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

Abstract

The present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer, and a molded article comprising the polycarbonate-polyorganosiloxane copolymer and the polycarbonate-based resin composition. The polycarbonate-polyorganosiloxane copolymer contains a polycarbonate block containing a structural unit (A-1) represented by general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by general formula (2), and satisfies the following conditions (I) and (II). # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate-based resin composition and a molded product. Background Art

[0002] Polycarbonate resins are known to have excellent properties such as transparency, impact resistance, and flame retardancy, and are therefore expected to be widely used in various fields such as the electrical and electronic equipment field and the automotive field.

[0003] In recent years, from the viewpoint of carbon neutrality, there has been a demand for the development of polycarbonate resins using plant-derived monomers as raw materials. As technologies related to such polycarbonate resins, for example, the technologies described in Patent Documents 1 and 2 can be cited.

[0004] Patent Document 1 describes a polycarbonate copolymer for the purpose of providing a polycarbonate copolymer comprising a plant-derived structural unit having excellent mechanical strength, heat resistance, a small refractive index, a large Abbe number, a small birefringence, and excellent transparency. The polycarbonate copolymer is characterized in that the polycarbonate copolymer comprises a structural unit derived from a specific dihydroxy compound and a structural unit derived from an alicyclic dihydroxy compound, has an Abbe number of 50 or more, and has a 5% thermal weight loss temperature of 340° C. or more.

[0005] Patent document 2 describes a molded product for the purpose of providing a resin molded product having excellent thin-wall moldability, impact resistance, surface hardness, and moisture-heat resistance, and low optical strain. The molded product is characterized in that the molded product is formed using a resin composition containing a polycarbonate resin, wherein the polycarbonate resin has structural units derived from a specific dihydroxy compound and structural units derived from other dihydroxy compounds, and the proportion of the structural units derived from the specific dihydroxy compounds in the polycarbonate resin accounts for more than 70 mol% of the structural units derived from all dihydroxy compounds constituting the polycarbonate resin, and the polycarbonate resin has a reduced viscosity of 0.45 dL / g or less, and the thickness of the molded product is more than 0.1 mm and less than 1 mm.

[0006] Patent Document 3 describes a civil engineering and construction material component, which aims to provide a material component having properties suitable for the civil engineering and construction field while making slight improvements in environmental and resource conservation, and is composed of a polycarbonate containing a structural unit derived from a specific dihydroxy compound.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2008-24919

[0010] Patent Document 2: Japanese Patent Application Publication No. 2014-198761

[0011] Patent Document 3: Japanese Patent Application Publication No. 2009-144013 Summary of the invention

[0012] Problems to be solved by the invention

[0013] According to the research conducted by the present inventors, for example, the polycarbonate copolymer molded article described in Patent Document 1, the molded article described in Patent Document 2, and the civil engineering and construction material parts made of polycarbonate described in Patent Document 3 have excellent damage resistance, but there is room for improvement in impact resistance.

[0014] The present invention has been made in view of the above circumstances, and provides a polycarbonate-polyorganosiloxane copolymer and a polycarbonate-based resin composition capable of obtaining a molded product having excellent impact resistance and scratch resistance.

[0015] Means for solving problems

[0016] The present inventors have found that a polycarbonate-polyorganosiloxane copolymer containing a specific structural unit and a polycarbonate-based resin composition containing the copolymer can provide a molded product having excellent impact resistance and scratch resistance.

[0017] That is, according to the present invention, there are provided the polycarbonate-polyorganosiloxane copolymer, the polycarbonate-based resin composition, and the molded article shown below.

[0018] [1]

[0019] A polycarbonate-polyorganosiloxane copolymer comprises a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2), and satisfies the following conditions (I) and (II).

[0020] [Chemical formula 1]

[0021]

[0022] [In general formula (2), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. a represents an integer of 2 to 500.]

[0023] Condition (I): Charpy impact strength of the molded sheet measured at a temperature of 23°C in accordance with ISO 179-1:2010 is 15 kJ / m 2The molded sheet is obtained by post-processing a long molded sheet having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm and giving a notch (r = 0.25 mm ± 0.05 mm) to the polycarbonate-polyorganosiloxane copolymer;

[0024] Condition (II): The pencil hardness of the molded article of the polycarbonate-polyorganosiloxane copolymer measured in accordance with JIS K 5600-5-4:1999 is HB or more.

[0025] [2]

[0026] The polycarbonate-polyorganosiloxane copolymer according to [1], wherein the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0 mass % or more and 25.0 mass % or less, and the content of the structural unit (A-1) represented by the general formula (1) is 73.0 mass % or more.

[0027] [Chemical formula 2]

[0028]

[0029] [In the general formula (XX), R 1 and R 2 represents the same as R in the above general formula (2) 1 and R 2 Same meaning.]

[0030] [3]

[0031] The polycarbonate-polyorganosiloxane copolymer according to [1], further comprising at least one structural unit (A-3) selected from the group consisting of structures represented by the following general formulas (3) and (4).

[0032] [Chemical formula 3]

[0033]

[0034] [In general formulas (3) and (4), R 11 represents a divalent linear or branched aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 12 represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.]

[0035] [4]

[0036] The polycarbonate-polyorganosiloxane copolymer according to [3], wherein the structural unit (A-3) has at least one structure selected from the group consisting of the structures represented by the following general formulas (31) to (34).

[0037] [Chemical formula 4]

[0038]

[0039] [In the general formula (31), n ​​represents an integer of 2 to 18.]

[0040] [5]

[0041] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) comprises a structural unit (A-32) represented by the general formula (32), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x,

[0042] The total content of the structural units (A-1) and (A-32) in the polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer is 90.0 mol % or more.

[0043] The molar ratio (A-32 / A-1) of the structural unit (A-32) to the structural unit (A-1) and the content x of the structural unit represented by the following general formula (XX) satisfy the following condition (C2) or (D2).

[0044] Condition (C2): A-32 / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0045] Condition (D2): A-32 / A-1 is 1.0 / 99.0 or more and 27.0 / 73.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0046] [Chemical formula 5]

[0047]

[0048] [In the general formula (XX), R 1 and R 2 represents the same as R in the above general formula (2) 1 and R 2 Same meaning.]

[0049] [6]

[0050] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) comprises a structural unit (A-31) represented by the general formula (31), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x,

[0051] The molar ratio (A-31 / A-1) of the structural unit (A-31) to the structural unit (A-1) and the content x of the structural unit represented by the following general formula (XX) satisfy the following condition (C1) or (D1).

[0052] Condition (C1): A-31 / A-1 is 1.0 / 99.0 or more and 25.0 / 75.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0053] Condition (D1): A-31 / A-1 is 1.0 / 99.0 or more and 30.0 / 70.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0054] [Chemical formula 6]

[0055]

[0056] [In the general formula (XX), R 1 and R 2 represents R in the above general formula (2) 1 and R 2 Same meaning.]

[0057] [7]

[0058] The polycarbonate-polyorganosiloxane copolymer according to [4], wherein the structural unit (A-3) comprises a structural unit (A-32) represented by the general formula (32) and a structural unit (A-33) represented by the general formula (33), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x,

[0059] The molar ratio of the sum of the structural units (A-32) and (A-33) to the structural unit (A-1) ((sum of A-32 and A-33) / A-1)), the molar ratio of the structural unit (A-32) to the structural unit (A-33) (A-32 / A-33), and the content x of the structural unit represented by the general formula (XX) satisfy the following conditions (C41), (C42), (C43), (D41), (D42), or (D43).

[0060] Condition (C41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 39.0 / 61.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0061] Condition (C42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 31.0 / 69.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0062] Condition (C43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 46.0 / 54.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0063] Condition (D41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 32.0 / 68.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0064] Condition (D42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 36.0 / 64.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0065] Condition (D43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 41.0 / 59.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0066] [Chemical formula 7]

[0067]

[0068] [In the general formula (XX), R 1 and R 2 represents the same as R in the above general formula (2) 1 and R 2 Same meaning.]

[0069] [8]

[0070] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [7], wherein a is an integer of 2 to 300.

[0071] [9]

[0072] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [8], wherein R 1 and R 2 It is methyl.

[0073]

[10]

[0074] A polycarbonate resin composition comprising the polycarbonate-polyorganosiloxane copolymer described in any one of [1] to [9].

[0075]

[11]

[0076] A molded article comprising the polycarbonate resin composition described in

[10] .

[0077] Effects of the Invention

[0078] According to the present invention, a polycarbonate-polyorganosiloxane copolymer and a polycarbonate-based resin composition capable of obtaining a molded product having excellent impact resistance and scratch resistance can be provided. DETAILED DESCRIPTION

[0079] Hereinafter, the polycarbonate-polyorganosiloxane copolymer of the present invention, the polycarbonate resin composition containing the copolymer, and the molded product of the resin composition are described in detail. In this specification, any preferred stipulation can be adopted, and a combination of preferred stipulations can be said to be more preferred. In this specification, the description of "XX to YY" means "XX or more and YY or less".

[0080] When there are a plurality of lower limit values ​​such as "or greater than x" or a plurality of upper limit values ​​such as "or less than y" for one technical matter, any upper limit value and lower limit value may be selected and combined.

[0081] When the compounds and chemical structures described in the present specification have a plurality of stereoisomers and structural isomers, all stereoisomers and structural isomers are included, unless otherwise specified.

[0082] 1. Polycarbonate-polysiloxane copolymer

[0083] The polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2).

[0084] According to the polycarbonate-polyorganosiloxane copolymer of the present invention, a molded product having excellent impact resistance and scratch resistance can be obtained.

[0085] [Chemical formula 8]

[0086]

[0087] In general formula (2), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. a represents an integer of 2 to 500.

[0088] <Polycarbonate block>

[0089] The polycarbonate block is represented by the following general formula (X), and includes a structural unit (A-1) represented by general formula (1).

[0090] [Chemical formula 9]

[0091]

[0092] In the above general formula (X), R 10 It represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which 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.

[0093] In the present specification, various "divalent" hydrocarbon groups refer to substituents obtained by removing two hydrogen atoms from a hydrocarbon.

[0094] The structural unit (A-1) represented by the general formula (1) preferably includes a structural unit represented by the following general formula (11), and more preferably includes only a structural unit represented by the following general formula (11).

[0095] [Chemical formula 10]

[0096]

[0097] The polycarbonate block of the polycarbonate-polyorganosiloxane copolymer of the present invention may further include at least one structural unit (A-3) selected from the structural units represented by the following general formulas (3) and (4). When the polycarbonate-polyorganosiloxane copolymer includes the structural unit (A-3), the impact resistance of the molded article can be further improved.

[0098] [Chemical formula 11]

[0099]

[0100] In the above general formula (3), R 11It represents a divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent branched-chain aliphatic hydrocarbon group having 3 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and is preferably a divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent branched-chain aliphatic hydrocarbon group having 3 to 40 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.

[0101] In the above general formula (4), R 12 It represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, preferably a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and more preferably a divalent alicyclic hydrocarbon group having 5 to 15 carbon atoms.

[0102] From the viewpoint of reducing the melt flow rate of the polycarbonate-polyorganosiloxane copolymer and increasing the tensile elastic modulus, tensile strength (yield) and glass transition temperature, in the above general formulas (3) and (4), R 11 and R 12 It preferably contains at least one carbon atom selected from tertiary carbon atoms and quaternary carbon atoms, more preferably contains at least one carbon atom selected from tertiary carbon atoms and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, further preferably contains at least one carbon atom selected from tertiary carbon atoms and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 8 carbon atoms, and particularly preferably contains at least one carbon atom selected from tertiary carbon atoms and quaternary carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 6 carbon atoms from the viewpoint of easy availability of raw materials.

[0103] In the above general formulas (3) and (4), by making R 11 and R 12 The reason why the melt flow rate of the polycarbonate-polyorganosiloxane copolymer decreases and the reason why the tensile elastic modulus, tensile strength (yield) and glass transition temperature increase when the polycarbonate-polyorganosiloxane copolymer contains at least one type of carbon atoms selected from tertiary carbon atoms and quaternary carbon atoms is not yet clear, but it is believed that the mobility of tertiary carbon atoms and quaternary carbon atoms is low, and the structure containing them tends to become rigid.

[0104] In the above general formulas (3) and (4), by making R 11 and R 12 The reason why the melt flow rate of the polycarbonate-polyorganosiloxane copolymer decreases and the reason why the tensile elastic modulus, tensile strength (yield) and glass transition temperature increase when the polycarbonate-polyorganosiloxane copolymer contains a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms is not yet clear, but it is believed that the cyclic structure restricts the mobility of the molecules and the structure containing them tends to become rigid.

[0105] It should be noted that the structural unit (A-1) is not included in the structural unit (A-3).

[0106] In the above general formula (3), R 11 The divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms and the divalent branched-chain aliphatic hydrocarbon group having 3 to 40 carbon atoms shown 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.

[0107] As R in the above general formula (3) 11 The divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms or the divalent branched-chain aliphatic hydrocarbon group having 3 to 40 carbon atoms shown in the above formula (I) may be exemplified by ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, 2-ethylhexylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene and n-octadecylene, and is preferably n-propylene, n-butylene, n-pentylene, neopentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene or n-decylene, and more preferably n-butylene, n-pentylene, neopentylene, n-hexylene, n-heptylene or n-octylene.

[0108] In the above general formula (3), R 11 The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms 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.

[0109] As R in the above general formula (3) 11 The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms as shown in the above formula (I) may be cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclotetradecylene, adamantylene, bicycloheptylene, bicyclodecylene, tricyclodecylene, spirobicyclohexylene, decahydronaphthylene, tricyclotetradecylene and pentacyclopentadecylene, preferably cyclohexylene, tricyclodecylene, pentacyclopentadecylene, decahydronaphthylene, tricyclotetradecylene, bicycloheptylene or adamantylene, and more preferably cyclohexylene or tricyclodecylene.

[0110] As R in the above general formula (3) 11 The cyclohexylene group shown in the figure includes various isomers represented by the following general formula (3a). Specific examples thereof include 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene.

[0111] [Chemical formula 12]

[0112]

[0113] In the general formula (3a), R 101 It is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

[0114] As R in the above general formula (3) 11 The tricyclodecanylene or pentacyclopentadecanylene group includes various isomers represented by the following general formula (3b). n' is 0 or 1.

