc+dd+ee+ll TX ４ =dd+ee+ll f ４ = aa / T ４ x 100g ４ = bb / T ４ x 100 h ４ = cc / T ４ ×100 i ４ = dd / T ４ x 100 j ４ = ee / T ４ x 100 m ４ = ll / T４ x100 TW ４ = f ４ x 93+g ４ ×74.1+h ４ ×44+i ４ x 172 + j ４ ×170+m ４ × 222 Content (mass%) of structural unit (A-1): i ４ ×172 / TW ４ x 100 Content (mass%) of structural unit (A-32): j ４ x170 / TW ４ × 100 Content (mass%) of structural unit (A-33): m ４ ×222 / TW ４ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f ４ ×93 / TW ４ × 100 Polycarbonate block content (mass%): (i ４ x 172 + j ４ ×170+m ４ ×222) / TW ４ × 100 Content (mass%) of the structural unit represented by general formula (XX): g ４ ×74.1 / TW ４ × 100 Polyorganosiloxane block content (mass%): (g ４ ×74.1+h ４ ×44) / TW ４ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: dd / TX ４ × 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: ee / TX ４ × 100 Molar fraction of the structural unit (A-33) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: 11 / TX ４×100 Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2) Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo Pellets containing polycarbonate-polyorganosiloxane copolymer produced in Example 21 and Comparative Example 9 T ５ =aa+bb+cc+dd+llTX ５ =dd+llf ５ = aa / T ５ x 100g ５ = bb / T ５ x 100 h ５ = cc / T ５ ×100 i ５ = dd / T ５ x 100 m ５ = ll / T ５ x100 TW ５ = f ５ x 93+g ５ ×74.1+h ５ ×44+i ５ ×172+m ５ × 222 Content (mass%) of structural unit (A-1): i ５ ×172 / TW ５ × 100 Content (mass%) of structural unit (A-33): m ５ ×222 / TW ５ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f ５ ×93 / TW ５ × 100 Polycarbonate block content (mass%): (i ５ ×172+m ５ ×222) / TW ５ × 100 Oil content (mass%) of the structural unit represented by general formula (XX): g ５ ×74.1 / TW ５ × 100 Polyorganosiloxane block content (mass%): (g ５ ×74.1+h ５ ×44) / TW ５× 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: dd / TX ５ × 100 Molar fraction of the structural unit (A-33) relative to the total amount of structural units represented by formula (X) contained in the PC-POS copolymer: 11 / TX ５ ×100 Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2) Average value of b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo Pellets containing polycarbonate produced in Comparative Example 5 T ６ =aa+dd+eeTX ６ =dd+ee f ６ = aa / T ６ ×100 i ６ = dd / T ６ x 100 j ６ = ee / T ６ x100 TW ６ = f ６ ×93+i ６ x 172 + j ６ × 170 Content (mass%) of structural unit (A-1): i ６ ×172 / TW ６ x 100 Content (mass%) of structural unit (A-32): j ６ x170 / TW ６ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f ６ ×93 / TW ６ × 100 Polycarbonate block content (mass%): (i ６ x 172 + j ６ ×170) / TW ６ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by formula (X) contained in the polycarbonate: dd / TX ６ × 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by formula (X) contained in the polycarbonate: ee / TX ６ × 100 Pellets containing polycarbonate produced in Comparative Example 8 T ７ =aa+dd+ee+llTX ７=dd+ee+ll f ７ = aa / T ７ ×100 i ７ = dd / T ７ x 100 j ７ = ee / T ７ x 100 m ７ = ll / T ７ x100 TW ７ = f ７ ×93+i ７ x 172 + j ７ ×170+m ７ × 222 Content (mass%) of structural unit (A-1): i ７ ×172 / TW ７ x 100 Content (mass%) of structural unit (A-32): j ７ x170 / TW ７ × 100 Content (mass%) of structural unit (A-33): m ７ ×222 / TW ７ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by ７ ×93 / TW ７ × 100 Polycarbonate block content (mass%): (i ７ x 172 + j ７ ×170+m ７ ×222) / TW ７ × 100 Molar fraction of the structural unit (A-1) relative to the total amount of structural units represented by formula (X) contained in the polycarbonate: dd / TX ７ × 100 Molar fraction of the structural unit (A-32) relative to the total amount of structural units represented by formula (X) contained in the polycarbonate: ee / TX ７ × 100 Molar fraction of the structural unit (A-33) relative to the total amount of structural units represented by formula (X) contained in the polycarbonate: 11 / TX ７ ×100

