Polycarbonate-based resin composition

Abstract

The present invention provides a polycarbonate-based resin composition which contains a polycarbonate-polyorganosiloxane copolymer (A), wherein: the polycarbonate-polyorganosiloxane copolymer (A) contains a polycarbonate block and a polyorganosiloxane block that comprises a structural unit (A-1) represented by general formula (1); and the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms is less than 8 mass ppm. The polycarbonate-based resin composition has excellent defoaming performance during production and excellent transparency. (In general formula (1), R1 and R2 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.)

Description

Polycarbonate resin composition

[0001] The present invention relates to a polycarbonate resin composition.

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

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

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

[0005] According to the studies of the present inventors, for example, the polycarbonate composition described in Patent Document 1 is prone to foaming during production, and it is necessary to adjust the stirring speed of the reaction solution in consideration of this. It has become clear that this makes the operation complicated and causes problems of reduced production efficiency. Furthermore, even if a silicone-based antifoaming agent is added in the hope of improving antifoaming performance during production, depending on the type of agent, problems can arise in the transparency of the resulting polycarbonate resin composition.

[0006] The present invention has been made in view of the above circumstances, and provides a polycarbonate resin composition that has excellent antifoaming performance during production and also has excellent transparency.

[0007] The present inventors have found that a polycarbonate resin composition having a total content of specified sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms exhibits excellent defoaming performance during production and also has excellent transparency.

[0008] That is, according to the present invention, there are provided the following polycarbonate resin composition and a method for producing the same.

[0009] [1] A polycarbonate-based resin composition comprising a polycarbonate-polyorganosiloxane copolymer (A), wherein the polycarbonate-polyorganosiloxane copolymer (A) comprises a polycarbonate block and a polyorganosiloxane block containing a structural unit (A-1) represented by the following general formula (1), and the polycarbonate-based resin composition has a total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms of less than 8 ppm by mass: [In general formula (1), R １ and R ２ and each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.] [2] The polycarbonate resin composition according to the above item [1], wherein the polycarbonate block contains at least one structural unit (A-2) represented by the following general formula (2-1) or (2-2): [In general formulas (2-1) and (2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a divalent heterocyclic group having 3 to 40 carbon atoms.] [3] The polycarbonate resin composition according to the above [2], wherein the structural unit (A-2) has at least one selected from structural units (A-21) to (A-25) represented by the following general formulas (21) to (25): [In the general formula (22), n represents an integer of 2 to 18.] [4] R in the general formula (1)１ and R ２ is a methyl group. [5] The polycarbonate-based resin composition according to any one of the above [1] to [4], wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms is 2 ppm by mass or less. [6] A method for producing a polycarbonate-based resin composition, comprising: using raw materials containing a diol monomer (a), a polyorganosiloxane (b), a carbonate ester compound, and a catalyst, and wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms is less than 4 ppm by mass, to obtain a polycarbonate-polyorganosiloxane copolymer (A) containing polycarbonate blocks and polyorganosiloxane blocks containing a structural unit (A-1) represented by the following general formula (1): [In general formula (1), R １ and R ２ and each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.] [7] The method for producing a polycarbonate resin composition according to the above [6], wherein the diol monomer (a) contains at least one diol monomer (a2) represented by the following general formula (a2-1) or (a2-2): [In general formulas (a2-1) and (a2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a divalent heterocyclic group having 3 to 40 carbon atoms.] [8] The method for producing a polycarbonate-based resin composition according to the above [6] or [7], wherein the ratio of the number of moles of the carbonate ester compound to the number of moles of the diol monomer (a) is 0.90 to 1.20. [9] The method for producing a polycarbonate-based resin composition according to any one of the above [6] to [8], which is carried out by melt polymerization.

[10] The method for producing a polycarbonate-based resin composition according to any one of the above [6] to [9], wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms in the raw materials is 2 ppm by mass or less.

[0010] According to the present invention, it is possible to provide a polycarbonate resin composition that has excellent antifoaming performance during production and also has excellent transparency.

[0011] The polycarbonate resin composition and its manufacturing method according to the present invention are described in detail below. In this specification, any preferred definition may be adopted arbitrarily, 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 may be selected. When compounds and chemical structures described herein have multiple stereoisomers and structural isomers, all stereoisomers and structural isomers are included, unless otherwise specified.

[0012] 1. Polycarbonate Resin Composition The polycarbonate resin composition according to this embodiment contains a polycarbonate-polyorganosiloxane copolymer (A).

[0013] The polycarbonate-based resin composition according to this embodiment may contain one or more of the polycarbonate-polyorganosiloxane copolymers (A), or may contain a polycarbonate-based resin other than the polycarbonate-polyorganosiloxane copolymer (A) (hereinafter, sometimes referred to as "polycarbonate-based resin (P)"), or may contain components other than these. From the viewpoint of improving the impact resistance of molded articles, the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more. The upper limit of the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate-based resin composition is not particularly limited, but from the viewpoint of obtaining a polycarbonate-based resin composition having the desired properties, it is, for example, less than 100% by mass.

[0014] The polycarbonate-based resin composition according to this embodiment exhibits excellent defoaming performance during production when the total content of sodium, magnesium, potassium, calcium, and cesium atoms is less than 8 ppm by mass. This is because the presence of any of sodium, magnesium, potassium, calcium, and cesium atoms during the synthesis of the polycarbonate-polyorganosiloxane copolymer (A) excessively accelerates the reaction, causing foaming in the reaction system. The total content of sodium, magnesium, potassium, calcium, and cesium atoms in the polycarbonate-based resin composition is preferably 5 ppm by mass or less, more preferably 4 ppm by mass or less, even more preferably 3 ppm by mass or less, and most preferably less than 1 ppm by mass. The total content can be calculated as the sum of the measurement results for each atom; however, if the measurement result for the content of a certain atom is below the measurement limit, the content of that atom is treated as 0 and the total is calculated. Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate resin composition according to this embodiment also preferably has a sodium atom, magnesium atom, potassium atom, calcium atom, and cesium atom content of 5 ppm by mass or less, more preferably 4 ppm by mass or less, even more preferably 3 ppm by mass or less, and most preferably less than 1 ppm by mass.