[0115] [Chemical formula 13]

[0116]

[0117] As R in the above general formula (3) 11 The decahydronaphthylene or tricyclotetradecylene shown in the formula (3c) includes various isomers represented by the following general formula (3c). Specifically, 2,6-decahydronaphthylene, 1,5-decahydronaphthylene, 2,3-decahydronaphthylene and the like are mentioned. n" is 0 or 1.

[0118] [Chemical formula 14]

[0119]

[0120] As R in the above general formula (3) 11 The bicycloheptylene group shown in the figure includes various isomers represented by the following general formula (3d). Specific examples thereof include 2,3-bicycloheptylene and 2,5-bicycloheptylene.

[0121] [Chemical formula 15]

[0122]

[0123] As R in the above general formula (3) 11 The adamantylene group shown in FIG. 3 includes various isomers represented by the following general formula (3e). Specifically, 1,3-adamantylene group and the like are mentioned.

[0124] [Chemical formula 16]

[0125]

[0126] In the above general formula (3), R 11 The divalent aromatic hydrocarbon group having 6 to 20 carbon atoms 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.

[0127] As R in the above general formula (3) 11 Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include an aromatic hydrocarbon group represented by the following general formula (3f), 1,4-phenylene, 1,3-phenylene and 1,2-phenylene, and an aromatic hydrocarbon group represented by the following general formula (3f) is preferred.

[0128] [Chemical formula 17]

[0129]

[0130] 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.

[0131] In the above general formula (3f), R 102 and R 103 Examples of the halogen atom independently represented include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0132] As R 102 and R 103 The alkyl groups independently represented by R include methyl, ethyl, n-propyl, isopropyl, various butyl groups ("various" means including straight-chain and all branched groups, the same below), various pentyl groups and various hexyl groups. 102 and R 103 The alkoxy groups independently represented include those in which the alkyl moiety is the above-mentioned alkyl group.

[0133] Examples of the alkylene group represented by X include methylene, ethylene, trimethylene, tetramethylene, hexamethylene, etc., and preferably an alkylene group having 1 to 5 carbon atoms. Examples of the alkylidene group represented by X include ethylidene, isopropylidene, etc. Examples of the cycloalkylene group represented by X include cyclopentanediyl, cyclohexanediyl, etc., and preferably a cycloalkylene group having 5 to 10 carbon atoms. Examples of the arylene group represented by X include phenylene, naphthylene, biphenylene, etc. Examples of the cycloalkylidene group represented by X include cyclohexylidene, 3-methylcyclohexylidene, 3,5,5-trimethylcyclohexylidene, cyclododecylidene, 2-adamantylidene, etc., and preferably a cycloalkylene group having 5 to 12 carbon atoms, and more preferably a cycloalkylene group having 5 to 8 carbon atoms. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl, naphthyl, biphenyl, anthracenyl, etc. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl, naphthyl, biphenylyl and anthracenyl.

[0134] s and t each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1. Among them, suitable is the case where s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or the case where s and t are 0 and X is an alkylidene group, particularly an isopropylidene group.

[0135] As R in the above general formula (4) 12 The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by the formula (3) may be any of the following: 11 The same divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms is preferably cyclohexylene, tricyclodecanylene, pentacyclopentadecanylene, decahydronaphthylene, tricyclotetradecylene, bicycloheptylene, or adamantylene, and more preferably cyclohexylene or tricyclodecanylene.

[0136] From the viewpoint of further improving the impact resistance of the molded article, the structural unit (A-3) preferably contains at least one selected from the structural units (A-31) to (A-34) represented by the following general formulas (31) to (34), more preferably contains at least one selected from the structural units (A-31) to (A-33), and even more preferably contains at least one selected from the structural units (A-31) to (A-33).

[0137] [Chemical formula 18]

[0138]

[0139] In the general formula (31), n ​​represents an integer of 2-18, preferably 3-10, and more preferably 4-8.

[0140] When the structural unit (A-3) contains at least one selected from the structural units (A-31) to (A-34), the total content of the structural units (A-31) to (A-34) in the structural unit (A-3) is preferably 90.0 mass % or more, more preferably 93.0 mass % or more, further preferably 95.0 mass % or more, and is preferably 100.0 mass % or less, more preferably 100.0 mass %.

[0141] From the viewpoint of obtaining a molded body having excellent damage resistance and impact resistance, the content of the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 65.0% by mass or more, more preferably 80.0% by mass or more, and further preferably 85.0% by mass or more, and preferably 99.0% by mass or less, more preferably 97.0% by mass or less, and further preferably 95.0% by mass or less. Furthermore, the content of the polycarbonate block in the polycarbonate-polyorganosiloxane copolymer is preferably 65.0 to 99.0% by mass, more preferably 80.0 to 97.0% by mass, and further preferably 85.0 to 95.0% by mass.

[0142] From the viewpoint of further improving the damage resistance of the molded body, the content of the structural unit (A-1) in the polycarbonate-polyorganosiloxane copolymer is preferably 45.0% by mass or more, more preferably 55.0% by mass or more, and more preferably 65.0% by mass or more, and is preferably 99.0% by mass or less, more preferably 95.0% by mass or less, and more preferably 90.0% by mass or less. Furthermore, the content of the structural unit (A-1) in the polycarbonate-polyorganosiloxane copolymer is preferably 45.0 to 99.0% by mass, more preferably 55.0 to 95.0% by mass, and more preferably 65.0 to 90.0% by mass.

[0143] When the polycarbonate-polyorganosiloxane copolymer contains the structural unit (A-3), from the viewpoint of further improving the impact resistance of the molded article, the content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer is preferably 1.0% by mass or more, more preferably 5.0% by mass or more, and more preferably 10.0% by mass or more, and is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and more preferably 35.0% by mass or less. Furthermore, the content of the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer is preferably 1.0 to 50.0% by mass, more preferably 5.0 to 40.0% by mass, and more preferably 10.0 to 35.0% by mass.

[0144] From the viewpoint of improving the damage resistance of the molded body, the content of the structural unit (A-1) in the polycarbonate block is preferably 60.0 mol% or more, more preferably 70.0 mol% or more, and is preferably 100.0 mol% or less, more preferably 90.0 mol% or less, and further preferably 80.0 mol% or less. Furthermore, from the viewpoint of improving the damage resistance of the molded body, the content of the structural unit (A-1) in the polycarbonate block is preferably 60.0 to 100.0 mol%, more preferably 70.0 to 90.0 mol%, and further preferably 70.0 to 80.0 mol%.

[0145] When the polycarbonate block contains the structural unit (A-3), from the viewpoint of improving the scratch resistance of the molded article, the content of the structural unit (A-1) in the polycarbonate block is preferably 50.0 mol% or more, more preferably 60.0 mol% or more, and further preferably 70.0 mol% or more, and is preferably 99.0 mol% or less, more preferably 90.0 mol% or less, and further preferably 80.0 mol% or less. Furthermore, when the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-1) in the polycarbonate block is preferably 50.0 to 99.0 mol%, more preferably 60.0 to 90.0 mol%, and further preferably 70.0 to 80.0 mol%.

[0146] When the polycarbonate block contains the structural unit (A-3), from the viewpoint of improving the impact resistance of the molded article, the content of the structural unit (A-3) in the polycarbonate block is preferably 3.0 mol% or more, more preferably 5.0 mol% or more, further preferably 8.0 mol% or more, further preferably 10.0 mol% or more, and from the viewpoint of obtaining a molded article excellent in scratch resistance and impact resistance, it is preferably 50.0 mol% or less, more preferably 40.0 mol% or less, further preferably 30.0 mol% or less. Furthermore, when the polycarbonate block contains the structural unit (A-3), the content of the structural unit (A-3) in the polycarbonate block is preferably 3.0 to 50.0 mol%, more preferably 5.0 to 40.0 mol%, further preferably 8.0 to 30.0 mol%, further preferably 10.0 to 30.0 mol%.

[0147] The contents of the polycarbonate block, the structural unit (A-1), and the structural unit (A-3) in the polycarbonate-polyorganosiloxane copolymer were calculated by nuclear magnetic resonance (NMR) measurement.

[0148] <Terminal structure of polycarbonate-polyorganosiloxane copolymer>

[0149] As an embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may contain -OR T The terminal structure shown. T is Ar 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 or p-(tert-butyl)phenyl, preferably Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 ,Ar 5 ,Ar 6 , or p-(tert-butyl)phenyl.

[0150] Ar 1 ,Ar 2 ,Ar 3 ,Ar 4 ,Ar 5 , or Ar 6Preferred is phenyl, o-tolyl, m-tolyl, p-tolyl, chlorophenyl, or naphthyl, and more preferred is phenyl.

[0151] -OR in polycarbonate-polyorganosiloxane copolymer T The content of the terminal structure shown is preferably 0.01 mass % or more, more preferably 0.2 mass % or more, further preferably 0.5 mass % or more, and preferably 3.0 mass % or less, more preferably 2.5 mass % or less, further preferably 2.0 mass % or less. T The content of the terminal structure shown 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. -OR T As the number of terminal structures shown increases, the number of terminal hydroxyl groups derived from the diol monomer decreases, and the heat resistance and glass transition temperature of the resin increase.

[0152] -OR T The content of the terminal structure shown was calculated by nuclear magnetic resonance (NMR) measurement.

[0153] <Polyorganosiloxane block>

[0154] The polyorganosiloxane block contained in the polycarbonate-polyorganosiloxane copolymer of the present invention contains at least a structure (A-2) represented by the following general formula (2). The polyorganosiloxane block is a structural unit existing between the two closest polycarbonate bonds on the main chain of the polycarbonate-polyorganosiloxane copolymer and containing at least one structure represented by the following general formula (XX).

[0155] [Chemical formula 19]

[0156]

[0157] In general formula (2), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. a represents an integer of 2 to 500.

[0158] [Chemical formula 20]

[0159]

[0160] In the general formula (XX), R 1 and R 2 represents the same as R in the above general formula (2) 1 and R 2 Same meaning.

[0161] In the formula, as 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 include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 1 and R 2 The alkoxy group having 1 to 10 carbon atoms represented by is exemplified by an alkoxy group having the same alkyl moiety as the above-mentioned alkyl group. 1 and R 2 The aryl group having 6 to 12 carbon atoms represented by , includes phenyl and naphthyl. 1 ~R 4 Examples of the alkylaryl group having 7 to 22 carbon atoms include alkylaryl groups having the same alkyl moiety as the above-mentioned alkyl group and the same aryl moiety as the above-mentioned aryl group.

[0162] As R 1 ~R 4 , preferably all are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, or arylalkyl groups having 7 to 22 carbon atoms, more preferably all are alkyl groups having 1 to 6 carbon atoms, and further preferably R 1 ~R 4 All are methyl.

[0163] The polyorganosiloxane block preferably has a structure represented by the following general formula (21).

[0164] [Chemical formula 21]

[0165]

[0166] In general formula (21), R 1 , R 2 and a represents the same as R in the above general formula (2) 1 , R 2 Same meaning as a. 3 and R 4 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, wherein at least one of the main chain and the side chain of these groups may contain -O-, -COO-, -CO-, -S-, -NH- and -NR 111 -At least one group. 8Each of them may be the same or different and 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 may contain -O-, -COO-, -CO-, -S-, -NH- and -NR in at least one of the main chain and the side chain. 111 -At least one group in R 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.

[0167] In addition, the polyorganosiloxane block preferably has a structure represented by the following general formula (22).

[0168] [Chemical formula 22]

[0169]

[0170] In general formula (22), R 1 ~R 4 , R 6 , R 8 , a, b, u and z represent the same as R in the above general formula (2) and general formula (21). 1 ~R 4 , R 6 , R 8 , a, b, u and z have the same meaning. 5 represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups may contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. 111 -At least one group in R 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, wherein at least one of the main chain and the side chain of these groups may contain -O-, -COO-, -CO-, -S-, -NH- and -NR 111 -At least one group in R 111 b1 represents an integer of 2 to 200. u1 and z1 represent 0 or 1.

[0171] The polyorganosiloxane block may have at least one structure represented by the following general formulae (23) to (26).

[0172] [Chemical formula 23]

[0173]

[0174] In the general formulas (23) to (26), R 1~R 8 , a, b, b1, u, u1, z and z1 represent the same as R in the above general formula (2), general formula (21) and general formula (22). 1 ~R 8 , a, b, b1, u, u1, z and z1 have the same meanings. z -and- (O) z1 -, 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.

[0175] In the formula, as R 3 and R 4 The halogen atoms shown include those corresponding to R 1 and R 2 The halogen atoms shown are the same as the halogen atoms shown in FIG. 1 ~R 4 The alkyl group having 1 to 10 carbon atoms represented by 1 and R 2 The same group as the alkyl group shown. 3 and R 4 The alkoxy group having 1 to 10 carbon atoms represented by 1 and R 2 The same group as the alkoxy group shown. 3 and R 4 The aryl group having 6 to 12 carbon atoms represented by 1 and R 2 The same group as the aryl group shown. 3 and R 4 The alkylaryl group having 7 to 22 carbon atoms represented by 1 and R 2 The same groups as the alkylaryl groups shown.

[0176] As R 3 and R 4 , preferably all are hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aryl groups having 6 to 12 carbon atoms, or arylalkyl groups having 7 to 22 carbon atoms, more preferably all are alkyl groups having 1 to 6 carbon atoms, and further preferably R 3 and R 4 All are methyl.

[0177] As R 5 , R 6 , R 7 or R 8 The arylene group having 6 to 20 carbon atoms represented by , includes phenylene and naphthylene. 5 , R 6 , R 7 , or R8 The alkylene groups having 1 to 10 carbon atoms as shown in R include methylene, dimethylene, trimethylene, methyl-substituted dimethylene, and various butylene groups. The various butylene groups are preferably tetramethylene. 5 , R 6 , R 7 or R 8 The alkylarylene group having 7 to 22 carbon atoms as shown in the figure may include an alkylarylene group having the same alkyl moiety as the above-mentioned alkylene group and the same arylene moiety as the above-mentioned arylene group. In particular, these groups may contain -O-, -COO-, -CO-, -S-, -NH-, and NR in at least one of the main chain and the side chain. 111 -At least one group in R 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 include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 111 Examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl.

[0178] R 5 and R 6 Preferably, they are all alkylene groups having 1 to 10 carbon atoms or alkylarylene groups having 7 to 22 carbon atoms, more preferably, they are all alkylene groups having 1 to 5 carbon atoms or alkylarylene groups having 7 to 11 carbon atoms, and further preferably, they are all trimethylene groups or trimethylenephenylene groups (-CH2CH2CH2-Ph-).