[0169] (2) Charpy impact strength Pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and pellets containing polycarbonate produced in the comparative examples were dried at 100 ° C. for 5 hours, and then injection-molded into strip-shaped test pieces for evaluating mechanical properties with a length of 80 mm, a width of 10 mm, and a thickness of 3 mm at a cylinder temperature of 220 ° C. and a mold temperature of 80 ° C. Furthermore, using test pieces to which a notch (r = 0.25 mm ± 0.05 mm) had been given by post-processing, the Charpy impact strength at 23 ° C. was measured using a Charpy impact tester (Charpy Impact Tester, Model 611, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with ISO 179-1:2010. In Examples 1, 7, 8, and 13, the cylinder temperature during injection molding was set to 250°C, in Comparative Example 2, the cylinder temperature during injection molding was set to 240°C, and in Examples 2, 5, 9, 10, 12, 13, and 15 to 17 and Comparative Example 4, the cylinder temperature during injection molding was set to 230°C.

[0170] (3) Scratch Hardness The scratch hardness of a surface of 80 mm long and 10 mm wide strips of mechanical property evaluation test pieces obtained from pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples, and pellets containing polycarbonate produced in Comparative Examples, similar to those for Charpy impact strength, was measured in accordance with JIS K 5600-5-4:1999, at a load of 750 g and a measurement temperature of 23°C.

[0171] (4) Weight average molecular weight The weight average molecular weight of the pellets containing polycarbonate-polyorganosiloxane copolymer produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples, was 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: 10 mM lithium bromide containing dimethylformamide (DMF) 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 weight average molecular weight of the pellets containing polycarbonate-polyorganosiloxane copolymer produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples, was measured as follows. 10 mg was taken from the pellets, 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.

[0172] The differential molecular weight distribution curve can be obtained by the following method. 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 weight average molecular weight (Mw) is defined by the number of molecules (Ni) of the molecular weight (Mi) at each elution position on the obtained differential molecular weight distribution curve, as follows: Weight average molecular weight: Mw = Σ(Ni·Mi) 2) / Σ(Ni·Mi) The series of operations up to obtaining the differential molecular weight distribution curve and the weight average molecular weight (Mw) can usually be performed using analysis software built into the GPC measuring device.

[0173] (5) Melt Flow Rate (MFR) Pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples, and pellets containing polycarbonate produced in the Comparative Examples were dried at 100°C for 5 hours, and then measured in accordance with JIS K 7210 under conditions of 230°C and a load of 2.13 kg.

[0174] (6) Tensile modulus Pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and pellets containing polycarbonate produced in the comparative examples were dried at 100 ° C. for 5 hours, and then injection-molded at a cylinder temperature of 220 ° C. and a mold temperature of 80 ° C., using JIS K7139 dumbbell-shaped tensile test specimen Type A1, measured at a measurement temperature of 23 ° C. under the conditions of a tensile speed of 1 mm / min in accordance with ISO 527-1,2:2012. In Examples 1, 7, 8, and 13, the cylinder temperature during injection molding was 250 ° C., in Comparative Example 2, the cylinder temperature during injection molding was 240 ° C., and in Examples 2, 5, 9, 10, 12, 13, and 15 to 17, and Comparative Example 4, the cylinder temperature during injection molding was 230 ° C.

[0175] (7) Tensile strength (yield) Pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and pellets containing polycarbonate produced in the comparative examples were dried at 100 ° C. for 5 hours, and then injection-molded at a cylinder temperature of 220 ° C. and a mold temperature of 80 ° C., using a JIS K7139 dumbbell-shaped tensile test piece Type A1, measured at a measurement temperature of 23 ° C. under conditions of a tensile speed of 50 mm / min in accordance with ISO 527-1,2:2012. In Examples 1, 7, 8, and 13, the cylinder temperature during injection molding was 250 ° C., in Comparative Example 2, the cylinder temperature during injection molding was 240 ° C., and in Examples 2, 5, 9, 10, 12, 13, and 15 to 17 and Comparative Example 4, the cylinder temperature during injection molding was 230 ° C.

[0176] (8) Glass Transition Temperature Using a PerkinElmer DSC8500 in accordance with JIS K 7121, 10 mg of pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and pellets containing polycarbonate produced in the comparative examples, were collected in an aluminum pan, held at 50 ° C. for 1 minute, heated to 200 ° C., held as is for 5 minutes, cooled to 50 ° C., held as is for 5 minutes, and then heated from 50 ° C. to 200 ° C. at a rate of 20 ° C. / min. The midpoint glass transition temperature was measured.