[0015] Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate-based resin composition according to this embodiment also has a total content of aluminum atoms, barium atoms, cadmium atoms, cobalt atoms, copper atoms, manganese atoms, lead atoms, vanadium atoms, and zinc atoms that is preferably less than 7 ppm by mass, more preferably 5 ppm by mass or less, even more preferably 3 ppm by mass or less, and most preferably less than 1 ppm by mass. The total content can be calculated as the sum of the measurement results for each atom, but if the measurement result for the content of a certain atom is below the measurement limit, the content of that atom is treated as 0 and the total is added up. Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate-based resin composition according to this embodiment also has a total content of aluminum atoms, barium atoms, cadmium atoms, cobalt atoms, copper atoms, manganese atoms, lead atoms, vanadium atoms, and zinc atoms that is preferably less than 5 ppm by mass, more preferably 4 ppm by mass or less, even more preferably 3 ppm by mass or less, and most preferably less than 1 ppm by mass.

[0016] [Polycarbonate-Polyorganosiloxane Copolymer (A)] The polycarbonate-polyorganosiloxane copolymer (A) contains a polyorganosiloxane block containing a structural unit (A-1) represented by the following general formula (1).

[0017]

[0018] In general formula (1), 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.

[0019] <Polycarbonate Block> The polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer (A) preferably contains at least one structural unit (A-2) represented by the following general formula (2-1) or (2-2).

[0020]

[0021] In the general formulas (2-1) and (2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a divalent heterocyclic group having 3 to 40 carbon atoms. In this specification, the various "divalent" hydrocarbon groups are substituents formed by removing two hydrogen atoms from a hydrocarbon.

[0022] From the viewpoint of reducing the melt flow rate of the polycarbonate-polyorganosiloxane copolymer (A) and improving the tensile modulus, tensile strength (yield), and glass transition temperature, it is preferable that L １ and L ２ 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 or a divalent saturated heterocyclic 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 or a divalent saturated heterocyclic group having 3 to 8 carbon atoms, and particularly from the viewpoint of availability of raw materials, it is 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 6 carbon atoms or a divalent saturated heterocyclic group having 3 to 8 carbon atoms. １ and L ２ However, the reason why the inclusion of at least one carbon atom selected from tertiary and quaternary carbon atoms reduces the melt flow rate of the polycarbonate-polyorganosiloxane copolymer (A) and improves the tensile modulus, tensile strength (yield), and glass transition temperature is not clear, but it is thought that this is because tertiary and quaternary carbon atoms have low mobility, and structures containing these carbon atoms tend to be rigid. １ and L２ 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 (A) and why the tensile modulus, tensile strength (yield), and glass transition temperature are improved 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.

[0023] L in the above general formula (2-1) １ 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 the formula (2-1) may be substituted with a substituent, and may contain at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms in the carbon chain of the hydrocarbon group. １ Examples 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.

[0024] L in the above general formula (2-1) １ The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by 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. １Examples 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.

[0025] L in the above general formula (2-1) １ The 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.

[0026]

[0027] In general formula (3a), R １０１ is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0028] L in the above general formula (2-1) １ 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.

[0029]

[0030] L in the above general formula (2-1) １ 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.

[0031]

[0032] L in the above general formula (2-1) １ 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.

[0033]

[0034] L in the above general formula (2-1) １ 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.

[0035]

[0036] L in the above general formula (2-1) １ The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by 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. １ 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:

[0037]

[0038] 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.

[0039] In the above general formula (3f), R１０２ 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.

[0040] 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.

[0041] 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.

[0042] L in the above general formula (2-1) １ The divalent heterocyclic group having 3 to 40 carbon atoms represented by the formula (I) 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. Examples of the core atom of the heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom.

[0043] L in the above general formula (2-2) ２ The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by １ 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.

[0044] From the viewpoint of obtaining a polycarbonate resin composition having excellent impact resistance, the structural unit (A-2) preferably contains at least one selected from structural units (A-21) to (A-25) represented by the following general formulas (21) to (25), more preferably contains at least one selected from structural units (A-21) to (A-24), and even more preferably consists of at least one selected from structural units (A-21) to (A-24).

[0045]

[0046] In the general formula (22), n represents an integer of 2 to 18, preferably 3 to 10, and more preferably 4 to 8.

[0047] When the structural unit (A-2) contains at least one selected from the structural units (A-21) to (A-25), the total content of the structural units (A-21) to (A-25) in the structural unit (A-2) 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] The polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer (A) more preferably contains a structural unit (A-21) represented by general formula (21) and at least one selected from the structural units (A-22) to (A-25) represented by general formulas (22) to (25), and even more preferably contains a structural unit (A-21) represented by general formula (21) and a structural unit (A-23) represented by general formula (23).

[0049] From the viewpoint of obtaining a polycarbonate resin composition having excellent impact resistance, the content of the structural unit (A-21) in the polycarbonate block is preferably 40.0 mol% or more, more preferably 50.0 mol% or more, even more preferably 60.0 mol% or more, and preferably 100.0 mol% or less, more preferably 98.0 mol% or less, and even more preferably 96.0 mol% or less. When the polycarbonate block contains the structural units (A-22) to (A-25), from the viewpoint of obtaining a polycarbonate resin composition having even more excellent impact resistance, the total content of the structural units (A-22) to (A-25) in the polycarbonate block is preferably 1.0 mol% or more, more preferably 2.0 mol% or more, even more preferably 4.0 mol% or more, and preferably 60.0 mol% or less, more preferably 50.0 mol% or less, and even more preferably 40.0 mol% or less. The content of each structural unit in the polycarbonate block is calculated by nuclear magnetic resonance (NMR) measurement.

[0050] From the viewpoint of obtaining a polycarbonate-based resin composition having excellent impact resistance, the content of the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 75.0% by mass or more, more preferably 80.0% by mass or more, even more preferably 85.0% by mass or more, and preferably 100.0% by mass or less, more preferably 95.0% by mass or less, even more preferably 90.0% by mass or less. From the viewpoint of obtaining a polycarbonate-based resin composition having excellent impact resistance and a molded article thereof, the content of the structural unit (A-21) in the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 73.0% by mass or more, more preferably 80.0% by mass or more, even more preferably 85.0% by mass or more, and preferably 100.0% by mass or less, more preferably 97.0% by mass or less, even more preferably 95.0% by mass or less. The content of the polycarbonate block and the structural units (A-21) to (A-25) in the polycarbonate-polyorganosiloxane copolymer (A) is calculated by nuclear magnetic resonance (NMR) measurement.

[0051] <Polyorganosiloxane Block> The polyorganosiloxane block contained in the polycarbonate-polyorganosiloxane copolymer (A) contains at least a repeating structure (A-1) of a structure represented by the following general formula (1): The polyorganosiloxane block is a structural unit containing at least one structure represented by the following general formula (1) that is present between the two most adjacent polycarbonate bonds on the main chain of the polycarbonate-polyorganosiloxane copolymer (A), and is preferably a repeating structure of the structure represented by general formula (1) represented by the following general formula (1-1).