[0179] R 7 and R 8 Preferably, they are all alkylene groups having 1 to 10 carbon atoms, more preferably, they are all alkylene groups having 1 to 5 carbon atoms, further preferably, they are all dimethylene, methyl-substituted dimethylene (-CH2CHMe-), trimethylene, or tetramethylene, and further preferably, they are all dimethylene.

[0180] In the general formula (2) and the general formulae (21) to (26), a represents the number obtained by adding 1 to the number of repetitions of the structural unit represented by the general formula (XX), and is preferably an integer of 2 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, and preferably 300 or less, more preferably 95 or less, further preferably 70 or less, further preferably 50 or less. Furthermore, in the general formulae (2) and the general formulae (21) to (26), a is preferably an integer of 2 to 300, more preferably 10 to 95, further preferably 15 to 70, further preferably 20 to 50.

[0181] The average value of a in the polycarbonate-polyorganosiloxane copolymer is preferably 2 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, and preferably 300 or less, more preferably 95 or less, further preferably 70 or less, further preferably 50 or less. Furthermore, the average value of a in the polycarbonate-polyorganosiloxane copolymer is preferably 2 to 300, more preferably 10 to 95, further preferably 15 to 70, further preferably 15 to 50, further preferably 20 to 50. If the average value of a in the polycarbonate-polyorganosiloxane copolymer is 10 to 95, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and is a highly transparent copolymer, which is preferred. In addition, if the average value of a in the polycarbonate-polyorganosiloxane copolymer is 15 to 50, it is preferred because the mechanical properties such as the surface hardness, tensile strength and tensile elongation of the molded product obtained from the polycarbonate-polyorganosiloxane copolymer can be improved, and a good molded appearance can be obtained.

[0182] The average value of a in the polycarbonate-polyorganosiloxane copolymer is calculated by nuclear magnetic resonance (NMR) measurement.

[0183] In the general formulae (21) to (26), b and b1 represent the number of repeating units, and each independently represents an integer of preferably 2 or more, more preferably 5 or more, further preferably 8 or more, further preferably 10 or more, further preferably 12 or more, and preferably 200 or less, more preferably 100 or less, further preferably 50 or less, further preferably 30 or less, further preferably 25 or less, further preferably 20 or less. Furthermore, in the general formulae (21) to (26), b and b1 each independently represent an integer of preferably 2 to 200, more preferably 5 to 100, further preferably 8 to 50, further preferably 10 to 30, further preferably 12 to 25, further preferably 12 to 20.

[0184] The average value of b, the average value of b1, and the average value b2 when b and b1 are added in the polycarbonate-polyorganosiloxane copolymer are preferably 2 or more, more preferably 5 or more, further preferably 8 or more, further preferably 10 or more, further preferably 12 or more, and preferably 200 or less, more preferably 100 or less, further preferably 50 or less, further preferably 30 or less, further preferably 25 or less, further preferably 20 or less. If it is within the above range, the raw material is easy to obtain, which is preferred. In addition, the average value of b, the average value of b1, and the average value b2 when b and b1 are added in the polycarbonate-polyorganosiloxane copolymer are preferably 2 to 200, more preferably 5 to 100, further preferably 8 to 50, further preferably 10 to 30, further preferably 12 to 25, further preferably 12 to 20. If the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 10 or more, the impact resistance and damage resistance of the obtained molded body can be further improved, and it is therefore more preferred. If the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 100 or less, the reduction in handleability caused by the increase in the viscosity and melting point of the polyorganosiloxane can be suppressed, and it is therefore more preferred. If the average value b2 in the polycarbonate-polyorganosiloxane copolymer is 50 or less, the physical property improvement effect brought about by the polycarbonate-polyorganosiloxane copolymer containing the polyorganosiloxane block is further improved, and it is therefore further preferred.

[0185] The average value b2 in the polycarbonate-polyorganosiloxane copolymer is calculated by nuclear magnetic resonance (NMR) measurement.

[0186] In the general formula (21), u is preferably 1. In the general formulas (22) to (26), u and u1 are each preferably 1, and more preferably both u and u1 are 1.

[0187] In the general formula (21), z is preferably 1. In the general formulas (22) to (26), z and z1 are each preferably 1, and more preferably both z and z1 are 1.

[0188] In the general formula (21), R 1 ~R 4 All are methyl, R 6 is trimethylene, R 8 is dimethylene, z is 1, and R 1 ~R 4 All are methyl, R 6 is trimethylene, R 8 is a dimethylene group, z is 1, and u is 1.

[0189] In the general formulas (22) to (26), R is more preferably 1 ~R 4All are methyl, R 5 and R 6 All are trimethylene, R 7 and R 8 Both are dimethylene, z and z 1 are both 1, u and u 1 Both are 1.

[0190] In general formulae (23) to (26), β is a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid compound. Examples of dicarboxylic acid compounds include dicarboxylic acids, anhydrides of dicarboxylic acids, halides of dicarboxylic acids, 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 formulae (i) to (v).

[0191] [Chemical formula 24]

[0192]

[0193] From the viewpoint of improving impact resistance, the polyorganosiloxane block preferably does not include a branched structure.

[0194] From the viewpoint of improving the impact resistance of the molded article, the content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 2.0% by mass or more, more preferably 3.0% by mass or more, further preferably 4.0% by mass or more, and further preferably 5.0% by mass or more, and is preferably 25.0% by mass or less, more preferably 20.0% by mass or less, further preferably 15.0% by mass or less, and further preferably 7.5% by mass or less. Furthermore, the content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0 to 25.0% by mass, more preferably 3.0 to 20.0% by mass, further preferably 4.0 to 15.0% by mass, and further preferably 5.0 to 7.5% by mass.

[0195] When the content of the structural unit represented by the general formula (XX) is within the above range, from the viewpoint of further improving the damage resistance and impact resistance of the molded article, the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-polyorganosiloxane copolymer is preferably 73.0% by mass or more, more preferably 76.0% by mass or more, and even more preferably 78.0% by mass or more, and is preferably 96.0% by mass or less, more preferably 92.0% by mass or less, and even more preferably 88.0% by mass or less. In this case, the content of the structural unit (A-1) represented by the general formula (1) in the polycarbonate-polyorganosiloxane copolymer is preferably 73.0 to 96.0% by mass, more preferably 76.0 to 92.0% by mass, and even more preferably 78.0 to 88.0% by mass.

[0196] In this specification, the “content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer” means the mass of the structural unit represented by the general formula (XX) relative to the structural unit (A-1), the structural unit represented by the general formula (XX), the structural unit represented by the following general formula (Y), -OR T The terminal structure and the percentage of the total mass of the structural unit (A-3) as required are shown.

[0197] [Chemical formula 25]

[0198]

[0199] In the general formula (Y), R Y For R 7 or R 8 In R Y For R 8 In the case of 0 For z 2 , in R Y For R 7 In the case of 0 For z 1 . R 7 , R 8 、z 1 and z 2 Means the same as above.

[0200] From the viewpoint of improving the impact resistance of the molded body, the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0% by mass or more, more preferably 4.0% by mass or more, and further preferably 9.0% by mass or more, and preferably 25.0% by mass or less, more preferably 16.0% by mass or less, and further preferably 13.0% by mass or less. Furthermore, the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer is preferably 2.0 to 25.0% by mass, more preferably 4.0 to 16.0% by mass, and further preferably 9.0 to 13.0% by mass.

[0201] In the present specification, the “content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer” refers to the total mass of the structural unit represented by the general formula (XX) and the structural unit represented by the general formula (Y) relative to the structural unit (A-1), the structural unit represented by the general formula (XX), the structural unit represented by the general formula (Y), -OR T The terminal structure and the percentage of the total mass of the structural unit (A-3) as required are shown.

[0202] The contents of the polyorganosiloxane block and the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer were calculated by nuclear magnetic resonance (NMR) measurement.

[0203] In one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention is a polycarbonate-polyorganosiloxane copolymer (S-1), wherein the polycarbonate-polyorganosiloxane copolymer (S-1) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1) and a structural unit (A-31) represented by the general formula (31), and a polyorganosiloxane block comprising a structure (A-2) represented by the general formula (2), wherein the molar ratio (A-31 / A-1) of the structural unit (A-31) to the structural unit (A-1) and the content x of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer satisfy the following condition (C1) or (D1).

[0204] Condition (C1): A-31 / A-1 is 1.0 / 99.0 or more and 25.0 / 75.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0205] Condition (D1): A-31 / A-1 is 1.0 / 99.0 or more and 30.0 / 70.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0206] In the above condition (C1), A-31 / A-1 is preferably 20.0 / 80.0 or less, and more preferably 17.0 / 83.0 or less. Furthermore, A-31 / A-1 in the condition (C1) is preferably 1.0 / 99.0 to 20.0 / 80.0, and more preferably 1.0 / 99.0 to 17.0 / 83.0.

[0207] A-31 / A-1 in the above condition (D1) is preferably 25.0 / 75.0 or less, and more preferably 17.0 / 83.0 or less. Furthermore, A-31 / A-1 in the condition (D1) is preferably 1.0 / 99.0 to 25.0 / 75.0, and more preferably 1.0 / 99.0 to 17.0 / 83.0.

[0208] In the polycarbonate-polyorganosiloxane copolymer (S-1), the total content of the structural units (A-1) and (A-31) in the polycarbonate block is preferably 70.0 mol % or more, more preferably 80.0 mol % or more, further preferably 90.0 mol % or more, and further preferably 100.0 mol %.

[0209] As one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-2), wherein the polycarbonate-polyorganosiloxane copolymer (S-2) comprises a polycarbonate block comprising a structural unit (A-1) represented by the above general formula (1) and a structural unit (A-32) represented by the above general formula (32), and a polyorganosiloxane block comprising a structure (A-2) represented by the above general formula (2), wherein the total content of the structural units (A-1) and (A-32) in the polycarbonate block contained in the polycarbonate-polyorganosiloxane copolymer is 90.0 mol % or more, and the molar ratio (A-32 / A-1) of the structural unit (A-32) to the structural unit (A-1) and the content x of the above general formula (XX) satisfy the following condition (C2) or (D2).

[0210] Condition (C2): A-32 / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0211] Condition (D2): A-32 / A-1 is 1.0 / 99.0 or more and 27.0 / 73.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0212] In the above condition (C2), A-32 / A-1 is preferably 32.0 / 68.0 or less, and more preferably 28.0 / 72.0 or less. Furthermore, A-32 / A-1 in the condition (C2) is preferably 1.0 / 99.0 to 32.0 / 68.0, and more preferably 1.0 / 99.0 to 28.0 / 72.0.

[0213] In the above condition (D2), A-32 / A-1 is preferably 24.0 / 76.0 or less, and more preferably 21.0 / 79.0 or less. Furthermore, A-32 / A-1 in the condition (D2) is preferably 1.0 / 99.0 to 24.0 / 76.0, and more preferably 1.0 / 99.0 to 21.0 / 79.0.

[0214] In the polycarbonate-polyorganosiloxane copolymer (S-2), the total content of the structural units (A-1) and (A-32) in the polycarbonate block is preferably 100.0 mol %.

[0215] As one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-3), wherein the polycarbonate-polyorganosiloxane copolymer (S-3) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1) and a structural unit (A-33) represented by the general formula (33), and a polyorganosiloxane block comprising a structure (A-2) represented by the general formula (2), wherein the molar ratio (A-33 / A-1) of the structural unit (A-33) relative to the structural unit (A-1) and the content x of the general formula (XX) satisfy the following condition (C3) or (D3).

[0216] Condition (C3): A-33 / A-1 is 1.0 / 99.0 or more and 40.0 / 60.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0217] Condition (D3): A-33 / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0218] In the above condition (C3), A-33 / A-1 is preferably 35.0 / 65.0 or less, and more preferably 30.0 / 70.0 or less. Furthermore, A-33 / A-1 in the condition (C3) is preferably 1.0 / 99.0 to 35.0 / 65.0, and more preferably 1.0 / 99.0 to 30.0 / 70.0.

[0219] A-33 / A-1 in the above condition (D3) is preferably 33.0 / 67.0 or less, and more preferably 31.0 / 69.0 or less. Furthermore, A-33 / A-1 in the condition (D3) is preferably 1.0 / 99.0 to 33.0 / 67.0, and more preferably 1.0 / 99.0 to 31.0 / 69.0.

[0220] In the polycarbonate-polyorganosiloxane copolymer (S-3), the total content of the structural units (A-1) and (A-33) in the polycarbonate block is preferably 70.0 mol % or more, more preferably 80.0 mol % or more, further preferably 90.0 mol % or more, and further preferably 100.0 mol %.

[0221] As an embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-4), wherein the polycarbonate-polyorganosiloxane copolymer (S-4) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1), a structural unit (A-32) represented by the general formula (32), and a structural unit (A-33) represented by the general formula (33), and a polycarbonate block comprising a structural unit (A-2) represented by the general formula (2). In the organosiloxane block, the molar ratio of the sum of the structural units (A-32) and (A-33) to the structural unit (A-1) ((the sum of A-32 and A-33) / A-1)), the molar ratio of the structural unit (A-32) to the structural unit (A-33) (A-32 / A-33) and the content x of the general formula (XX) satisfy the following conditions (C41), (C42), (C43), (D41), (D42) or (D43).

[0222] Condition (C41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 39.0 / 61.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0223] Condition (C42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 31.0 / 69.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0224] Condition (C43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 46.0 / 54.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0225] Condition (D41): A-32 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 32.0 / 68.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0226] Condition (D42): A-32 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 36.0 / 64.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0227] Condition (D43): A-32 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-32 and A-33) / A-1 is 1.0 / 99.0 or more and 41.0 / 59.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0228] In the above condition (C41), (the total of A-32 and A-33) / A-1 is preferably 35.0 / 65.0 or less, and more preferably 31.0 / 69.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (C41) is preferably 1.0 / 99.0 to 35.0 / 65.0, and more preferably 1.0 / 99.0 to 31.0 / 69.0.

[0229] In the above condition (C42), (the total of A-32 and A-33) / A-1 is preferably 30.0 / 70.0 or less, and more preferably 25.0 / 75.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (C42) is preferably 1.0 / 99.0 to 30.0 / 70.0, and more preferably 1.0 / 99.0 to 25.0 / 75.0.