[0177] 3. Production of Polycarbonate-Polyorganosiloxane (PC-POS) Copolymer Example 1: Production of PC-POS1 Polycarbonate-polyorganosiloxane PC-POS1 was produced under the following production condition 1, and the resulting pellets containing PC-POS1 were evaluated using the method described above. The results are shown in Table 1. (Production Condition 1) A 10-liter 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 diol monomer is taken as 100, and polyether-modified polyorganosiloxane PDMS-1 in the amounts shown in Table 1, which corresponds to the mass of the resulting PC-POS copolymer (theoretical value). These were then completely melted at a reactor temperature of 100°C, and the atmosphere inside the reactor was purged with nitrogen. 1.6 mL of 0.01 N sodium hydroxide was added to start polymerization, and the temperature inside the reactor was raised to 180°C over a period of about 50 to 100 minutes, and the pressure inside the reactor was raised to 2.66 × 10 ４ The pressure was reduced to 1.33×10 Pa, and these conditions were maintained until the amount of phenol distilled reached 0.6 L. Next, the temperature inside the reactor was raised to 190° C. over about 50 minutes, and the pressure inside the reactor was reduced to 1.33×10 ３ The pressure was reduced to 1.33 x 10 Pa, and these conditions were maintained until 2.0 L of phenol was distilled out. Next, the temperature inside the reactor was raised to 220°C over about 15 minutes, and after maintaining this temperature for about 10 minutes, the temperature inside the reactor was raised to the final polymerization temperature shown in Table 1 over about 10 minutes. Thereafter, the pressure inside the reactor was reduced to 1.33 x 10 ２The pressure was reduced to 0.2 Pa or less, and the reaction was continued until the predetermined stirring torque was reached. Nitrogen was then introduced to raise the pressure to atmospheric pressure, and p-butyl toluenesulfonate was added as a polymerization deactivator in the amount shown in Table 1, as needed. Furthermore, Irganox 1010 and Irgafos 168 were each added so that their contents in the resulting polymer were 1,000 ppm, and the mixture was stirred for 10 minutes or more. High-pressure nitrogen was then 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 polycarbonate-polyorganosiloxane copolymer PC-POS1. Note that in the above production condition 1, the "mass (theoretical value) of the resulting PC-POS copolymer" 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.

[0178] Examples 2 and 5, and Comparative Example 1: Production of PC-POS 2, 5, and 31 Pellets containing PC-POS 2, 5, and 31 were obtained in the same manner as in Example 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 Table 1. The obtained pellets containing PC-POS 2, 5, and 31 were evaluated by the methods described above. The results are shown in Table 1.

[0179] Example 3: Production of PC-POS3 Polycarbonate-polyorganosiloxane (PC-POS3) was produced under the following production condition 2, and the resulting PC-POS3 was evaluated by the method described above. The results are shown in Table 1. (Production Condition 2) A 10-liter 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 diol monomers is taken as 100, and polyether-modified polyorganosiloxane PDMS-1 in the amounts shown in Table 1, which corresponds to the mass of the resulting PC-POS copolymer (theoretical value). These were then completely melted at a reactor temperature of 100°C, and the atmosphere inside the reactor was purged with nitrogen. 1.64 mL of 0.01 N sodium hydroxide was added to start polymerization, and the temperature inside the reactor was raised to 180°C over a period of about 50 to 100 minutes, and the pressure inside the reactor was raised to 2.66 x 10 ４ The pressure was reduced to 1.33×10 Pa, and these conditions were maintained until the amount of phenol distilled reached 0.2 L. Next, the temperature inside the reactor was raised to 200° C. over a period of about 150 minutes, and the pressure inside the reactor was reduced to 1.33×10 ３ The pressure was reduced to 1.33×10 Pa, and this condition was maintained until 1.8 L of phenol was distilled. Next, the temperature inside the reactor was raised to the final polymerization temperature shown in Table 1 over a period of about 60 minutes, and then the pressure inside the reactor was reduced to 1.33×10 ２ The pressure was reduced to 0.2 Pa or less, and 2 L or more of phenol was distilled off. The reaction was continued until the specified stirring torque was reached. Nitrogen was then introduced to raise the pressure to atmospheric pressure, and p-butyl toluenesulfonate was added as a polymerization deactivator, in the amounts shown in Table 1, if necessary. Furthermore, Irganox 1010 and Irgafos 168 were each added so that their contents in the resulting polymer were 1,000 ppm, and the mixture was stirred for 10 minutes or more. High-pressure nitrogen was then 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 polycarbonate-polyorganosiloxane copolymer PC-POS3. Note that the "mass (theoretical value) of the resulting PC-POS copolymer" in the above-mentioned Production Condition 2 is the same as that in Production Condition 1.