[0052]

[0053] In general formula (1), 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.

[0054]

[0055] In general formula (1-1), R １ and R ２ represents R in the general formula (1). １ and R ２ a is the number of repetitions of the structure represented by general formula (1), and a is an integer of 2 to 500.

[0056] In general formula (1-1), R １ and R ２ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １ and R ２ Examples of the alkyl group having 1 to 10 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. １ and R ２ Examples of the alkoxy group having 1 to 10 carbon atoms represented by the formula (I) include an alkoxy group in which the alkyl group moiety is the same as the alkyl group described above. １ and R ２ Examples of the aryl group having 6 to 12 carbon atoms represented by R include a phenyl group and a naphthyl group. １ and R ２ Examples of the alkylaryl group having 7 to 22 carbon atoms represented by the formula (I) include alkylaryl groups in which the alkyl group moiety is the same as the alkyl group described above and the aryl group moiety is the same as the aryl group described above. １ and R ２ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group.

[0057] The polyorganosiloxane block preferably has a structure represented by the following general formula (1-2).

[0058]

[0059] In general formula (1-2), R １ , R ２ and a is R in the general formula (1-1). １ , R ２ , and a have the same meaning. ３ and R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. ６ represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of a plurality of R ８ may be the same or different and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. a represents an integer of 2 to 500, and b represents an integer of 2 to 200. u and z represent 0 or 1.

[0060] The polyorganosiloxane block preferably has a structure represented by the following general formula (1-3).

[0061]

[0062] In general formula (1-3), R １ ~R ４ , R ６ , R ８ , a, b, u, and z are R in the general formula (1-1) and the general formula (1-2). 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 ７ represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents the same meaning as above. b1 represents an integer of 2 to 200. u1 and z1 represent 0 or 1.

[0063] The polyorganosiloxane block may have at least one of the structures represented by the following general formulas (1-4) to (1-7).

[0064]

[0065] In general formulas (1-4) to (1-7), R １ ~R ８ , a, b, b1, u, u1, z, and z1 are R in the general formula (1-1), the general formula (1-2), and the general formula (1-3). 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.

[0066] In general formulas (1-4) to (1-7), 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 R１ 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 ４ The aryl group having 6 to 12 carbon atoms represented by R １ and R ２ The aryl group may be the same as the aryl group shown in R ３ and R ４ The alkylaryl group having 7 to 22 carbon atoms represented by R １ and R ２ The alkylaryl group may be the same as the alkylaryl group shown in R ３ and R ４ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and R ３ and R ４ More preferably, all of are methyl groups.

[0067] R ５ , R ６ , R ７ , or R ８ Examples of the arylene group having 6 to 20 carbon atoms represented by the formula (R) include a phenylene group and a naphthylene group. ５ , R ６ , R ７ , or R ８ Examples of the alkylene group having 1 to 10 carbon atoms represented by the formula (R) include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and various butylene groups. The various butylene groups are preferably tetramethylene groups. ５ , R ６ , R ７ , or R ８Examples of the alkylarylene group having 7 to 22 carbon atoms and represented by the formula (I) include alkylarylene groups having the same alkyl group moiety as the alkylene group and the same arylene group moiety as the arylene group. However, these groups do not contain -O-, -COO-, -CO-, -S-, -NH-, or NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. １１１ Examples of the alkyl group having 1 to 10 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. １１１ The aryl group having 6 to 10 carbon atoms represented by the formula (I) includes a phenyl group and a naphthyl group.

[0068] 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.

[0069] 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.

[0070] In general formulas (1-1) to (1-7), a represents the number of repeating structural units represented by general formula (1) plus 1, i.e., the number of repeating Si atoms, also referred to as the chain length. a is preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, even 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 even more preferably 50 or less. In general formulas (1-1) to (1-7), a is preferably an integer of 2 to 300, more preferably 10 to 95, even more preferably 15 to 70, and even more preferably 20 to 50. The average value of a in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, and is preferably 300 or less, more preferably 95 or less, even more preferably 70 or less, and even more preferably 50 or less. The average value of a in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2 to 300, more preferably 10 to 95, even more preferably 15 to 70, still more preferably 15 to 50, and even more preferably 20 to 50. The average value of a in the polycarbonate-polyorganosiloxane copolymer (A) is calculated by nuclear magnetic resonance (NMR) measurement.

[0071] In general formulas (1-2) to (1-7), 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 (1-2) to (1-7), 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 (A) 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 (A) are preferably 2 to 200, more preferably 5 to 100, even more preferably 8 to 50, even more preferably 10 to 30, even more preferably 12 to 25, and even more preferably 12 to 20. The average value b2 in the polycarbonate-polyorganosiloxane copolymer (A) is calculated by nuclear magnetic resonance (NMR) measurement.

[0072] In general formula (1-2), u is preferably 1. In general formulas (1-3) to (1-7), u and u1 are each preferably 1, and it is more preferable that u and u1 are both 1. In general formula (1-2), z is preferably 1. In general formulas (1-3) to (1-7), z and z1 are each preferably 1, and it is more preferable that z and z1 are both 1.

[0073] In the general formula (1-2), 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.

[0074] In general formulas (1-4) to (1-7), 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).

[0075]

[0076] The polyorganosiloxane block preferably does not contain a branched structure in order to obtain a polycarbonate resin composition having excellent impact resistance.

[0077] From the viewpoint of obtaining a polycarbonate-based resin composition having excellent impact resistance, the content of the structural unit represented by general formula (1) in the polycarbonate-polyorganosiloxane copolymer (A) is 2.0% by mass or more, preferably 3.0% by mass or more, more preferably 4.0% by mass or more, and 25.0% by mass or less, preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 10.0% by mass or less. The method for measuring the content of the structural unit represented by general formula (1) in the polycarbonate-polyorganosiloxane copolymer (A) is not particularly limited, and examples thereof include nuclear magnetic resonance (NMR) analysis.

[0078] (Terminal Structure of Polycarbonate-Polyorganosiloxane Copolymer (A)) In one embodiment, the polycarbonate-polyorganosiloxane copolymer (A) has the following terminal structure: -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. ＴThe content of the terminal structure represented by the formula (I) is preferably 0.01% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, and is preferably 3.0% by mass or less, more preferably 2.5% by mass or less, even more preferably 2.0% by mass or less. Ｔ The content of the terminal structure represented by the formula (I) is preferably 0.01 to 3.0% by mass, more preferably 0.2 to 2.5% by mass, and even more preferably 0.5 to 2.0% by mass. Ｔ The more terminal structures represented by the formula -OR, the fewer terminal hydroxyl groups derived from the diol monomer, and the higher the heat resistance and glass transition temperature of the resin. Ｔ The content of the terminal structure represented by the formula (I) is calculated by nuclear magnetic resonance (NMR) measurement.