[0230] In the above condition (C43), (the total of A-32 and A-33) / A-1 is preferably 42.0 / 58.0 or less, and more preferably 37.0 / 63.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (C43) is preferably 1.0 / 99.0 to 42.0 / 58.0, and more preferably 1.0 / 99.0 to 37.0 / 63.0.

[0231] In the above condition (D41), (the total of A-32 and A-33) / A-1 is preferably 28.0 / 72.0 or less, and more preferably 25.0 / 75.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (D41) is preferably 1.0 / 99.0 to 28.0 / 72.0, and more preferably 1.0 / 99.0 to 25.0 / 75.0.

[0232] In the above condition (D42), (the total of A-32 and A-33) / A-1 is preferably 31.0 / 69.0 or less, and more preferably 28.0 / 72.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (D42) is preferably 1.0 / 99.0 to 31.0 / 69.0, and more preferably 1.0 / 99.0 to 28.0 / 72.0.

[0233] In the above condition (D43), (the total of A-32 and A-33) / A-1 is preferably 35.0 / 65.0 or less, and more preferably 32.0 / 68.0 or less. Furthermore, (the total of A-32 and A-33) / A-1 in the condition (D43) is preferably 1.0 / 99.0 to 35.0 / 65.0, and more preferably 1.0 / 99.0 to 32.0 / 68.0.

[0234] In the polycarbonate-polyorganosiloxane copolymer (S-4), the total content of the structural units (A-1), (A-32) and (A-33) in the polycarbonate block is preferably 70.0 mol % or more, more preferably 80.0 mol % or more, further preferably 90.0 mol % or more, and further preferably 100.0 mol %.

[0235] As an embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-5), wherein the polycarbonate-polyorganosiloxane copolymer (S-5) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1), a structural unit (A-31) represented by the general formula (31), and a structural unit (A-33) represented by the general formula (33), and a polycarbonate block comprising a structural unit (A-2) represented by the general formula (2). In the organosiloxane block, the molar ratio of the sum of the structural units (A-31) and (A-33) to the structural unit (A-1) ((the sum of A-31 and A-33) / A-1)), the molar ratio of the structural unit (A-31) to the structural unit (A-33) (A-31 / A-33) and the content x of the general formula (XX) satisfy the following conditions (C51), (C52), (C53), (D51), (D52) or (D53).

[0236] Condition (C51): A-31 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 39.0 / 61.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0237] Condition (C52): A-31 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 43.0 / 57.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0238] Condition (C53): A-31 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 46.0 / 54.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0239] Condition (D51): A-31 / A-33 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 34.0 / 66.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0240] Condition (D52): A-31 / A-33 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 38.0 / 62.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0241] Condition (D53): A-31 / A-33 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 41.0 / 59.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0242] In the above condition (C51), (the total of A-31 and A-33) / A-1 is preferably 34.0 / 66.0 or less, and more preferably 29.0 / 71.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (C51) is preferably 1.0 / 99.0 to 34.0 / 66.0, and more preferably 1.0 / 99.0 to 29.0 / 71.0.

[0243] In the above condition (C52), (the total of A-31 and A-33) / A-1 is preferably 38.0 / 62.0 or less, and more preferably 33.0 / 67.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (C52) is preferably 1.0 / 99.0 to 38.0 / 62.0, and more preferably 1.0 / 99.0 to 33.0 / 67.0.

[0244] In the above condition (C53), (the total of A-31 and A-33) / A-1 is preferably 41.0 / 59.0 or less, and more preferably 36.0 / 64.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (C53) is preferably 1.0 / 99.0 to 41.0 / 59.0, and more preferably 1.0 / 99.0 to 36.0 / 64.0.

[0245] In the above condition (D51), (the total of A-31 and A-33) / A-1 is preferably 28.0 / 72.0 or less, and more preferably 22.0 / 78.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (D51) is preferably 1.0 / 99.0 to 28.0 / 72.0, and more preferably 1.0 / 99.0 to 22.0 / 78.0.

[0246] In the above condition (D52), (the total of A-31 and A-33) / A-1 is preferably 32.0 / 68.0 or less, and more preferably 26.0 / 74.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (D52) is preferably 1.0 / 99.0 to 32.0 / 68.0, and more preferably 1.0 / 99.0 to 26.0 / 74.0.

[0247] In the above condition (D53), (the total of A-31 and A-33) / A-1 is preferably 35.0 / 65.0 or less, and more preferably 31.0 / 69.0 or less. Furthermore, (the total of A-31 and A-33) / A-1 in the condition (D53) is preferably 1.0 / 99.0 to 35.0 / 65.0, and more preferably 1.0 / 99.0 to 31.0 / 69.0.

[0248] In the polycarbonate-polyorganosiloxane copolymer (S-5), the total content of the structural units (A-1), (A-31) and (A-33) in the polycarbonate block is preferably 70.0 mol % or more, more preferably 80.0 mol % or more, further preferably 90.0 mol % or more, and further preferably 100.0 mol %.

[0249] As an embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-6), wherein the polycarbonate-polyorganosiloxane copolymer (S-6) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1), a structural unit (A-31) represented by the general formula (31), and a structural unit (A-32) represented by the general formula (32), and a polycarbonate block comprising a structural unit (A-2) represented by the general formula (2). In the organosiloxane block, the molar ratio of the sum of the structural units (A-31) and (A-32) to the structural unit (A-1) ((the sum of A-31 and A-32) / A-1)), the molar ratio of the structural unit (A-31) to the structural unit (A-32) (A-31 / A-32) and the content x of the general formula (XX) satisfy the following conditions (C61), (C62), (C63), (D61), (D62) or (D63).

[0250] Condition (C61): A-31 / A-32 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0251] Condition (C62): A-31 / A-32 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 35.0 / 65.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0252] Condition (C63): A-31 / A-32 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-33) / A-1 is 1.0 / 99.0 or more and 43.0 / 57.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %.

[0253] Condition (D61): A-31 / A-32 is 60.0 / 40.0 or more and 99.0 / 1.0 or less, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 29.0 / 71.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0254] Condition (D62): A-31 / A-32 is 40.0 / 60.0 or more and less than 60.0 / 40.0, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 29.0 / 71.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0255] Condition (D63): A-31 / A-32 is 1.0 / 99.0 or more and less than 40.0 / 60.0, (total of A-31 and A-32) / A-1 is 1.0 / 99.0 or more and 37.0 / 63.0 or less, and x is 4.0 mass % or more and 10.0 mass % or less.

[0256] In the above condition (C61), (the total of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, and more preferably 26.0 / 74.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (C61) is preferably 1.0 / 99.0 to 31.0 / 69.0, and more preferably 1.0 / 99.0 to 26.0 / 74.0.

[0257] In the above condition (C62), (the total of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, and more preferably 27.0 / 73.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (C62) is preferably 1.0 / 99.0 to 31.0 / 69.0, and more preferably 1.0 / 99.0 to 27.0 / 73.0.

[0258] In the above condition (C63), (the total of A-31 and A-32) / A-1 is preferably 38.0 / 62.0 or less, and more preferably 33.0 / 67.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (C63) is preferably 1.0 / 99.0 to 38.0 / 62.0, and more preferably 1.0 / 99.0 to 33.0 / 67.0.

[0259] In the above condition (D61), (the total of A-31 and A-32) / A-1 is preferably 25.0 / 75.0 or less, and more preferably 18.0 / 82.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (D61) is preferably 1.0 / 99.0 to 25.0 / 75.0, and more preferably 1.0 / 99.0 to 18.0 / 82.0.

[0260] In the above condition (D62), (the total of A-31 and A-32) / A-1 is preferably 25.0 / 75.0 or less, and more preferably 19.0 / 81.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (D62) is preferably 1.0 / 99.0 to 25.0 / 75.0, and more preferably 1.0 / 99.0 to 19.0 / 81.0.

[0261] In the above condition (D63), (the total of A-31 and A-32) / A-1 is preferably 31.0 / 69.0 or less, and more preferably 27.0 / 73.0 or less. Furthermore, (the total of A-31 and A-32) / A-1 in the condition (D63) is preferably 1.0 / 99.0 to 31.0 / 69.0, and more preferably 1.0 / 99.0 to 27.0 / 73.0.

[0262] In the polycarbonate-polyorganosiloxane copolymer (S-6), the total content of the structural units (A-1), (A-31) and (A-32) in the polycarbonate block is preferably 70.0 mol % or more, more preferably 80.0 mol % or more, further preferably 90.0 mol % or more, and further preferably 100.0 mol %.

[0263] As one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-7), wherein the polycarbonate-polyorganosiloxane copolymer (S-7) comprises a polycarbonate block comprising a structural unit (A-1) represented by the above general formula (1) and a polyorganosiloxane block comprising a structure (A-2) represented by the above general formula (2), and satisfies at least one condition selected from the following conditions (E1) to (E5).

[0264] Condition (E1): The weight average molecular weight of the polycarbonate-polyorganosiloxane copolymer in terms of polystyrene is 27,000 or more;

[0265] Condition (E2): The melt flow rate (MFR) of the polycarbonate-polyorganosiloxane copolymer measured at 230° C. and a load of 2.13 kg in accordance with JIS K 7210 is 25 g / 10 min or less;

[0266] Condition (E3): Using a JIS K7139 dumbbell-shaped tensile test piece A1 type injection molded at a cylinder temperature of 200 to 270° C. and a mold of 80° C., the tensile modulus of the polycarbonate-polyorganosiloxane copolymer measured at 1 mm / min in accordance with ISO 527-1, 2:2012 is 2500 MPa or more;

[0267] Condition (E4): Using a JIS K7139 dumbbell-shaped tensile test piece A1 type injection molded at a cylinder temperature of 200 to 270°C and a mold temperature of 80°C, the tensile strength (yield) of the polycarbonate-polyorganosiloxane copolymer measured in accordance with ISO 527-1, 2:2012 is 65 MPa or more;

[0268] Condition (E5): According to JIS K 7121, after holding at 50°C for 1 minute, the temperature is increased to 200°C, after holding at 200°C for 5 minutes, the temperature is cooled to 50°C, after holding at 50°C for 5 minutes, the temperature is increased from 50°C to 200°C at a rate of 20°C / min, and the midpoint glass transition temperature at this time is 115°C or higher.

[0269] The content x in the above conditions (C1), (C2), (C3), (C41), (C42), (C43), (C51), (C52), (C53), (C61), (C62) and (C63) is preferably 2.0 mass % or more, more preferably 3.0 mass % or more.

[0270] The content x in the above conditions (D1), (D2), (D3), (D41), (D42), (D43), (D51), (D52), (D53), (D61), (D62), and (D63) is preferably 4.3% by mass or more, more preferably 4.5% by mass or more, and is preferably 9.0% by mass or less, more preferably 6.0% by mass or less. Furthermore, the content x under these conditions is preferably 4.3 to 9.0% by mass, more preferably 4.5 to 6.0% by mass.

[0271] The polycarbonate-polyorganosiloxane copolymer (S-7) preferably satisfies at least two conditions selected from the above conditions (E1) to (E5), more preferably satisfies at least three conditions selected from the above conditions (E1) to (E5), further preferably satisfies at least four conditions selected from the above conditions (E1) to (E5), and most preferably satisfies all of the above conditions (E1) to (E5).

[0272] The weight average molecular weight in the above condition (E1) is preferably 32,000 or more.

[0273] The melt flow rate in the above condition (E2) is preferably 15 g / 10 min or less.

[0274] The tensile modulus in the above condition (E3) is preferably 2600 MPa or more.

[0275] The tensile strength (yield) in the above condition (E4) is preferably 70 MPa or more.

[0276] The glass transition temperature in the above condition (E5) is preferably 120° C. or higher.

[0277] As one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention may be a polycarbonate-polyorganosiloxane copolymer (S-8), wherein the polycarbonate-polyorganosiloxane copolymer (S-8) comprises a polycarbonate block comprising a structural unit (A-1) represented by the general formula (1) and a polyorganosiloxane block comprising a structure (A-2) represented by the general formula (2), wherein the content of the structural unit represented by the general formula (XX) is 2.0 mass % or more and 25.0 mass % or less.

[0278] The content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (S-8) is preferably 4.0% by mass or more, more preferably 6.0% by mass or more, and even more preferably 8.0% by mass or more, and is preferably 20.0% by mass or less, more preferably 15.0% by mass or less, and even more preferably 13.0% by mass or less. Furthermore, the content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer (S-8) is preferably 4.0 to 20.0% by mass, more preferably 6.0 to 15.0% by mass, and even more preferably 8.0 to 13.0% by mass.

[0279] The polycarbonate-polyorganosiloxane copolymer of the present invention is preferably the above-mentioned polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5), (S-6), (S-7), or (S-8), more preferably the above-mentioned polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), or (S-7), and further preferably (S-2), (S-4), or (S-7).

[0280] From the viewpoint of improving scratch resistance and impact resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, further preferably 11,500 or more, and preferably 30,000 or less, more preferably 25,000 or less, further preferably 20,000 or less, further preferably 15,000 or less. Furthermore, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 5,000 to 30,000, more preferably 8,000 to 25,000, further preferably 10,000 to 20,000, further preferably 11,500 to 15,000.

[0281] In particular, from the viewpoint of further improving scratch resistance, the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 10,000 or more, more preferably 11,000 or more, and even more preferably 11,500 or more.

[0282] The weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer is preferably 20,000 or more, more preferably 25,000 or more, further preferably 30,000 or more, further preferably 33,000 or more, and preferably 60,000 or less, more preferably 50,000 or less, further preferably 45,000 or less, further preferably 43,000 or less. Furthermore, the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer is preferably 20,000 to 60,000, more preferably 25,000 to 50,000, further preferably 30,000 to 45,000, further preferably 33,000 to 43,000.

[0283] In particular, from the viewpoint of further improving scratch resistance, the weight average molecular weight (Mw) of the polycarbonate-polyorganosiloxane copolymer is preferably 30,000 or more, more preferably 31,000 or more, and even more preferably 33,000 or more.

[0284] The reason why the scratch resistance is improved by adjusting the number average molecular weight and the weight average molecular weight to the above range is not yet clear, but is presumed as follows.

[0285] It is considered that by setting the number average molecular weight and the weight average molecular weight to a certain level or more, the entanglement and interaction between polymer chains are strengthened, and the rigidity of the entire resin is improved, thereby improving the scratch resistance.