[0180] Examples 4 and 6: Production of PC-POS 4 and 6 Pellets containing PC-POS 4 and 6 were obtained in the same manner as in Example 3, 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 Table 1. The obtained pellets containing PC-POS 4 and 6 were evaluated by the methods described above. The results are shown in Table 1.

[0181]

[0182] As shown in Table 1, the molded articles PC-POS1 to PC-POS6, in which the content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer was 2.0% by mass or more and 25.0% by mass or less, and the content of the structural unit (A-1) represented by general formula (1) was 73.0% by mass or more, satisfied conditions (I) and (II). When the content of the structural unit represented by general formula (XX) and the weight-average molecular weight were similar, surprisingly, the impact resistance improved as the content of the structural unit (A-1) increased. Note that PC-POS6 is a polycarbonate-polyorganosiloxane copolymer that satisfies condition (C1), and PC-POS2 to PC-POS5 are polycarbonate-polyorganosiloxane copolymers that satisfy condition (D1). On the other hand, the molded article PC-POS31, which did not satisfy condition (C1), did not satisfy conditions (I) and (II).

[0183] Examples 7 to 10 and 12 to 15, and Comparative Examples 2 and 4: Production of PC-POS 7 to 10, 12 to 15, 32, and 34 Pellets containing PC-POS 7 to 10, 12 to 15, 32, and 34 were obtained in the same manner as in Example 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 Table 2. The obtained pellets containing PC-POS 7 to 10, 12 to 15, 32, and 34 were evaluated by the methods described above. The results are shown in Table 2.

[0184] Example 11 and Comparative Examples 3 and 5: Production of PC-POS 11 and 33, and PC35 Pellets containing PC-POS 11 and 33, and PC35 were obtained in the same manner as in Example 3, 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 Table 2. The obtained pellets containing PC-POS 11 and 33, and PC35 were evaluated by the methods described above. The results are shown in Table 2.

[0185]

[0186] As shown in Table 2, the molded articles of PC-POS 7 to 10, 13, and 14, in which the content of the structural unit represented by general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0% by mass or more and 25.0% by mass or less and the content of the structural unit (A-1) represented by general formula (1) is 73.0% by mass or more, satisfy conditions (I) and (II), and when the content of the structural unit represented by general formula (XX) and the weight-average molecular weight are similar, surprisingly, the impact resistance is improved as the content of structural unit (A-1) increases. Note that PC-POS 13 and 14 are polycarbonate-polyorganosiloxane copolymers that satisfy condition (C2), and PC-POS 8 and 7 to 10 are polycarbonate-polyorganosiloxane copolymers that satisfy condition (D2). The molded article of PC-POS15, which has a content of the structural unit (A-1) represented by general formula (1) of less than 73.0 and satisfies condition (C2), and the molded articles of PC-POS11 and 12, which satisfy condition (D2), also satisfied conditions (I) and (II). Furthermore, a comparison of PC-POS2 to 6 with PC-POS7 to 15 reveals that the polycarbonate-polyorganosiloxane copolymer containing the structural unit (A-32) as the structural unit (A-3) has better impact resistance and scratch resistance than the polycarbonate-polyorganosiloxane copolymer containing the structural unit (A-31) as the structural unit (A-3). On the other hand, the molded article of PC-POS34, which does not satisfy condition (C2), and the molded articles of PC-POS32 and 33, which do not satisfy condition (D2), did not satisfy condition (II). Furthermore, a molded article of PC35, which does not contain polyorganosiloxane blocks like the polycarbonate shown in the examples of JP 2009-144013 A and has structural units derived from isosorbide and 1,4-cyclohexanedimethanol, did not satisfy condition (I).It should be noted that the examples of JP 2009-144013 A state that the impact resistance of the polycarbonate decreases as the content of the structural unit derived from isosorbide increases. However, as is clear from a comparison of Examples 2 and 3, a comparison of Examples 4 and 5, a comparison of Examples 8 to 10, and a comparison of Examples 13 and 14, in which the content and weight average molecular weight of the structural unit represented by the general formula (XX) are similar, the polycarbonate-polyorganosiloxane copolymer of the present invention containing polyorganosiloxane blocks exhibits the surprising effect that the impact resistance is superior as the content of the structural unit (A-1) represented by the general formula (1) corresponding to the structural unit derived from isosorbide increases.