[0079] From the viewpoint of obtaining a polycarbonate-based resin composition having excellent impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, even more preferably 15,000 or less. The number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 to 30,000, more preferably 8,000 to 25,000, even more preferably 8,000 to 20,000, even more preferably 8,000 to 15,000. In particular, from the viewpoint of obtaining a polycarbonate resin composition having superior impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 8,000 or more, more preferably 9,000 or more, and even more preferably 10,000 or more.

[0080] The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 20,000 or more, more preferably 23,000 or more, even more preferably 25,000 or more, and is preferably 60,000 or less, more preferably 50,000 or less, even more preferably 45,000 or less, even more preferably 43,000 or less. The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 20,000 to 60,000, more preferably 23,000 to 50,000, even more preferably 25,000 to 45,000, even more preferably 25,000 to 43,000. In particular, from the viewpoint of obtaining a polycarbonate resin composition having superior impact resistance, the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 25,000 or more, more preferably 26,000 or more, and even more preferably 27,000 or more.

[0081] The viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 or more, more preferably 7,000 or more, even more preferably 8,000 or more, and particularly preferably 9,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, even more preferably 20,000 or less, and particularly preferably 20,000 or less. The viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 to 30,000, more preferably 7,000 to 25,000, even more preferably 8,000 to 20,000, and particularly preferably 9,000 to 20,000. The preferred range of the viscosity average molecular weight (Mv) of the polycarbonate resin composition is the same as that described above for the viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A).

[0082] The reason why impact resistance is improved by adjusting the number-average molecular weight, weight-average molecular weight, and viscosity-average molecular weight to fall within the above ranges is unclear, but is presumed to be as follows: When the number-average molecular weight, weight-average molecular weight, and viscosity-average molecular weight are at or above a certain level, the entanglement and interaction between polymer chains is strengthened, which is thought to improve impact resistance.

[0083] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 1.8 or more, more preferably 2.2 or more, even more preferably 2.5 or more, and is preferably 3.2 or less, more preferably 3.0 or less, even more preferably 2.9 or less. The ratio (Mw / Mn) is preferably 1.8 to 3.2, more preferably 2.2 to 3.0, even more preferably 2.5 to 2.9.

[0084] <Polycarbonate-based resin (P)> Examples of the polycarbonate-based resin (P) include polycarbonate-based resins that do not contain the structural unit (A-1) represented by the general formula (1) above, but contain at least one structural unit (A-2) selected from the structures represented by the general formulas (2-1) and (2-2) above. The structural unit (A-1) and structural structure (A-2) contained in the polycarbonate-based resin (P) include the same as the structural unit (A-1) and structural unit (A-2) contained in the polycarbonate-polyorganosiloxane copolymer (A). Preferred embodiments are also the same.

[0085] The polycarbonate resin composition of the present embodiment may further contain other components such as a light stabilizer, an elastomer, a colorant, glittering particles, an inorganic filler, a flame retardant, an acrylic resin, a hydrolysis stabilizer, an antioxidant, and resins other than those mentioned above.

[0086] 2. Method for Producing Polycarbonate Resin Composition The polycarbonate resin composition described above can be produced using raw materials containing a diol monomer (a), a polyorganosiloxane (b), a carbonate ester compound, and a catalyst.

[0087] The method for producing a polycarbonate-based resin composition according to this embodiment uses raw materials having a total content of sodium, magnesium, potassium, calcium, and cesium atoms of less than 4 ppm by mass, thereby achieving excellent defoaming performance during production. This is because the presence of calcium atoms in the process of synthesizing the polycarbonate-polyorganosiloxane copolymer (A) excessively promotes the reaction, causing foaming in the reaction system. The total content of sodium, magnesium, potassium, calcium, and cesium atoms in the raw materials is preferably 3 ppm by mass or less, more preferably 2 ppm by mass or less, and even more preferably less than 1 ppm by mass. The total content can be calculated as the sum of the measurement results for each atom; however, if the measurement result for the content of a certain atom is below the measurement limit, the content of that atom is treated as 0 and the total is calculated. Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate resin composition according to this embodiment also has a content of each of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms in the raw materials that is preferably less than 4 ppm by mass, more preferably 3 ppm by mass or less, even more preferably 2 ppm by mass or less, and most preferably less than 1 ppm by mass.

[0088] Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate resin composition according to this embodiment also has a total content of aluminum atoms, barium atoms, cadmium atoms, cobalt atoms, copper atoms, manganese atoms, lead atoms, vanadium atoms, and zinc atoms in the raw materials of preferably less than 4 ppm by mass, more preferably 3 ppm by mass or less, even more preferably 2 ppm by mass or less, and most preferably less than 1 ppm by mass. The total content can be calculated as the sum of the measurement results for each atom, but when the measurement result for the content of a certain atom is below the measurement limit, the content of that atom is treated as 0 and the total is calculated. Furthermore, from the viewpoint of antifoaming properties during production, the polycarbonate resin composition according to this embodiment also has a content of each of aluminum atoms, barium atoms, cadmium atoms, cobalt atoms, copper atoms, manganese atoms, lead atoms, vanadium atoms, and zinc atoms in the raw materials that is preferably less than 4 ppm by mass, more preferably 3 ppm by mass or less, even more preferably 2 ppm by mass or less, and most preferably less than 1 ppm by mass.

[0089] <<Diol Monomer (a)>> The diol monomer (a) preferably contains at least one diol monomer (a2) represented by the following general formula (a2-1) or (a2-2).

[0090]

[0091] [In general formulas (a2-1) and (a2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.]

[0092] L in general formulae (a2-1) and (a2-2) １ and L ２ The details of L in the above general formulas (2-1) and (2-2) are as follows: １ and L ２ The same applies to each of the above, and the preferred ones are also the same.

[0093] The diol monomer (a2) preferably contains at least one of the following general formulae (a21) to (a25).

[0094]

[0095] [In general formula (a22), n represents an integer of 2 to 18.]

[0096] The details of n in the general formula (a22) are the same as those of n in the above-mentioned general formula (22), and the preferred examples are also the same.

[0097] The diol monomer (a2) represented by the above general formula (a21) preferably contains a diol represented by the following general formula (a21-1), and more preferably consists of only a diol represented by the following general formula (a21-1).