[0286] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer is preferably 1.8 or more, more preferably 2.2 or more, and further preferably 2.5 or more, and is preferably 3.2 or less, more preferably 3.0 or less, and further preferably 2.9 or less. Furthermore, the ratio (Mw / Mn) is preferably 1.8 to 3.2, more preferably 2.2 to 3.0, and further preferably 2.5 to 2.9.

[0287] <Method for producing polycarbonate-polyorganosiloxane copolymer>

[0288] The polycarbonate-polyorganosiloxane copolymer can be produced, for example, by using a diol monomer (a1) and a polyorganosiloxane (a2), and if necessary, a diol monomer (a3) ​​as raw material monomers.

[0289] <<Diol monomer (a1)>>

[0290] The diol monomer (a1) has a structure represented by the following general formula (1a). The diol monomer (a1) preferably contains a diol represented by the following general formula (11a), and more preferably consists of a diol represented by the following general formula (11a).

[0291] [Chemical formula 26]

[0292]

[0293] [Chemical formula 27]

[0294]

[0295] <<Diol monomer (a3)>>

[0296] When the polycarbonate-polyorganosiloxane copolymer contains the structural unit (A-3), a diol monomer (a3) ​​is further contained as a raw material monomer.

[0297] The diol monomer (a3) ​​is preferably at least one diol selected from the group consisting of diols represented by the general formulae (3a) and (4a).

[0298] [Chemical formula 28]

[0299]

[0300] In the general formulas (3a) and (4a), R 11 and R 12 As described above, the preferred examples are also the same.

[0301] In addition, the diol monomer (a1) is not included in the diol monomer (a3).

[0302] <<Polyorganosiloxane (a2)>>

[0303] The polyorganosiloxane (a2) preferably includes a polyorganosiloxane structure represented by the following general formula (21a).

[0304] [Chemical formula 29]

[0305]

[0306] In the general formula (21a), R 1 ~R 8 , a, b, u and z are as described above, and preferred examples are also the same. Among them, z present at the terminal is 1, that is, the hydrogen atoms at both terminals are bonded to oxygen atoms.

[0307] The polyorganosiloxane (a2) preferably contains a polyorganosiloxane represented by the following general formula (22a).

[0308] [Chemical formula 30]

[0309]

[0310] In the general formula (22a), R 1 ~R 8, a, b, u, u1, z and z1 are as described above, and preferred examples are also the same. Among them, z and z1 present at both ends are 1, that is, the hydrogen atoms at both ends are bonded to oxygen atoms.

[0311] The polyorganosiloxane (a2) preferably contains at least one of the polyorganosiloxanes represented by the following general formulas (23a) to (26a).

[0312] [Chemical formula 31]

[0313]

[0314] In the general formulas (23a) to (26a), R 1 ~R 8 , a, b, b1, u, u1, z, z1 and β are as described above, and the preferred examples are also the same. In general formulae (23a) to (26a), z and z1 present at the terminal are 1, that is, the terminal hydrogen atom is bonded to the oxygen atom.

[0315] The method for producing the polyorganosiloxane (a2) is not particularly limited. For example, according to the method described in Japanese Patent Application Laid-Open No. 11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α,ω-dihydroorganopentasiloxane, and then, in the presence of a catalyst for a hydrosilylation reaction, the α,ω-dihydroorganopentasiloxane is subjected to an addition reaction with an oligomer or polymer (such as polyalkylene ether, polyester, polycarbonate, etc.) modified at one end with an allyl group, thereby obtaining the polyorganosiloxane. In addition, according to the method described in Japanese Patent Gazette No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the obtained α,ω-dihydroorganopolysiloxane is subjected to addition reaction with an oligomer or polymer modified at one end with an allyl group in the presence of a catalyst for hydrosilylation reaction in the same manner as above, thereby obtaining. It should be noted that α,ω-dihydroorganopolysiloxane can also be used after its average chain length is appropriately adjusted by its polymerization conditions, and commercially available α,ω-dihydroorganopolysiloxane can also be used. In addition, the oligomer modified at one end with an allyl group can also be used after its average number of repeating units is appropriately adjusted by its polymerization conditions, and commercially available single-end allyl-modified oligomers can also be used. The single-end allyl-modified polyethylene glycol among the single-end allyl-modified oligomers can be manufactured with reference to Japanese Patent No. 5652691, etc. Examples of 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.

[0316] The polycarbonate-polyorganosiloxane copolymer can be produced by polymerizing a mixture of raw material monomers by using an interfacial polymerization method or a melt polymerization method (ester exchange method). When the interfacial polymerization method is used for production, for example, the method described in Japanese Patent Publication No. 2014-80462 can be used. Preferably, the polyorganosiloxane (a2), the diol monomer (a1) and the carbonate compound described later as the raw material monomers can be reacted by a melt polymerization method in the presence of a basic catalyst to produce the polycarbonate-polyorganosiloxane copolymer. As the raw material monomer, a diol monomer (a3) ​​can be used as needed. In addition, a capping agent can be further added to carry out the polymerization reaction.

[0317] The melt polymerization method is environmentally and economically advantageous because it does not require solvents such as dichloromethane required in the interfacial polymerization method. In addition, it is also advantageous in terms of manufacturing because it does not use the highly toxic phosgene used in the interfacial polymerization method. Therefore, the polycarbonate-polyorganosiloxane copolymer is preferably manufactured by the melt polymerization method.

[0318] (Carbonate compounds)

[0319] Examples of the carbonate compound include diaryl carbonate compounds, dialkyl carbonate compounds, and alkyl aryl carbonate compounds.

[0320] 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).

[0321] [Chemical formula 32]

[0322]

[0323] In the general formulas (41) and (42), Ar 1 and Ar 2 represent aromatic groups, and may be the same or different from each other. 3 and Ar 4 represent aryl groups, which may be the same or different from each other, D 1 It represents the above-mentioned divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms, the above-mentioned divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the above-mentioned divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the above-mentioned divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0324] 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).

[0325] [Chemical formula 33]

[0326]

[0327] In general formulas (43) and (44), R 21 and R 22 Each of them represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and they may be the same or different from each other. 23 and R 24 Each of them represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and they may be the same or different from each other. 2 It represents the above-mentioned divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms, the above-mentioned divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the above-mentioned divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the above-mentioned divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0328] 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).

[0329] [Chemical formula 34]

[0330]

[0331] In the general formulas (45) and (46), Ar 5 Represents 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 Represents an aryl group, R 26 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D 3 It represents the above-mentioned divalent straight-chain aliphatic hydrocarbon group having 2 to 40 carbon atoms, the above-mentioned divalent branched aliphatic hydrocarbon group having 3 to 40 carbon atoms, the above-mentioned divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or the above-mentioned divalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0332] Examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, dichlorophenyl carbonate, dinaphthyl carbonate, bis(biphenyl) carbonate, and bisphenol A bisphenyl carbonate.

[0333] Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A dimethyl carbonate.

[0334] Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate.

[0335] A preferred carbonate compound is diphenyl carbonate.

[0336] In the production of the polycarbonate-polyorganosiloxane copolymer, one or two or more carbonate compounds may be used.

[0337] (Capping agent)

[0338] When the polycarbonate-polyorganosiloxane copolymer is manufactured, an end-capping agent may be used as required. As the end-capping agent, any known end-capping agent used in the manufacture of polycarbonate resins may be used, and specific compounds thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. Each of these monohydric phenols may be used alone, or two or more may be used in combination.

[0339] (Branching Agent)

[0340] When the polycarbonate-polyorganosiloxane copolymer is produced, a branching agent may be used. Examples of the branching agent include phloroglucinol, 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 indigo carmine di(o-cresol).

[0341] Specifically, for example, the polycarbonate-polyorganosiloxane copolymer can be produced by the melt polymerization method according to the following steps.

[0342] A mixture of raw material monomers including a diol monomer (a1), a polyorganosiloxane (a2) and a carbonate compound is subjected to an ester exchange reaction. The mixture of raw material monomers may contain a diol monomer (a3) ​​as required. The amount of the carbonate compound relative to the total amount of the diol monomers (a1) and (a3) ​​is preferably 0.9 to 1.2 times the mole, and more preferably 0.95 to 1.05 times the mole.

[0343] When the diol monomers (a1) and (a3) ​​are more volatile than the carbonate compound under polymerization conditions, the ratio of the amount of the carbonate compound to the total amount of the diol monomers (a1) and (a3) ​​is preferably 1 or less.

[0344] When the diol monomers (a1) and (a3) ​​are less volatile than the carbonate compound under polymerization conditions, the ratio of the amount of the carbonate compound to the total amount of the diol monomers (a1) and (a3) ​​is preferably 1 or more.

[0345] By adjusting the ratio of the amount of the carbonate compound to the total amount of the diol monomers (a1) and (a3) ​​to the above range, the number average molecular weight and the weight average molecular weight of the obtained polycarbonate-polyorganosiloxane copolymer can be increased.

[0346] In the above-mentioned transesterification reaction, when a capping agent is used, if the amount of the capping agent is in the range of 0.05 to 10 mol% relative to the total amount of the diol monomer (a1), the polyorganosiloxane (a2) and the polyorganosiloxane (a3) ​​as required, the hydroxyl terminal of the obtained polycarbonate-polyorganosiloxane copolymer is sufficiently capped, which is preferred from the viewpoint of being able to obtain a polycarbonate resin with excellent heat resistance and water resistance. The amount of the capping agent is more preferably 1 to 6 mol% relative to the total amount of the diol monomer (a1), the polyorganosiloxane (a2) and the polyorganosiloxane (a3) ​​as required. The capping agent may be added to the reaction system in total in advance, or a portion may be added to the reaction system in advance and the remaining portion may be added as the reaction proceeds.

[0347] It is preferred that an antioxidant is simultaneously introduced into a reactor together with the diol monomer (a1), the polyorganosiloxane (a2) and the carbonate compound, and the transesterification reaction is carried out in the presence of the antioxidant.

[0348] When the transesterification reaction is carried out, the reaction temperature is not particularly limited, and may be, for example, in the range of 100 to 330° C., preferably in the range of 150 to 300° C., and more preferably in the range of 170 to 240° C. In addition, a method of gradually raising the temperature from 150° C. to 300° C. in accordance with the progress of the reaction is preferred, and a method of gradually raising the temperature from 170° C. to 240° C. is more preferred. If the temperature of the transesterification reaction is 100° C. or higher, the reaction rate becomes sufficiently high, while if it is 330° C. or lower, side reactions do not occur in large quantities, and problems such as coloration of the generated polycarbonate-polyorganosiloxane copolymer are less likely to occur.

[0349] The final temperature in the reactor is preferably 210°C or higher, more preferably 225°C or higher.

[0350] The reaction pressure is set according to the vapor pressure of the monomers used and the reaction temperature. There is no particular limitation as long as the reaction is carried out efficiently. For example, it is preferably set to 1.01×10 5 ~5.07×10 6 Pa atmospheric pressure (normal pressure) or pressurized state, in the later stage of the reaction, it is set to a reduced pressure state, and finally set to 1.33~1.33×10 4 Pa.

[0351] The reaction time may be carried out until the target molecular weight is reached, for example, 0.2 to 10 hours.

[0352] The above-mentioned transesterification reaction is carried out, for example, in the absence of an inert solvent, but can also be carried out in the presence of 1 to 150 parts by mass of an inert solvent based on 100 parts by mass of the obtained polycarbonate resin as required. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene and methylnaphthalene; and tricyclic [5.2.1.0 2，6 ]Cycloalkanes such as decane, cyclooctane and cyclodecane, etc.

[0353] If necessary, the reaction may be carried out in an inert gas atmosphere. Examples of the inert gas include various inert gases such as argon, carbon dioxide, nitrous oxide, nitrogen, chlorofluorocarbons, alkanes such as ethane and propane, and olefins such as ethylene and propylene.

[0354] In the melt polymerization method, a basic catalyst is preferably used as a catalyst. As the basic catalyst, at least one selected from metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing aromatic groups, and metal compounds can be cited. These compounds can be used alone or in combination.

[0355] As the basic catalyst, it is preferred to use at least one selected from organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alcoholates of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing an aryl group, and it is more preferred to use an alkali metal hydroxide. The basic catalyst may be used alone or in combination of two or more.

[0356] Examples of the alkali metal compound 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 phenyl phosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, and sodium salt, potassium salt, cesium salt, lithium salt of phenol.

[0357] Examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate.

[0358] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having an alkyl group, an aryl group, and the like such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. In addition, examples include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. In addition, examples include alkalis or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0359] Examples of the metal compound include zinc-aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0360] Specific examples of the quaternary phosphonium salt containing an aryl group include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide and the like tetra(aryl or alkyl)phosphonium hydroxides, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-tert-butylphenyl)phosphonium diphenyl phosphate, triphenylbutylphosphonium phenolate, triphenylbutylphosphonium tetraphenylborate and the like.

[0361] The quaternary phosphonium salt containing an aromatic group is preferably combined with a nitrogen-containing organic basic compound, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0362] The amount of the basic catalyst used may be preferably 1×10 -9 ~1×10 -2 mole, preferably 1×10 -8 ~1×10 -4 mole, more preferably 1×10 -7 ~1×10 -5 Select from the range of moles.

[0363] A catalyst deactivator may be added at the later stage of the reaction. As the catalyst deactivator used, a known catalyst deactivator is effectively used. Examples of the catalyst deactivator include sulfonic acid esters, ammonium salts of sulfonic acid, and phosphonium salts of sulfonic acid.

[0364] Regarding the amount of the catalyst deactivator used, when using at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds, it can be preferably used in a ratio of 0.5 to 50 mol, more preferably in a ratio of 1.0 to 30 mol, and further preferably in a ratio of 5.0 to 15 mol, relative to 1 mol of the catalyst.

[0365] It is preferred to add a catalyst deactivator and mix an antioxidant after the polymerization reaction is completed.

[0366] The reaction in the melt polymerization method can be carried out in any of a continuous method and an intermittent method. The reaction device used in the melt polymerization can be a vertical reaction device equipped with an anchor-type stirring blade, a maximum blade (MAXBLEND) stirring blade, or a spiral ribbon stirring blade, or a horizontal reaction device equipped with a paddle blade, a grid blade, or a spectacle blade. In addition, it can also be an extruder type equipped with a screw. In the case of a continuous method, it is preferred to use these reaction devices in appropriate combination.