[0187] Examples 16 to 18 and Comparative Example 6: Production of PC-POS 16 to 18 and 36 Pellets containing PC-POS 16 to 18 and 36 were obtained in the same manner as in Example 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 Table 3. The obtained pellets containing PC-POS 16 to 18 and 36 were evaluated by the methods described above. The results are shown in Table 3.

[0188] Examples 19 and 20 and Comparative Examples 7 and 8: Production of PC-POS 19, 20, and 37, and PC38 Pellets containing PC-POS 19, 20, and 37, and PC38 were obtained in the same manner as in Example 2, 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 Table 3. The obtained pellets containing PC-POS 19, 20, and 37, and PC38 were evaluated by the methods described above. The results are shown in Table 3.

[0189]

[0190] As shown in Table 3, the content of the structural unit (A-1) represented by general formula (1) was less than 73.0, and the molded product of PC-POS17, which satisfied condition (D41), the molded products of PC-POS18 to PC-POS20, and the molded product of PC-POS16, which satisfied condition (D43), all satisfied conditions (I) and (II). On the other hand, the molded product of PC38, which did not contain a polyorganosiloxane block, did not satisfy condition (I). Furthermore, the molded product of PC-POS38, which did not satisfy any of conditions (C41) to (C43), did not satisfy condition (II). Furthermore, the molded product of PC-POS39, which did not satisfy any of conditions (D41) to (D43), did not satisfy condition (II).

[0191] Example 21: Production of PC-POS21 Pellets containing PC-POS21 were obtained in the same manner as in Example 3, 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 Table 4. The obtained pellets containing PC-POS21 were evaluated by the methods described above. The results are shown in Table 4.

[0192] Comparative Example 9: Production of PC-POS39 Pellets containing PC-POS39 were obtained in the same manner as in Example 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 Table 4. The obtained pellets containing PC-POS39 were evaluated by the methods described above. The results are shown in Table 4.

[0193]

[0194] As shown in Table 4, the molded product of PC-POS21, which had a content of the structural unit (A-1) represented by general formula (1) of less than 73.0 and satisfied condition (D3), satisfied conditions (I) and (II). On the other hand, the molded product of PC-POS39, which did not satisfy condition (D3), did not satisfy condition (I).

[0195] The polycarbonate-based resin composition containing the polycarbonate-polyorganosiloxane copolymer of the present invention has excellent impact resistance and scratch resistance in its molded articles, and therefore can be suitably used in impact-resistant and scratch-resistant applications. Examples of impact-resistant and scratch-resistant applications include structures whose outer surfaces are formed from the polycarbonate-based resin composition, and more specific examples include plastic windows, touch panels, interior goods, exterior goods, interior or exterior parts of vehicles, housings, electrical appliance parts, building materials, and office automation equipment parts. The polycarbonate-based resin composition of the present invention can be suitably used to produce the above-mentioned articles.

[0196] Molded articles made from the polycarbonate resin composition of the present invention can be suitably used for, for example, 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.

Claims

1. A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2), and satisfying the following conditions (I) and (II). 【Chemistry 1】 [In general formula (2), R １ and R ２ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C12 aryl group, or a C7-C22 alkylaryl group. a represents an integer from 2 to 500. Condition (I): The Charpy impact strength of a molded piece obtained by molding the polycarbonate-polyorganosiloxane copolymer, measuring 80 mm in length, 10 mm in width, and 3 mm in thickness, with a notch (r = 0.25 mm ± 0.05 mm) added by post-processing, measured in accordance with ISO 179-1:2010 at a measurement temperature of 23°C, is 15 kJ / m². ２ That's all. Condition (II): The scratch hardness (pencil method) of the molded polycarbonate-polyorganosiloxane copolymer, measured in accordance with JIS K 5600-5-4:1999, is HB or higher.

2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0% by mass or more and 25.0% by mass or less, and the content of the structural unit (A-1) represented by the general formula (1) is 73.0% by mass or more. 【Chemistry 2】 [In general formula (XX), R １ and R ２ R in the general formula (2) is １ and R ２ It expresses the same meaning as [this].