[0098]

[0099] <<Polyorganosiloxane>> The polyorganosiloxane preferably contains a modified silicone (b1). The hydroxyl value of the modified silicone (b1) is preferably 10 to 100 mgKOH / g, more preferably 15 to 80 mgKOH / g, and particularly preferably 20 to 70 mgKOH / g. In this specification, the hydroxyl value refers to the value measured in accordance with JIS K0070:1192.

[0100] The modified silicone (b1) preferably has two or more hydroxyl groups in one molecule, and more preferably is represented by the following general formula (b1-1):

[0101] [In general formula (b1-1), R ３３ ~R ４０ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a group represented by the following general formula (ii), and a plurality of R ３３ and R ３４ may be the same or different from each other. ３３ ~R ４０At least two of the groups are groups represented by the following general formula (ii), and c is an integer of 5 to 200.

[0102]

[0103] [In general formula (ii), L ５ and L ６ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and d is an integer of 0 to 20.

[0104] In general formula (b1-1), R ３３ ~R ４０ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ３３ ~R ４０ Examples of the alkyl group having 1 to 6 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. ３３ ~R ４０ Examples of the alkoxy group having 1 to 6 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. ３３ ~R ４０ Examples of the aryl group having 6 to 12 carbon atoms represented by the formula (b1-1) include a phenyl group and a naphthyl group. c in general formula (b1-1) is preferably 7 to 100, more preferably 10 to 60, and even more preferably 13 to 35.

[0105] In general formula (ii), L ５ and L ６ Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by the formula (ii) include an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, and an alkylarylene group having 7 to 20 carbon atoms, and are preferably alkylene groups having 2 to 6 carbon atoms, and more preferably alkylene groups having 2 to 4 carbon atoms. d in general formula (ii) is preferably 2 to 100, more preferably 5 to 50, and even more preferably 8 to 25.

[0106] There are no particular restrictions on the method for producing the modified silicone (b1). 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 an α,ω-dihydrogenorganopentasiloxane, and then, in the presence of a hydrosilylation catalyst, the α,ω-dihydrogenorganopentasiloxane is subjected to an addition reaction with a monomer, oligomer, or polymer (for example, carbinol, 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 a monomer, 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 modified at one end 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 at one end with an allyl group can be used. Among the oligomers modified at one end with an allyl group, polyethylene glycol modified at one end with an allyl group 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.

[0107] The amount of polyorganosiloxane used in the method for producing a polycarbonate-based resin composition of this embodiment is preferably 1.0 to 45 mass %, more preferably 2.0 to 30 mass %, and even more preferably 3.0 to 11.0 mass %, based on the total amount of the raw materials.

[0108] Polycarbonate-based resin compositions 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-based resin composition can be produced by reacting a diol monomer (a), a carbinol-modified silicone (b), a carbonate ester compound described below, and an optionally used modified silicone (c), etc., by melt polymerization, preferably in the presence of a basic catalyst. Here, a terminal terminator may be further added to carry out the polymerization reaction. Since melt polymerization does not require a solvent such as methylene chloride required in interfacial polymerization, it is environmentally and economically advantageous. In addition, since it does not use the highly toxic phosgene used in interfacial polymerization, it is also advantageous in terms of production. Therefore, polycarbonate-based resin compositions are preferably produced by melt polymerization.

[0109] (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).

[0110]

[0111] 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.

[0112] 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).

[0113]

[0114] 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.

[0115] 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).

[0116]

[0117] 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.

[0118] Examples of diaryl carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, and bisphenol A bisphenyl carbonate. Examples of dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of alkyl aryl carbonate compounds include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. A preferred carbonate ester compound is diphenyl carbonate. One or more carbonate ester compounds can be used to produce the polycarbonate-polyorganosiloxane copolymer (A).

[0119] (Terminator) When producing a polycarbonate resin composition, 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.

[0120] (Branching Agent) A branching agent can also be used when producing a polycarbonate resin composition. 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).

[0121] In the raw materials used in the method for producing a polycarbonate resin composition of this embodiment, the total content of the diol monomer (a), the carbinol-modified silicone (b), and the carbonate ester is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0122] In the method for producing a polycarbonate-based resin composition according to this embodiment, specifically, a polycarbonate-based resin composition can be produced by melt polymerization, for example, by the following procedure. Raw materials containing a diol monomer (a), a carbinol-modified silicone (b), a carbonate ester compound, and an optional modified silicone (c) are subjected to a transesterification reaction. The amount of the carbonate ester compound relative to the total amount of the diol monomer (a) and the optional modified silicone (c) is preferably 0.9 to 1.2 times by mole, and more preferably 0.95 to 1.05 times by mole. Under polymerization conditions, if the diol monomer (a) and the optional modified silicone (c) are more volatile than the carbonate ester compound, the molar ratio of the carbonate ester compound relative to the total amount of the diol monomer (a) and the optional modified silicone (c) is preferably 1 or less. Under polymerization conditions, if the diol monomer (a) and the optional modified silicone (c) are less volatile than the carbonate ester compound, the molar ratio of the carbonate ester compound relative to the total amount of the diol monomer (a) and the optional modified silicone (c) is preferably 1 or more. By adjusting the ratio of the amount of carbonate ester compound to the total amount of diol monomer (a) and the optionally used modified silicone (c) within the above range, the number average molecular weight and weight average molecular weight of the resulting polycarbonate-polyorganosiloxane copolymer (A) can be increased. When a terminal terminator is used in the above transesterification reaction, it is preferable that the amount of terminal terminator is within the range of 0.05 to 10 mol % relative to the total amount of diol monomer (a) and the optionally used modified silicone (c), since this sufficiently caps the hydroxyl terminals of the resulting polycarbonate-polyorganosiloxane copolymer (A), 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 (a) and the optionally used modified silicone (c) 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, with the remainder added as the reaction progresses.It is preferred that the diol monomer (a), the carbonate ester compound, and the optionally used modified silicone (c) are simultaneously charged with an antioxidant into a reactor, and the transesterification reaction is carried out in the presence of the antioxidant.

[0123] The reaction temperature for carrying out the transesterification reaction is not particularly limited, and may be, for example, in the range of 100 to 260 ° C, preferably in the range of 100 to 250 ° C. Furthermore, a method in which the temperature is gradually increased from 150 ° C to 250 ° C as the reaction progresses is preferred, and a method in which the temperature is gradually increased from 170 ° C to 250 ° C is more preferred. If the temperature of the transesterification reaction is 100 ° C or higher, the reaction rate is sufficiently fast, while if it is 250 ° C or lower, many side reactions do not occur, and problems such as discoloration of the resulting polycarbonate-polyorganosiloxane copolymer (A) are unlikely to occur. The temperature in the final reactor is preferably 210 ° C or higher, more preferably 225 ° C or higher.