[0367] From the viewpoint of improving the impact resistance of the obtained molded body, the Charpy impact strength of the molded piece obtained by post-processing the polycarbonate-polyorganosiloxane copolymer of the present invention to form a long strip-shaped molded piece with a length of 80 mm, a width of 10 mm, and a thickness of 3 mm and giving a notch (r = 0.25 mm ± 0.05 mm) was 15 kJ / m 2 Above, preferably 18 kJ / m 2 More preferably 30 kJ / m 2 More preferably, 40 kJ / m 2 From the viewpoint of further improving the impact resistance of the obtained molded body, the higher the Charpy impact strength, the better. Therefore, the upper limit is not particularly limited. From the viewpoint of improving tensile properties, it is preferably 110 kJ / m 2 Below, more preferably 95 kJ / m 2 Below, more preferably 85 kJ / m 2 the following.

[0368] As the ratio of the polyorganosiloxane block increases, the Charpy impact strength of the polycarbonate-polyorganosiloxane copolymer can be improved. When the ratio of the polyorganosiloxane unit (A-2) is high, the Charpy impact strength of the polycarbonate-polyorganosiloxane copolymer of the present invention becomes high.

[0369] The method for adjusting the Charpy impact strength of the molded article of the polycarbonate-polyorganosiloxane copolymer to the above range is not particularly limited, and examples thereof include a method using the above-mentioned polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5) or (S-6).

[0370] The Charpy impact strength can be measured at a measurement temperature of 23° C. in accordance with ISO-179-1:2010, and specifically, can be measured by the method described in the examples described below.

[0371] The forming conditions of the above-mentioned formed sheet are a barrel temperature of 200 to 270° C., a mold temperature of 80° C., and a cycle time of 60 seconds. It should be noted that the barrel temperature can be appropriately set according to the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer used. Specifically, the formed sheet can be obtained by the method described in the examples described below.

[0372] From the viewpoint of improving the scratch resistance of the obtained molded body, the scratch hardness (pencil method) of the molded body of the polycarbonate-polyorganosiloxane copolymer of the present invention is HB or more, preferably F or more. From the viewpoint of further improving the scratch resistance of the obtained molded body, the harder the scratch hardness is, the more preferable it is, so the upper limit is not particularly limited.

[0373] The higher the ratio of the structure having a rigid skeleton, the higher the scratch hardness of the polycarbonate-polyorganosiloxane copolymer. When the ratio of the structural unit (A-1) represented by the general formula (1) is high, the scratch hardness of the polycarbonate-polyorganosiloxane copolymer of the present invention becomes high.

[0374] The method for adjusting the scratch hardness of the molded body of the polycarbonate-polyorganosiloxane copolymer to the above range is not particularly limited, and examples thereof include a method using the above-mentioned polycarbonate-polyorganosiloxane copolymer (S-1), (S-2), (S-3), (S-4), (S-5) or (S-6).

[0375] The scratch hardness can be measured in accordance with JIS K 5600-5-4: 1999, and specifically, can be measured by the method described in the examples described below.

[0376] From the viewpoint of obtaining a molded product having excellent transparency, the total transmittance of a flat plate having a thickness of 1.0 mm obtained by molding the polycarbonate-polyorganosiloxane copolymer of the present invention to visible light is preferably 60% or more, more preferably 70% or more, further preferably 80% or more, further preferably 85% or more, further preferably 90% or more.

[0377] The total light transmittance can be measured according to ISO 13468-1:1996.

[0378] From the viewpoint of fluidity, the melt flow rate (MFR) of the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 1.0 g / 10 min or more, more preferably 2.5 g / 10 min or more, and further preferably 3.0 g / 10 min or more, and from the viewpoint of improving damage resistance, it is preferably 25.0 g / 10 min or less, more preferably 20.0 g / 10 min or less, and further preferably 15.0 g / 10 min or less. The higher the MFR, the better the fluidity. The MFR is measured by the measurement method specified in ISO 1133:1997, and specifically, can be measured by the method described in the examples described below.

[0379] The reason why the scratch resistance is improved by adjusting the melt flow rate to the above range is not yet clear, but is presumed as follows.

[0380] If the melt flow rate is within the above range, the resin pressure during molding becomes high, and a high pressure is applied to the surface of the molded product. Therefore, it is considered that the polymer on the surface of the molded product becomes dense, resulting in an increase in surface hardness.

[0381] From the viewpoint of further improving the mechanical strength and damage resistance of the obtained molded body, the tensile modulus of the polycarbonate resin composition of the present invention, measured using a JIS K7139 dumbbell tensile test piece A1 type according to ISO 527-1, 2: 2012, is preferably 2400 MPa or more, more preferably 2500 MPa or more, further preferably 2600 MPa or more, and further preferably 2700 MPa or more. From the viewpoint of further improving the damage resistance of the obtained molded body, the higher the tensile modulus, the more preferred, so the upper limit is not particularly limited, but from the viewpoint of improving impact resistance, it is preferably 10000 MPa or less, more preferably 5000 MPa or less, and further preferably 3500 MPa or less.

[0382] The reason why the scratch resistance is improved by adjusting the tensile elastic modulus to the above range is not yet clear, but is presumed as follows.

[0383] When the tensile modulus is within the above range, the rigidity of the resin surface is similarly improved, and when the resin surface is subjected to external pressure or displacement, deformation caused by the pressure or displacement is reduced, so that the scratch resistance is improved.

[0384] As the ratio of the structure having a rigid skeleton increases, the tensile modulus of the polycarbonate-polyorganosiloxane copolymer can be increased. When the ratio of the structural unit (A-1) represented by the general formula (1) is high, the tensile modulus of the polycarbonate-polyorganosiloxane copolymer of the present invention becomes high.

[0385] The tensile modulus can be measured under the conditions of a tensile speed of 1 mm / min and a measurement temperature of 23° C. Specifically, it can be measured by the method described in the Examples described below.

[0386] The forming conditions of the above-mentioned formed sheet are a barrel temperature of 200 to 270° C., a mold temperature of 80° C., and a cycle time of 60 seconds. It should be noted that the barrel temperature can be appropriately set according to the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer used. Specifically, the formed sheet can be obtained by the method described in the examples described below.

[0387] From the viewpoint of further improving the mechanical strength and damage resistance of the obtained molded body, the tensile strength (yield) obtained by molding the polycarbonate resin composition of the present invention and measured using a JIS K7139 dumbbell-shaped tensile test piece A1 type in accordance with ISO 527-1, 2: 2012 is preferably 45 MPa or more, more preferably 50 MPa or more, and even more preferably 55 MPa or more. From the viewpoint of further improving the mechanical strength and damage resistance of the obtained molded body, the higher the tensile strength (yield), the more preferred it is, so the upper limit is not particularly limited, but from the viewpoint of improving impact resistance, it is preferably 200 MPa or less, more preferably 150 MPa or less, even more preferably 100 MPa or less, and even more preferably 80 MPa or less.

[0388] The reason why the scratch resistance is improved by adjusting the tensile strength (yield) to the above range is not yet clear, but is presumed as follows.

[0389] It is believed that when the tensile strength (yield) is within the above range, the resin surface deforms when subjected to pressure or displacement, thereby requiring large pressure or displacement. Therefore, it is believed that when the tensile strength (yield) is within the above range, the damage resistance is improved.

[0390] The tensile strength (yield) can be measured under the conditions of a tensile speed of 50 mm / min and a measurement temperature of 23° C. Specifically, it can be measured by the method described in the examples described below.

[0391] The molding conditions of the molded sheet are as follows: a cylinder temperature of 200 to 270° C., a mold temperature of 80° C., and a cycle time of 60 seconds. The cylinder temperature can be appropriately set according to the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer used.

[0392] From the viewpoint of further improving the damage resistance of the obtained molded body, the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 115° C. or higher, more preferably 120° C. or higher, more preferably 130° C. or higher, and further preferably 140° C. or higher. The higher the glass transition temperature, the more preferred it is, so the upper limit is not particularly limited, but from the viewpoint of improving processability, it is preferably 200° C. or lower, more preferably 180° C. or lower, and further preferably 160° C. or lower.

[0393] The reason why the scratch resistance is improved by adjusting the glass transition temperature to the above range is not yet clear, but is presumed as follows.

[0394] It is believed that when the glass transition temperature is within the above range, the molecular mobility of the resin surface at the use temperature or the test temperature is low, or the interaction between molecules is high. In such a state, there is a tendency that the flexibility of the resin surface is low and the rigidity is improved. As a result, it is believed that the deformation of the resin surface when subjected to pressure and displacement is suppressed, and the damage resistance is improved.

[0395] As the ratio of the structure having a rigid skeleton increases, the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer increases. When the ratio of the structural unit (A-1) represented by the general formula (1) is high, the glass transition temperature of the polycarbonate-polyorganosiloxane copolymer of the present invention increases.

[0396] The glass transition temperature can be specifically measured by the method described in Examples described below.

[0397] 2. Polycarbonate resin composition

[0398] The polycarbonate resin composition of the present invention (hereinafter, sometimes referred to as “resin composition”) may be composed only of the above-mentioned polycarbonate-polyorganosiloxane copolymer, or may contain a polycarbonate resin (P) other than the above-mentioned polycarbonate-polyorganosiloxane copolymer (hereinafter, sometimes referred to as “polycarbonate resin (P)”).

[0399] From the viewpoint of improving the impact resistance, tensile properties and chemical resistance of the molded body, the content of the polycarbonate-polyorganosiloxane copolymer in the polycarbonate resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, further preferably 98% by mass or more, further preferably 99% by mass or more. The upper limit of the content of the polycarbonate-polyorganosiloxane copolymer in the polycarbonate resin composition is not particularly limited, and from the viewpoint of obtaining a resin composition with a desired property, it is, for example, 100% by mass or less.

[0400] From the viewpoint of improving the impact resistance of the molded body, the content of the structural unit represented by the general formula (XX) in the polycarbonate resin composition is preferably 2 mass % or more, more preferably 3 mass % or more, further preferably 4 mass % or more, and is preferably 25 mass % or less, more preferably 20 mass % or less, further preferably 15 mass % or less.

[0401] The number average molecular weight (Mn) of the polycarbonate resin composition is preferably 5,000 or more, more preferably 6,000 or more, further preferably 7,000 or more, further preferably 8,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, further preferably 20,000 or less, further preferably 15,000 or less.

[0402] It should be noted that the number average molecular weight (Mn) of the polycarbonate-based resin composition is a weighted average of the number average molecular weights (Mn) of the copolymers or resins contained in the resin composition, and each number average molecular weight (Mn) can be measured by the same method as the number average molecular weight (Mn) of the polycarbonate-polyorganosiloxane copolymer.

[0403] The number average molecular weight (Mw) of the polycarbonate resin composition is preferably 20,000 or more, more preferably 25,000 or more, further preferably 30,000 or more, further preferably 33,000 or more, and is preferably 60,000 or less, more preferably 50,000 or less, further preferably 45,000 or less, further preferably 43,000 or less.

[0404] <Polycarbonate resin (P)>

[0405] The polycarbonate-based resin (P) is not particularly limited, and various known polycarbonate-based resins can be used.

[0406] The polycarbonate resin (P) preferably does not contain the polyorganosiloxane unit (A-2) containing the structural unit represented by the general formula (2) above, but contains a polycarbonate block (A-1) containing the structural unit represented by the general formula (1) above and / or at least one structural unit (A-3) selected from the structures represented by the general formulas (3) and (4).

[0407] Examples of the structural unit (A-1) and the structural unit (A-3) contained in the polycarbonate-based resin (P) include the same structural units as those contained in the polycarbonate-polyorganosiloxane copolymer, and the preferred embodiments are also the same.

[0408] The polycarbonate resin (P) preferably contains the structural unit (A-1) and the structural unit (A-3) as main components. The polycarbonate resin (P) preferably contains the structural unit (A-1) and the structural unit (A-3) in an amount of 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and further preferably 98% by mass or more, based on the entire structure of the polycarbonate resin (P).

[0409] The number average molecular weight (Mn) of the polycarbonate resin (P) is preferably 5,000 or more, more preferably 6,000 or more, further preferably 7,000 or more, further preferably 8,000 or more, and is preferably 30,000 or less, more preferably 25,000 or less, further preferably 20,000 or less, further preferably 15,000 or less.

[0410] <Antioxidants>

[0411] The polycarbonate resin composition of the present invention may contain an antioxidant appropriately within a range not impairing the purpose of the present invention.

[0412] The antioxidant can suppress the decomposition of the resin during the production and molding of the polycarbonate resin composition. As the antioxidant, a known antioxidant can be used, and at least one selected from a phosphorus antioxidant and a phenolic antioxidant can be preferably used.

[0413] From the viewpoint of suppressing oxidative degradation of a molded body composed of a polycarbonate resin composition during high temperature molding, the phosphorus-based antioxidant is more preferably a phosphorus-based antioxidant having an aromatic group, and more preferably a compound represented by the following general formula (51).

[0414] [Chemical formula 35]

[0415]

[0416] In formula (2), R C21 ~R C25 is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and they may be the same or different. C21 ~R C25 Not all hydrogen atoms, R C21 ~R C25 At least two of them are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms. C21 ~R C25 A compound in which any two of them are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms, and the rest are hydrogen atoms, and more preferably R C21 ~RC25 In a compound in which any two of R are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms, and the rest are hydrogen atoms, C21 or R C25 A compound in which at least one of the above is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms.

[0417] Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, etc. Among them, from the viewpoint of imparting long-term moisture-heat resistance and long-term heat resistance, preferably at least one selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, various hexyl groups, and various octyl groups, more preferably at least one selected from the group consisting of methyl, ethyl, isopropyl, and tert-butyl groups, and further preferably tert-butyl groups.

[0418] Examples of the aryl group having 6 to 14 carbon atoms include phenyl, tolyl, and xylyl. Among them, R C21 ~R C25 More preferably, it is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, further preferably, it is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group or a tert-butyl group, and further preferably, it is a hydrogen atom or a tert-butyl group.

[0419] R is particularly preferred C21 and R C23 is tert-butyl, R C22 , R C24 and R C25 Tris(2,4-di-tert-butylphenyl) phosphite containing a hydrogen atom.