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1, further comprising at least one structural unit (A-3) selected from the structures represented by the following general formulas (3) and (4). 【Transformation 3】 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.]

4. The polycarbonate-polyorganosiloxane copolymer according to claim 3, wherein the structural unit (A-3) has at least one selected from the structures represented by the following general formulas (31) to (34). 【Chemistry 4】 [In general formula (31), n ​​represents an integer between 2 and 18.]

5. The structural unit (A-3) has a structural unit (A-32) represented by the general formula (32), and when x is the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer, The total content of the aforementioned structural units (A-1) and (A-32) in the polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer is 90.0 mol% or more. The polycarbonate-polyorganosiloxane copolymer according to claim 4, wherein the molar ratio (A-32 / A-1) of the structural unit (A-1) to the structural unit (A-32) and the content x of the structural unit represented by the following general formula (XX) satisfy the following conditions (C2) or (D2). Condition (C2): A-32 / A-1 is between 1.0 / 99.0 and 35.0 / 65.0, and x is between 1.0 mass% and less than 4.0 mass%. Condition (D2): A-32 / A-1 is between 1.0 / 99.0 and 27.0 / 73.0, and x is between 4.0 mass% and 10.0 mass%. 【Transformation 5】 [In general formula (XX), R １ and R ２ R in the general formula (2) is １ and R ２ It expresses the same meaning as [this].

6. When the structural unit (A-3) has a structural unit (A-31) represented by the general formula (31), and the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x, The polycarbonate-polyorganosiloxane copolymer according to claim 4, wherein the molar ratio (A-31 / A-1) of the structural unit (A-1) to the structural unit (A-31) and the content x of the structural unit represented by the following general formula (XX) satisfy the following conditions (C1) or (D1). Condition (C1): A-31 / A-1 is between 1.0 / 99.0 and 25.0 / 75.0, and x is between 1.0 mass% and less than 4.0 mass%. Condition (D1): A-31 / A-1 is between 1.0 / 99.0 and 30.0 / 70.0, and x is between 4.0% by mass and 10.0% by mass. 【Transformation 6】 [In general formula (XX), R １ and R ２ R in the general formula (2) is １ and R ２ It expresses the same meaning as [this].

7. The structural unit (A-3) has a structural unit (A-32) represented by the general formula (32) and a structural unit (A-33) represented by the general formula (33), and when x is the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer, The polycarbonate-polyorganosiloxane copolymer according to claim 4, wherein the molar ratio of the total of structural units (A-32) and (A-33) to the structural unit (A-1) ((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 structural unit represented by the general formula (XX) satisfy the following conditions (C41), (C42), (C43), (D41), (D42), or (D43). Condition (C41): A-32 / A-33 is between 60.0 / 40.0 and 99.0 / 1.0, (total of A-32 and A-33) / A-1 is between 1.0 / 99.0 and 39.0 / 61.0, and x is between 1.0 mass% and less than 4.0 mass%. Condition (C42): A-32 / A-33 is 40.0 / 60.0 or greater and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or greater and less than 31.0 / 69.0, and x is 1.0 mass% or greater and less than 4.0 mass%. Condition (C43): A-32 / A-33 is 1.0 / 99.0 or greater and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or greater and less than 46.0 / 54.0, and x is 1.0 mass% or greater and less than 4.0 mass%. Condition (D41): A-32 / A-33 is between 60.0 / 40.0 and 99.0 / 1.0, (total of A-32 and A-33) / A-1 is between 1.0 / 99.0 and 32.0 / 68.0, and x is between 4.0 mass% and 10.0 mass%. Condition (D42): A-32 / A-33 is 40.0 / 60.0 or greater and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or greater and 36.0 / 64.0 or less, and x is 4.0 mass% or greater and 10.0 mass% or less. Condition (D43): A-32 / A-33 is 1.0 / 99.0 or greater and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or greater and 41.0 / 59.0 or less, and x is 4.0 mass% or greater and 10.0 mass% or less. 【Transformation 7】 [In general formula (XX), R １ and R ２ R in the general formula (2) is １ and R ２ It expresses the same meaning as [this].

8. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 7, wherein a is an integer between 2 and 300.

9. The aforementioned R １ and R ２ A polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 7, wherein is a methyl group.

10. A polycarbonate-based resin composition comprising a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 7.

11. A molded article comprising the polycarbonate resin composition described in claim 10.

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