[0124] 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.

[0125] 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 composition. 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.

[0126] As the catalyst, it is preferable to use a basic catalyst, and it is particularly preferable to use a basic catalyst in a melt polymerization method. 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. As the basic catalyst, at least one selected from the group consisting of inorganic salts (excluding organic acid salts and silicates), oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing an aryl group is preferably used, with alkali metal hydroxides being more preferred. The basic catalysts can be used alone or in combination of two or more.

[0127] 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.

[0128] 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.

[0129] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0130] 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.

[0131] The amount of the basic catalyst used is preferably 1 × 10 relative to 1 mole of the total of the diol monomer (a) and the polyorganosiloxane (b). －９ ~1 x 10 －２ mole, more preferably 1 x 10 －９ ~1 x 10 －５ mole, more preferably 1 x 10 －９ ~1 x 10 －６ You can choose from a range of moles.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] 3. Molded Articles The molded article according to this embodiment 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 a molded article by injection molding or injection compression molding using the obtained pellets.

[0136] The thickness of the molded article can be set arbitrarily depending on the application, and when transparency of the molded article is particularly required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. If the thickness of the molded article is 0.2 mm or more, warping does not occur and good mechanical strength is obtained.

[0137] The molded article may be coated with a hard coat film, an anti-fogging film, an antistatic film, or an anti-reflection film as needed, or may be coated with a composite of two or more types of film. Among these, a hard coat film is preferred because it has good light resistance and can prevent wear of the molded article surface over time. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic hard coat agents can be used.

[0138] The polycarbonate-based resin composition according to the present embodiment can be suitably used for impact-resistant applications because the molded articles thereof have excellent impact resistance. Examples of impact-resistant applications include structures whose outer surfaces are formed from the polycarbonate-based resin composition, and more specifically, plastic windows, touch panels, interior and exterior products, vehicle interior and exterior parts, housings, electrical appliance parts, building materials, and office automation equipment parts. The polycarbonate-based resin composition according to the present invention can be suitably used for producing the above-mentioned articles.

[0139] Molded articles made from the polycarbonate resin composition according to this embodiment 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 vehicles 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 for greenhouses and the like, and 7) furniture parts such as lighting covers, blinds, and interior fixtures. The molded articles according to this embodiment may also be molded bodies that have high flexibility while maintaining a certain level of mechanical strength, and can be used, for example, as lighting covers without using a packing member, or as light guides with complex shapes. Furthermore, even in the case of an optical member having a void structure with an internal undercut draft angle, it can be integrally molded without performing an internal cutting process, and therefore can also be suitably used for a collimator lens.In addition, in the home appliance field, we have applications such as substrates, light guide plates, and housings for flexible displays, as well as water-repellent and oil-repellent films, optical adhesives, switch covers, heat sealants, waterproofing materials, sealants, connectors, adapters, and smartphone covers; in the optical field, we have applications such as lenses, eyeglass and sunglasses parts, and optical fiber parts; in the automotive field, we have applications such as cushioning materials for on-board batteries, wiper blades, convex mirrors, side mirrors, rearview mirrors, lamp covers, bumpers, windows, glass interlayers, exterior materials, interior materials, sound-absorbing materials, steering wheel covers, and sensor covers; and in the everyday field, we have applications such as watch parts, stationery, and cosmetic containers. The silicone rubber can be suitably used in a wide range of applications, including containers, aquariums for raising aquatic organisms, shoe soles, cups, nail art, toys, artificial bait, suction cups, cooking utensils such as steamers, clothing, silicone wipes, remote control covers, umbrellas, metal container linings, etc.; in the field of building materials, building material covers, doors, windows, glass interlayers, tents, mirrors, show window cases, greenhouses, etc.; in the medical field, medical device housings, infusion bags, infusion tubes, syringes, baby bottles, masks, face bands, filter parts, etc.; and in other applications, such as vibration-damping parts, robot housings, drone housings, shields, bulletproof shields, sports cushions, airplane windows, and resin compatibilizers.

[0140] The present invention will be described in more detail below with reference to examples, but is not limited to these examples. In these examples, the polycarbonate-polyorganosiloxane copolymer (A) may be abbreviated as PC-POS copolymer, and polydimethylsiloxane may be abbreviated as PDMS.

[0141] The polycarbonate resin compositions obtained in the Examples and Comparative Examples described below were evaluated as follows: (1) Measurement of Viscosity Average Molecular Weight (Mv) The viscosity average molecular weight (Mv) was determined by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20°C using an Ubbelohde viscometer, determining the intrinsic viscosity [η] from the measured viscosity, and calculating the intrinsic viscosity [η] using the following formula (Schnell's formula): [η] = 1.23 × 10 －５ Mv ０．８３

[0142] (2) Foam height and stirring speed: The raw materials were charged into the reactor and polymerization was allowed to proceed at a stirring speed of 250 rpm. Each time the foam reached the lid of the reactor, the stirring speed was reduced by 50 rpm. The height of the liquid surface was set to 0% and the height of the lid of the reactor to 100%, and the height of the foam at which the most foam occurred was visually evaluated based on the scale marked on the stirring blade, and the foam height and stirring speed at that time were recorded.

[0143] (3) Haze A press-molded product having a thickness of 1 mm was prepared using the obtained polycarbonate resin composition, and the haze value was measured in accordance with ISO 14782:1999 (JIS K 7136:2000).