[0420] Examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenyl (nonyl) phosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) phosphite, diphenyl (isooctyl) phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl (isodecyl) phosphite, diphenyl mono (tridecyl) phosphite, phenyl (diisodecyl) phosphite, phenyl di (tridecyl) phosphite, and 1,2-diisodecyl phosphite. Tris(2-ethylhexyl) phosphate, tris(isodecyl) phosphite, tris(tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, 4,4'-isopropylidene diphenol dodecyl phosphite, 4,4'-isopropylidene diphenol tridecyl phosphite, 4,4'-isopropylidene diphenol tetradecyl phosphite, 4,4'-isopropylidene diphenol pentadecyl phosphite, 4,4'-butylidene Bis(3-methyl-6-tert-butylphenyl) di(tridecyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris(2-methyl-4-diphosphite tridecyl-5-tert-butylphenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphine, triphenylphosphine, diphenyl butyl phosphine, diphenyl octadecyl phosphine, tri(p-tolyl) phosphine, tri(p-nonylphenyl) phosphine, tri(naphthyl) phosphine, diphenyl(hydroxymethyl) phosphine, diphenyl(acetoxymethyl) phosphine, diphenyl(β-ethylcarboxyethyl) phosphine, tri(p-chlorophenyl) phosphine, tri(p-fluorophenyl) phosphine, benzyl diphenyl phosphine, diphenyl(β-cyanoethyl) phosphine, diphenyl(p-hydroxyphenyl) phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, etc.

[0421] Specifically, examples of the phosphorus-based antioxidant include commercially available products such as “Irgafos 168” (manufactured by BASF Japan, Ltd., trademark), “Irgafos 12” (manufactured by BASF Japan, Ltd., trademark), “Irgafos 38” (manufactured by BASF Japan, Ltd., trademark), “ADKSTAB 329K” (manufactured by ADEKA Corporation, trademark), “ADKSTAB PEP-36” (manufactured by ADEKA Corporation, trademark), “ADKSTAB PEP-8” (manufactured by ADEKA Corporation, trademark), “Sandstab P-EPQ” (manufactured by Clariant, trademark), “Weston 618” (manufactured by GE, trademark), “Weston 619G” (manufactured by GE, trademark), and “Weston 624” (manufactured by GE, trademark), and “Doverphos S-9228PC” (manufactured by Dover Chemical).

[0422] The phenolic antioxidant is preferably a hindered phenol. Specific examples of the phenolic antioxidant include triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5.5)undecane, etc.

[0423] Specifically, as the phenolic antioxidant, commercially available products such as "Irganox 1010" (manufactured by BASF Japan, Ltd., trademark), "Irganox 1076" (manufactured by BASF Japan, Ltd., trademark), "Irganox 1330" (manufactured by BASF Japan, Ltd., trademark), "Irganox 3114" (manufactured by BASF Japan, Ltd., trademark), "Irganox 3125" (manufactured by BASF Japan, Ltd., trademark), "BHT" (manufactured by Takeda Pharmaceutical Company, Ltd., trademark), "Cyanox 1790" (manufactured by Cyanamid Co., Ltd., trademark), and "Sumilizer GA-80" (manufactured by Sumitomo Chemical Co., Ltd., trademark) can be cited.

[0424] The antioxidant may be used alone or in combination of two or more. The content of the antioxidant in the polycarbonate resin composition of the present invention is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.04 parts by mass or more, further preferably 0.08 parts by mass or more, preferably 1.0 parts by mass or less, more preferably 0.50 parts by mass or less, further preferably 0.25 parts by mass or less, further preferably 0.15 parts by mass or less, relative to 100 parts by mass of the polycarbonate resin composition. When two or more antioxidants are used, the total amount is within the above range.

[0425] 3. Molded body

[0426] The molded body of the present invention comprises the above-mentioned polycarbonate resin composition. The molded body can be manufactured by injection molding, injection compression molding, extrusion molding, blow molding, stamping molding, vacuum forming, foaming molding, etc. using a melt-kneaded product of the polycarbonate resin composition or pellets obtained by melt-kneading as raw materials. In particular, it is preferred to manufacture the molded body by injection molding or injection compression molding using the obtained pellets.

[0427] The thickness of the molded body can be set arbitrarily according to the application. In particular, when the transparency of the molded body is required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and further preferably 0.3 to 2.0 mm. If the thickness of the molded body is 0.2 mm or more, warping will not occur and good mechanical strength can be obtained. In addition, if the thickness of the molded body is 4.0 mm or less, high transparency can be obtained.

[0428] If necessary, a hard coat film, an antifogging film, an antistatic film, or an antireflection film may be formed on the molded article, and a composite film of two or more types may be formed.

[0429] Among them, a coating having a hard coating film is preferred from the perspective of good weather resistance and the ability to prevent wear of the molded body surface over time. The material of the hard coating film is not particularly limited, and known materials such as acrylate hard coating agents, silicone hard coating agents, and inorganic hard coating agents can be used.

[0430] Example

[0431] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples. In the present examples, polydimethylsiloxane may be abbreviated as PDMS.

[0432] 1. Preparation of terminal-modified polyorganosiloxane

[0433] Preparation Example 1: Preparation of PDMS-1

[0434] Under nitrogen atmosphere, in the following formula:

[0435] [Chemical formula 36]

[0436]

[0437] To α,ω-dihydroorganopolysiloxane (100 g) having an average chain length of 25 of the polyorganosiloxane structure shown above, a compound of the formula:

[0438] [Chemical formula 37]

[0439]

[0440] The single-end allyl-modified polyethylene glycol having an average repeating unit number of 15 oxyethylene units is shown. After adding 455 g of isopropyl alcohol (2.5 parts relative to the total mass of α,ω-dihydroorganopolysiloxane and the single-end allyl-modified polyethylene glycol), the mixture temperature is controlled to 80°C and stirred for more than 10 minutes. Next, a toluene solution of a platinum vinylsiloxane complex (platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) as a hydrosilylation catalyst is added in an amount such that the mass of platinum atoms is 5 ppm by mass relative to the siloxane in the above-mentioned polyorganosiloxane, and stirred for 10 hours. Isopropyl alcohol, toluene and platinum catalyst are removed from the obtained mixture to obtain polyether-modified polyorganosiloxane PDMS-1. The structure of the obtained PDMS-1 is shown below.

[0441] [Chemical formula 38]

[0442]

[0443] <Method for measuring the average chain length of polyorganosiloxane and the average number of oxyethylene repeating units of polyethylene glycol>

[0444] The average chain length of the polyorganosiloxane was measured by NMR and calculated from the integrated value ratio of the methyl groups of the polydimethylsiloxane. The average number of repeating units of the polyethylene glycol was measured by NMR and calculated from the integrated value ratio of the dimethylene groups of the polyethylene glycol.

[0445] 1 H-NMR measurement conditions

[0446] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0447] Probe: 50TH5AT / FG2

[0448] Observation range: -5~15ppm

[0449] Observation center: 5ppm

[0450] Pulse repetition time: 9 seconds

[0451] Pulse width: 45°

[0452] NMR sample tube: 5φ

[0453] Sample amount: 30-40 mg

[0454] Solvent: deuterated chloroform

[0455] Measurement temperature: 23°C

[0456] Total times: 256 times

[0457] Correction of chemical shift: The protons in deuterated chloroform ( 1 H) peak was set to 7.26 ppm

[0458] 2. Evaluation of polycarbonate-polyorganosiloxane copolymers

[0459] The following evaluations were performed on pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples, and pellets containing polycarbonate produced in Comparative Examples.

[0460] (1) 1 H-NMR measurement

[0461] Based on the following test conditions 1The integrated value of the peak derived from the following specific structure obtained by H-NMR measurement was used to calculate the contents of the structural unit represented by the general formula (XX), the structural unit (A-1), the structural unit (A-31), the structural unit (A-32) and the structural unit (A-33), the molar fraction of the structural units (A-1), (A-31), (A-32) and (A-33) relative to the total amount of the structural units represented by the formula (X) contained in the PC-POS copolymer, and the -OR T The terminal structure content shown is the average value of a in the polycarbonate-polyorganosiloxane copolymer, and the average value b2 when b and b1 in the polycarbonate-polyorganosiloxane copolymer are added together.

[0462] (Measurement conditions)

[0463] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0464] Probe: TH5 corresponds to 5φNMR sample tube

[0465] Observation range: -5~15ppm

[0466] Observation center: 5ppm

[0467] Pulse repetition time: 9 seconds

[0468] Pulse width: 45°

[0469] Total times: 256 times

[0470] NMR sample tube: 5φ

[0471] Sample amount: 30-40 mg

[0472] Solvent: deuterated chloroform

[0473] Measuring temperature: room temperature

[0474] Chemical shift calibration: The peak of protons derived from chloroform in deuterated chloroform was set to 7.26 ppm.

[0475] A: Peak integration value in the range of δ7.30 to 7.43

[0476] (It should be noted that the peak of protons derived from chloroform in deuterated chloroform also appears in this range, but since the sample concentration is sufficient, it has no effect on the assignment of the structure.)

[0477] B: Peak integration value in the range of δ-0.20 to 0.30

[0478] C: Peak integration value in the range of δ3.30 to 3.75

[0479] D: Peak integration value in the range of δ4.75 to 5.30

[0480] E: Peak integration value in the range of δ1.30 to 1.50

[0481] (It should be noted that the peak of protons derived from water in deuterated chloroform also appears in this range, but since the sample concentration is sufficient, it has no effect on the assignment of the structure.)

[0482] F: Peak integration value in the range of δ0.75 to 1.98

[0483] G: Peak integration value in the range of δ1.98 to 2.70

[0484] H: Peak integration value in the range of δ0.40 to 0.55

[0485] aa=A / 2

[0486] bb=B / 6

[0487] cc=C / 4

[0488] dd=D / 3

[0489] ee=(FG / 6×8-H) / 10

[0490] kk=E / 4

[0491] ll=G / 6

[0492] oo=H / 2

[0493] ・Pellets containing the polycarbonate-polyorganosiloxane copolymer produced in Example 1

[0494] T 1 =dd

[0495] TX 1 =dd

[0496] f 1 =aa / T 1 ×100

[0497] g 1 =bb / T 1 ×100

[0498] h 1 =cc / T 1 ×100

[0499] i 1 =dd / T 1 ×100

[0500] TW 1 =f 1×93+g 1 ×74.1+h 1 ×44+i 1 ×172

[0501] Content of structural unit (A-1) (mass %): i 1 ×172 / TW 1 ×100

[0502] -OR T Content of terminal structures shown (mass %): f 1 ×93 / TW 1 ×100

[0503] Content of polycarbonate block (mass %): (i 1 ×172) / TW 1 ×100

[0504] Content of the structural unit represented by the general formula (XX) (mass %): g 1 ×74.1 / TW 1 ×100

[0505] Content of polyorganosiloxane block (mass %): (g 1 ×74.1+h 1 ×44) / TW 1 ×100

[0506] The molar fraction of the structural unit (A-1) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): dd / TX 1 ×100

[0507] Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2)

[0508] Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo

[0509] ・Pellets containing the polycarbonate-polyorganosiloxane copolymers produced in Examples 2 to 6 and Comparative Example 1

[0510] T 2 =aa+bb+cc+dd+kk

[0511] TX 2 =dd+kk

[0512] f 2 =aa / T 2 ×100

[0513] g 2 =bb / T 2 ×100

[0514] h 2 =cc / T 2 ×100

[0515] i 2 =dd / T 2 ×100

[0516] n 2 =kk / T 2 ×100

[0517] TW 2 =f 2 ×93+g 2 ×74.1+h 2 ×44+i 2 ×172+n 2 ×144

[0518] Content of structural unit (A-1) (mass %): i 2 ×172 / TW 2 ×100

[0519] Content of structural unit (A-31) (mass %): n 2 ×144 / TW 2 ×100

[0520] -OR T Content of terminal structures shown: f 2 ×93 / TW 2 ×100

[0521] Content of polycarbonate block (mass %): (i 2 ×172+n 2 ×144) / TW 2 ×100

[0522] Content of the structural unit represented by the general formula (XX) (mass %): g 2 ×74.1 / TW 2 ×100

[0523] Content of polyorganosiloxane block (mass %): (g 2 ×74.1+h 2 ×44) / TW 3 ×100

[0524] The molar fraction of the structural unit (A-1) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): dd / TX 2 ×100

[0525] The molar fraction of the structural unit (A-31) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): kk / TX 2 ×100

[0526] Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2)

[0527] ・Pellets containing the polycarbonate-polyorganosiloxane copolymers produced in Examples 7 to 15 and Comparative Examples 2 to 4

[0528] T 3 =aa+bb+cc+dd+ee

[0529] TX 3 =dd+ee

[0530] f 3 =aa / T 3 ×100

[0531] g 3 =bb / T 3 ×100

[0532] h 3 =cc / T 3 ×100

[0533] i 3 =dd / T 3 ×100

[0534] j 3 =ee / T 3 ×100

[0535] TW 3 =f 3 ×93+g 3 ×74.1+h 3 ×44+i 3 ×172+j 3 ×170

[0536] Content of structural unit (A-1) (mass %): i 3 ×172 / TW 3 ×100

[0537] Content of structural unit (A-32) (mass %): j 3 ×170 / TW 3 ×100

[0538] -OR T Content of terminal structures shown (mass %): f 3 ×93 / TW 3 ×100

[0539] Content of polycarbonate block (mass %): (i 3 ×172+j 3 ×170) / TW 1 ×100

[0540] Content of the structural unit represented by the general formula (XX) (mass %): g 3 ×74.1 / TW 3 ×100

[0541] Content of polyorganosiloxane block (mass %): (g 3 ×74.1+h 3 ×44) / TW 3 ×100

[0542] The molar fraction of the structural unit (A-1) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): dd / TX 3 ×100

[0543] The molar fraction of the structural unit (A-32) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): ee / TX 3 ×100

[0544] Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2)

[0545] Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo

[0546] ・Pellets containing the polycarbonate-polyorganosiloxane copolymers produced in Examples 16 to 20 and Comparative Examples 6 and 7