[0144] (4) １ H-NMR measurement under the following conditions １ Based on the integrated values ​​of peaks derived from the following specific structures obtained by H-NMR measurement, the contents of the structural unit represented by general formula (1), the structural unit (A-21), the structural unit (A-22), the structural unit (A-23), and the structural unit (A-24), the molar fractions of the structural units (A-21), (A-22), (A-23), and (A-24) relative to the total amount of the structural unit (A-2) 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 (A), and the average value b2 when b and b1 in the polycarbonate-polyorganosiloxane copolymer (A) are combined were calculated. (Measurement conditions) NMR apparatus: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: TH5 5φ NMR sample tube compatible observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of accumulations: 256 times NMR sample tube: 5φ Sample amount: 30 to 40 mg Sample pretreatment: Drying at 100°C for 6 hours Solvent: deuterated chloroform Measurement temperature: room temperature Chemical shift correction: The peak derived from chloroform protons in deuterated chloroform was set as the reference at 7.26 ppm A: Peak integral value of the meta position of the phenyl group at the polymer terminal observed around δ 7.30 to 7.43 B: Peak integral value of the methyl group of the dimethylsiloxane structure represented by general formula (1) observed around δ -0.20 to 0.30 C: Peak integral value of the methylene group of the polyethylene glycol structure represented by general formula (i) observed at around δ 3.30 to 3.75 D: Peak integral value of the methine group of the structural unit (A-21) observed at around δ 4.75 to 5.30 E: Peak integral value of the methylene group of the structural unit (A-22) observed at around δ 1.30 to 1.50 F: Peak integral value of the methine group and methylene group of the structural unit (A-23) observed at around δ 0.8 to 1.98 G: Peak integral value of the methine group of the structural unit (A-24) observed at around δ 1.98 to 2.70 H: Peak integral value of the methylene group of the dimethylsiloxane terminal observed at around δ 0.4 to 0.55 aa = A / 2 bb = B / 6 cc = C / 4 dd = D / 3 ee = (F-G / 6 x 8-H) / 10 kk = E / 4 ll = G / 6 oo = H / 2 Average value b2 in polycarbonate-polyorganosiloxane copolymer (A): cc / oo

[0145] Pellets containing polycarbonate-polyorganosiloxane copolymer (A) produced in Example 1 and Comparative Example 1 T ２ =aa+bb+cc+dd+ee+ll TX ２ =dd+ee+ll f２ = aa / T ２ x 100g ２ = bb / T ２ x 100 h ２ = cc / T ２ ×100 i ２ = dd / T ２ x 100 j ２ = ee / T ２ x 100 m ２ = ll / T ２ x100 TW ２ = f ２ x 93+g ２ ×74.1+h ２ ×44+i ２ x 172 + j ２ ×170+m ２ × 222 Content (mass%) of structural unit (A-21): i ２ ×172 / TW ２ x 100 Content (mass%) of structural unit (A-23): j ２ x170 / TW ２ × 100 Content (mass%) of structural unit (A-24): m ２ ×222 / TW ２ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f ２ ×93 / TW ２ × 100 Polycarbonate block content (mass%): (i ２ x 172 + j ２ ×170+m ２ ×222) / TW ２ × 100 Content (mass%) of the structural unit represented by general formula (1): g ２ ×74.1 / TW ２ × 100 Polyorganosiloxane block content (mass%): (g ２ ×74.1+h ２ ×44) / TW ２ × 100 Molar fraction of the structural unit (A-21) relative to the total amount of the structural units represented by formula (A-2) contained in the PC-POS copolymer: dd / TX ２ × 100 Molar fraction of the structural unit (A-23) relative to the total amount of the structural units represented by formula (A-2) contained in the PC-POS copolymer: ee / TX２ × 100 Molar fraction of the structural unit (A-24) relative to the total amount of structural units represented by formula (A-2) contained in the PC-POS copolymer: 11 / TX ２ ×100 Average value of a in polycarbonate-polyorganosiloxane copolymer (A): bb / (oo / 2) Average value b2 in polycarbonate-polyorganosiloxane copolymer (A): cc / oo

[0146] Pellets containing polycarbonate-polyorganosiloxane copolymer (A) produced in Example 2 and Comparative Example 2 T １ =aa+bb+cc+dd+ee TX １ =dd+ee f １ = aa / T １ x 100g １ = bb / T １ x 100 h １ = cc / T １ ×100 i １ = dd / T １ x 100 j １ = ee / T １ x100 TW １ = f １ x 93+g １ ×74.1+h １ ×44+i １ x 172 + j １ × 170 Content (mass%) of structural unit (A-21): i １ ×172 / TW １ x 100 Content (mass%) of structural unit (A-23): j １ x170 / TW １ ×100 -OR Ｔ The content (mass%) of the terminal structure represented by: f １ ×93 / TW １ × 100 Polycarbonate block content (mass%): (i １ x 172 + j １ ×170) / TW １ × 100 Content (mass%) of the structural unit represented by general formula (1): 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-21) relative to the total amount of the structural unit (A-2) contained in the PC-POS copolymer: dd / TX １ × 100 Molar fraction of the structural unit (A-23) relative to the total amount of the structural unit (A-2) contained in the PC-POS copolymer: ee / TX １ ×100 Average value of a in polycarbonate-polyorganosiloxane copolymer (A): bb / (oo / 2) Average value b2 in polycarbonate-polyorganosiloxane copolymer (A): cc / oo

[0147] (5) ICP Optical Emission Spectroscopy The contents of Al, Ba, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, V, and Zn were analyzed using the following method. (Pretreatment Method) 2 g of sample was collected, concentrated sulfuric acid was added, and the sample was heated to carbonize it. It was then placed in an electric furnace and incinerated at 550°C for 12 hours. Hydrofluoric acid was added to the sample, followed by thermal decomposition and drying. Hydrochloric acid was then added and the sample was heated. After cooling, the sample was brought to a constant volume with ultrapure water. (Measurement Equipment) ICP Optical Emission Spectroscopy: 5100 manufactured by Agilent Technologies, Inc. Quantitative values ​​were determined based on a calibration curve prepared from a reference of known concentration, and the calibration curve solution had the same hydrochloric acid concentration as the sample solution.

[0148] (6) ICP Mass Spectrometry The Cs content was analyzed by the following method. (Pretreatment Method) 2 g of sample was collected, concentrated sulfuric acid was added, and the sample was heated to carbonize it. It was then placed in an electric furnace and incinerated at 550°C for 12 hours. Hydrofluoric acid was added to the sample, followed by thermal decomposition and drying. Hydrochloric acid was then added and the sample was heated. After cooling, the sample was made up to a constant volume with ultrapure water. (Measurement Device) ICP Mass Spectrometer: 8900 manufactured by Agilent Technologies, Inc. The quantitative value was determined based on a calibration curve prepared from a reference of known concentration, and the calibration curve solution had the same hydrochloric acid concentration as the sample solution.

[0149] Example 1 and Comparative Example 1 Polycarbonate resin compositions were produced by the following method. The evaluation results are shown in Tables 1 and 2. A 1-L SUS316 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 (90.00 g / 0.42 mol) having the molar fraction shown in Tables 1 and 2 when the total amount of the diol monomer is taken as 100, and polyether-modified silicone (KF-6123, manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value: 50 mgKOH / g) represented by the following formula in the amounts shown in Tables 1 and 2, based on the total mass (theoretical value) of the resulting PC-POS copolymer shown in Table 1. These were then completely melted at a temperature inside the reactor of 100°C, and the atmosphere inside the reactor was purged with nitrogen.

[0150] Aqueous sodium hydroxide solution was added as a catalyst in the amount shown in Table 1. The stirring speed was set to 250 rpm, the mantle heater was heated to 150°C, and the system was depressurized to 15 kPa. Thereafter, the mantle heater was heated to 190°C, and the system was depressurized to 7 kPa. Thereafter, when the amount of phenol distilled off reached 68%, the temperature was raised to 200°C, and when the amount of phenol distilled off reached 94%, the system was depressurized to full vacuum. The rotation speed was adjusted depending on the degree of foaming. The system was fully evacuated at the temperature shown in Table 1, and polymerization was terminated after confirming that the torque reading of the stirrer (Mazera, ZZ-1220 model) reached 40% at a stirring speed of 20 rpm. The resulting polycarbonate resin compositions were evaluated using the methods described above. The results are shown in Table 1.

[0151] Example 2 and Comparative Example 2 Polycarbonate resin compositions were produced by the following method. The evaluation results are shown in Tables 1 and 2. A 1-L SUS316 reactor equipped with a stirrer, a trap for capturing distilled phenol, and a pressure-reducing device was charged with the diol monomers shown in Table 1, diphenyl carbonate (90.00 g / 0.42 mol) having a molar fraction shown in Table 1 when the total amount of diol monomers is taken as 100, and the aforementioned polyether-modified silicone (KF-6123, manufactured by Shin-Etsu Chemical Co., Ltd., hydroxyl value: 50 mgKOH / g) in the amounts shown in Table 1, based on the total mass (theoretical value) of the PC-POS copolymer to be obtained. These were completely melted at a reactor temperature of 100°C, and the reactor interior was purged with nitrogen. A sodium hydroxide aqueous solution was added as a catalyst in the amount shown in Table 1. The stirring speed was set to 250 rpm, the mantle heater was heated to 150°C, and the system was depressurized to 15 kPa. The mantle heater was then heated to 190°C, and the pressure inside the system was reduced to 7 kPa. Thereafter, when the amount of phenol distilled off reached 68%, the temperature was raised to 200°C, and when the amount of phenol distilled off reached 94%, the pressure was reduced to full vacuum. The rotation speed was adjusted depending on the degree of foaming. A full vacuum was applied when the system temperature reached the temperature shown in Table 1, and the temperature inside the system was raised to 220°C and 240°C as the polymerization progressed. The polymerization was terminated when it was confirmed that the torque display had exceeded the torque limit at a stirring speed of 20 rpm using a stirrer (ZZ-1220 model, manufactured by Mazera). The resulting polycarbonate resin compositions were evaluated using the methods described above. The results are shown in Table 1. In this example, the structural unit (A-21) represented by general formula (21) may be referred to as an ISB structural unit, the structural unit (A-24) represented by general formula (24) may be referred to as a TCDDM structural unit, the structural unit (A-23) represented by general formula (23) may be referred to as a CHDM structural unit, and the structural unit represented by general formula (1) may be referred to as a PDMS structural unit.

[0152] Carbonate compounds: Diphenyl carbonate 1 (calcium atom content: 12 ppm by mass) Diphenyl carbonate 2 (calcium atom content: less than 1 ppm by mass)

[0153]

[0154]

[0155] *1: Represents the molar fraction when the total amount of diol monomers is taken as 100. *2: Represents the mass % of the charged polyorganosiloxane (b) relative to the mass (theoretical value) of the obtained PC-POS copolymer. The mass (theoretical value) of the obtained PC-POS copolymer was calculated from [mass of all diol monomers charged + mass of diphenyl carbonate charged + mass of polyorganosiloxane (b) charged - mass (theoretical value) of phenol produced from diphenyl carbonate]. *3: Represents mole ppm relative to the total amount of diol monomer (a).

[0156] The results in Tables 1 and 2 confirm that the polycarbonate resin compositions obtained in Examples 1 and 2, in which the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms was less than 8 ppm by mass, were less likely to foam during production and had excellent transparency. In contrast, the polycarbonate resin compositions obtained in Comparative Examples 1 and 2, in which the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms was 8 ppm by mass or more, were more likely to foam during production, resulting in poor production efficiency.

Claims

1. A polycarbonate-based resin composition comprising a polycarbonate-polyorganosiloxane copolymer (A), wherein the polycarbonate-polyorganosiloxane copolymer (A) comprises a polycarbonate block and a polyorganosiloxane block comprising a structural unit (A-1) represented by the following general formula (1), and wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms is less than 8 ppm by mass: [In general formula (1), R １ and R ２ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms.

2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block contains at least one structural unit (A-2) represented by the following general formula (2-1) or (2-2): [In general formulas (2-1) and (2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a divalent heterocyclic group having 3 to 40 carbon atoms.] 3. The polycarbonate resin composition according to claim 2, wherein the structural unit (A-2) has at least one selected from structural units (A-21) to (A-25) represented by the following general formulas (21) to (25): [In general formula (22), n represents an integer of 2 to 18.] 4. R in the general formula (1) １ and R ２ The polycarbonate resin composition according to any one of claims 1 to 3, wherein is a methyl group.

5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms is 2 ppm by mass or less.

6. A method for producing a polycarbonate-based resin composition, using raw materials containing a diol monomer (a), a polyorganosiloxane (b), a carbonate ester compound, and a catalyst, and having a total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms of less than 4 ppm by mass, to obtain a polycarbonate-polyorganosiloxane copolymer (A) containing polycarbonate blocks and polyorganosiloxane blocks containing structural units (A-1) represented by the following general formula (1): [In general formula (1), 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.

7. The method for producing a polycarbonate resin composition according to claim 6, wherein the diol monomer (a) contains at least one diol monomer (a2) represented by the following general formula (a2-1) or (a2-2): [In general formulas (a2-1) and (a2-2), L １ 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, a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a divalent heterocyclic group having 3 to 40 carbon atoms; L ２ represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms or a divalent heterocyclic group having 3 to 40 carbon atoms.] 8. The method for producing a polycarbonate resin composition according to claim 6 or 7, wherein the ratio of the number of moles of the carbonate ester compound to the number of moles of the diol monomer (a) is 0.90 to 1.

20.

9. A method for producing the polycarbonate resin composition according to any one of claims 6 to 8, which is carried out by melt polymerization.

10. The method for producing a polycarbonate resin composition according to any one of claims 6 to 9, wherein the total content of sodium atoms, magnesium atoms, potassium atoms, calcium atoms, and cesium atoms in the raw material is 2 ppm by mass or less.

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