[0547] T 4 =aa+bb+cc+dd+ee+ll

[0548] TX 4 =dd+ee+ll

[0549] f 4 =aa / T 4 ×100

[0550] g 4 =bb / T 4 ×100

[0551] h 4 =cc / T 4 ×100

[0552] i 4 =dd / T 4×100

[0553] j 4 =ee / T 4 ×100

[0554] m 4 =ll / T 4 ×100

[0555] TW 4 =f 4 ×93+g 4 ×74.1+h 4 ×44+i 4 ×172+j 4 ×170+m 4 ×222

[0556] Content of structural unit (A-1) (mass %): i 4 ×172 / TW 4 ×100

[0557] Content of structural unit (A-32) (mass %): j 4 ×170 / TW 4 ×100

[0558] Content of structural unit (A-33) (mass %): m 4 ×222 / TW 4 ×100

[0559] -OR T Content of terminal structures shown (mass %): f 4 ×93 / TW 4 ×100

[0560] Content of polycarbonate block (mass %): (i 4 ×172+j 4 ×170+m 4 ×222) / TW 4 ×100

[0561] Content of the structural unit represented by the general formula (XX) (mass %): g 4 ×74.1 / TW 4 ×100

[0562] Content of polyorganosiloxane block (mass %): (g 4 ×74.1+h 4 ×44) / TW 4 ×100

[0563] The molar fraction of the structural unit (A-1) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): dd / TX 4 ×100

[0564] The molar fraction of the structural unit (A-32) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): ee / TX 4 ×100

[0565] The molar fraction of the structural unit (A-33) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by formula (X): ll / TX 4 ×100

[0566] Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2)

[0567] Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo

[0568] Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo

[0569] ・Pellets containing the polycarbonate-polyorganosiloxane copolymer produced in Example 21 and Comparative Example 9

[0570] T 5 =aa+bb+cc+dd+ll

[0571] TX 5 =dd+ll

[0572] f 5 =aa / T 5 ×100

[0573] g 5 =bb / T 5 ×100

[0574] h 5 =cc / T 5 ×100

[0575] i 5 =dd / T 5 ×100

[0576] m 5 =ll / T 5 ×100

[0577] TW 5 =f 5 ×93+g 5 ×74.1+h 5 ×44+i 5×172+m 5 ×222

[0578] Content of structural unit (A-1) (mass %): i 5 ×172 / TW 5 ×100

[0579] Content of structural unit (A-33) (mass %): m 5 ×222 / TW 5 ×100

[0580] -OR T Content of terminal structures shown (mass %): f 5 ×93 / TW 5 ×100

[0581] Content of polycarbonate block (mass %): (i 5 ×172+m 5 ×222) / TW 5 ×100

[0582] Content of the structural unit represented by the general formula (XX) (mass %): g 5 ×74.1 / TW 5 ×100

[0583] Content of polyorganosiloxane block (mass %): (g 5 ×74.1+h 5 ×44) / TW 5 ×100

[0584] The molar fraction of the structural unit (A-1) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by the formula (X): dd / TX 5 ×100

[0585] The molar fraction of the structural unit (A-33) contained in the PC-POS copolymer relative to the total amount of the structural unit represented by formula (X): ll / TX 5 ×100

[0586] Average value of a in polycarbonate-polyorganosiloxane copolymer: bb / (oo / 2)

[0587] Average value b2 in polycarbonate-polyorganosiloxane copolymer: cc / oo

[0588] ・Pellets containing the polycarbonate produced in Comparative Example 5

[0589] T 6 =aa+dd+ee

[0590] TX 6=dd+ee

[0591] f 6 =aa / T 6 ×100

[0592] i 6 =dd / T 6 ×100

[0593] j 6 =ee / T 6 ×100

[0594] TW 6 =f 6 ×93+i 6 ×172+j 6 ×170

[0595] Content of structural unit (A-1) (mass %): i 6 ×172 / TW 6 ×100

[0596] Content of structural unit (A-32) (mass %): j 6 ×170 / TW 6 ×100

[0597] -OR T Content of terminal structures shown (mass %): f 6 ×93 / TW 6 ×100

[0598] Content of polycarbonate block (mass %): (i 6 ×172+j 6 ×170) / TW 6 ×100

[0599] The molar fraction of the structural unit (A-1) contained in the polycarbonate relative to the total amount of the structural unit represented by the formula (X): dd / TX 6 ×100

[0600] The molar fraction of the structural unit (A-32) contained in the polycarbonate relative to the total amount of the structural unit represented by the formula (X): ee / TX 6 ×100

[0601] ・Pellets containing the polycarbonate produced in Comparative Example 8

[0602] T 7 =aa+dd+ee+ll

[0603] TX 7 =dd+ee+ll

[0604] f7 =aa / T 7 ×100

[0605] i 7 =dd / T 7 ×100

[0606] j 7 =ee / T 7 ×100

[0607] m 7 =ll / T 7 ×100

[0608] TW 7 =f 7 ×93+i 7 ×172+j 7 ×170+m 7 ×222

[0609] Content of structural unit (A-1) (mass %): i 7 ×172 / TW 7 ×100

[0610] Content of structural unit (A-32) (mass %): j 7 ×170 / TW 7 ×100

[0611] Content of structural unit (A-33) (mass %): m 7 ×222 / TW 7 ×100

[0612] -OR T The content of the terminal structure shown (mass %) = f 7 ×93 / TW 7 ×100

[0613] Content of polycarbonate block (mass %): (i 7 ×172+j 7 ×170+m 7 ×222) / TW 7 ×100

[0614] The molar fraction of the structural unit (A-1) contained in the polycarbonate relative to the total amount of the structural unit represented by the formula (X): dd / TX 7 ×100

[0615] The molar fraction of the structural unit (A-32) contained in the polycarbonate relative to the total amount of the structural unit represented by the formula (X): ee / TX 7 ×100

[0616] The molar fraction of the structural unit (A-33) contained in the polycarbonate relative to the total amount of the structural unit represented by the formula (X): ll / TX 7 ×100

[0617] (2) Charpy impact strength

[0618] The pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples were dried at 100°C for 5 hours, and then injection molded into a strip-shaped test piece for mechanical property evaluation having a length of 80 mm, a width of 10 mm, and a thickness of 3 mm at a cylinder temperature of 220°C and a mold of 80°C. Then, a notch (r=0.25 mm±0.05 mm) was given by post-processing to obtain a test piece, and the Charpy impact strength at 23°C was measured using a Charpy impact tester (Charpy impact tester, model 611, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with ISO 179-1:2010.

[0619] It should be noted that in Examples 1, 7, 8 and 13, the barrel temperature during injection molding was set to 250°C, in Comparative Example 2, the barrel temperature during injection molding was set to 240°C, and in Examples 2, 5, 9, 10, 12, 13 and 15 to 17 and Comparative Example 4, the barrel temperature during injection molding was set to 230°C.

[0620] (3) Scratch hardness

[0621] The scratch hardness of the surface of the long strip-shaped test piece for evaluating mechanical properties having a length of 80 mm and a width of 10 mm obtained from the pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples and the pellets containing polycarbonate produced in the Comparative Examples, which is the same as the Charpy impact strength, was measured in accordance with JIS K 5600-5-4:1999 at a load of 750 g and a measurement temperature of 23°C.

[0622] (4) Weight average molecular weight

[0623] The weight average molecular weight of the pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples and the pellets containing polycarbonate produced in Comparative Examples were calculated by gel permeation chromatography (GPC) measurement under the following conditions.

[0624] Test equipment: Waters Acquity e2695 APC

[0625] Column: TOSOH TSK-GEL SuperAWM-H×2

[0626] Solvent: Dimethylformamide (DMF) containing 10 mM lithium bromide

[0627] Column temperature: 40°C

[0628] Flow rate: 0.6mL / min

[0629] Detector: RI

[0630] Injection concentration: 0.1w / v%

[0631] Injection volume: 20 μL

[0632] The calibration curve was prepared using the following standard polystyrene manufactured by Tosoh Corporation, and a cubic equation obtained by least squares approximation was used.

[0633] Standard polystyrene: F-450, F-288, F128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500

[0634] The weight average molecular weight of the pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples were measured as follows. 10 mg was collected from the above pellets, 10 mL of dimethylformamide containing 10 mM lithium bromide was added, and the above pellets were completely dissolved. The obtained solution was filtered with a membrane filter and subjected to GPC measurement.

[0635] The differential molecular weight distribution curve can be obtained by the following method. First, using a standard curve, the time curve (dissolution curve) of the intensity distribution detected in the RI detector is used as a molecular weight distribution curve relative to the logarithmic value (log (M)) of the molecular weight. Next, after obtaining the integrated molecular weight distribution curve relative to log (M) when the total area of ​​the distribution curve is set to 100%, the integrated molecular weight distribution curve is differentiated by log (M), thereby obtaining a differential molecular weight distribution curve relative to log (M).

[0636] The weight average molecular weight (Mw) is defined by the following formula as the number (Ni) of molecules passing through the molecular weight (Mi) at each elution position of the obtained differential molecular weight distribution curve.

[0637] Weight average molecular weight: Mw = Σ (Ni・Mi 2 ) / Σ(Ni・Mi)

[0638] In addition, a series of operations until the differential molecular weight distribution curve and the weight average molecular weight (Mw) are obtained can usually be performed using analysis software built into the GPC measurement device.

[0639] (5) Melt flow rate (MFR)

[0640] Pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples and pellets containing polycarbonate produced in Comparative Examples were dried at 100° C. for 5 hours and then measured at 230° C. and a load of 2.13 kg in accordance with JIS K 7210.

[0641] (6) Tensile elastic modulus

[0642] The pellets containing polycarbonate-polysiloxane copolymers produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples were dried at 100°C for 5 hours, and then injection molded at a barrel temperature of 220°C and a mold of 80°C to obtain JIS K7139 dumbbell-shaped tensile test specimen A1 type. The test specimens were used to perform measurements in accordance with ISO527-1, 2:2012 at a tensile speed of 1 mm / min and a measuring temperature of 23°C.

[0643] It should be noted that in Examples 1, 7, 8 and 13, the barrel temperature during injection molding was set to 250°C, in Comparative Example 2, the barrel temperature during injection molding was set to 240°C, and in Examples 2, 5, 9, 10, 12, 13 and 15 to 17 and Comparative Example 4, the barrel temperature during injection molding was set to 230°C.

[0644] (7) Tensile strength (yield)

[0645] The pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following examples and comparative examples, and the pellets containing polycarbonate produced in the comparative examples were dried at 100°C for 5 hours, and then injection molded at a barrel temperature of 220°C and a mold of 80°C to obtain JIS K7139 dumbbell-shaped tensile test specimens A1 type. Using the test specimens, measurements were performed in accordance with ISO 527-1, 2:2012 at a tensile speed of 50 mm / min and a measuring temperature of 23°C.

[0646] It should be noted that in Examples 1, 7, 8 and 13, the barrel temperature during injection molding was set to 250°C, in Comparative Example 2, the barrel temperature during injection molding was set to 240°C, and in Examples 2, 5, 9, 10, 12, 13 and 15 to 17 and Comparative Example 4, the barrel temperature during injection molding was set to 230°C.

[0647] (8) Glass transition temperature

[0648] Using DSC8500 manufactured by PerkinElmer, according to JIS K 7121, 10 mg of the pellets containing polycarbonate-polyorganosiloxane copolymers produced in the following Examples and Comparative Examples, and the pellets containing polycarbonate produced in the Comparative Examples were collected into an aluminum pan, kept at 50°C for 1 minute, heated to 200°C, kept in this state for 5 minutes, cooled to 50°C and kept in this state for 5 minutes, and then heated from 50°C to 200°C at 20°C / min, and the midpoint glass transition temperature at this time was measured.

[0649] 3. Manufacture of polycarbonate-polysiloxane (PC-POS) copolymer

[0650] Embodiment 1: Manufacturing of PC-POS 1

[0651] Polycarbonate-polyorganosiloxane PC-POS 1 was produced under the following production conditions 1, and the obtained pellets containing PC-POS 1 were evaluated by the above-mentioned method. The results are shown in Table 1.

[0652] (Manufacturing condition 1)

[0653] In a 10L stainless steel reactor equipped with a stirring device, a trap for capturing distilled phenol, and a decompression device, the diol monomers shown in Table 1, diphenyl carbonate (2,500.0 g / 11.7 mol) having a molar fraction shown in Table 1 when the total amount of the diol monomers is 100, and polyether-modified polyorganosiloxane PDMS-1 in an amount shown in Table 1 to give a mass (theoretical value) of the PC-POS copolymer obtained in Table 1 were added, and these were completely melted at a reactor temperature of 100°C, and the inside of the reactor was replaced with nitrogen. 1.6 mL of 0.01N sodium hydroxide was added to start polymerization, and the reactor temperature was raised to 180°C over about 50 to 100 minutes, and the pressure in the reactor was reduced to 2.66×10 4 Pa, and maintain this condition until the phenol distillation amount reaches 0.6L.

[0654] Next, the temperature in the reactor was raised to 190°C over about 50 minutes, and the pressure in the reactor was reduced to 1.33×10 3 Pa, and this condition was maintained until 2.0 L of phenol was distilled off.

[0655] Next, the temperature in the reactor was raised to 220° C. over about 15 minutes, maintained for about 10 minutes, and then raised to the final polymerization temperature shown in Table 1 over about 10 minutes. Then, the pressure in the reactor was reduced to 1.33×10 2Pa or less, and the reaction was continued until a predetermined stirring torque was reached. Then, nitrogen was introduced to raise the pressure to normal pressure, and butyl p-toluenesulfonate as a polymerization deactivator in an amount shown in Table 1 was added as required.

[0656] Furthermore, Irganox 1010 and Irgafos 168 were added respectively so that the content in the obtained polymer became 1,000 ppm, and stirred for more than 10 minutes. Then, high-pressure nitrogen was introduced into the reactor to extrude resin strands from the bottom of the reactor. The obtained strands were cut with a pelletizer to obtain pellets containing the polycarbonate-polyorganosiloxane copolymer PC-POS 1.

[0657] It should be noted that in the above-mentioned production condition 1, "the mass (theoretical value) of the obtained PC-POS copolymer" refers to the mass obtained by subtracting the mass (theoretical value) of phenol generated from the input diphenyl carbonate from the sum of the input mass of all diol monomers, the input mass of diphenyl carbonate and the input mass of PDMS-1.

[0658] Examples 2 and 5 and Comparative Example 1: Production of PC-POS 2, 5 and 31

[0659] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 1, pellets containing PC-POS 2, 5, and 31 were obtained by the same method as in Example 1. The obtained pellets containing PC-POS 2, 5, and 31 were evaluated by the above method. The results are shown in Table 1.

[0660] Example 3: Manufacturing of PC-POS 3

[0661] Polycarbonate-polyorganosiloxane (PC-POS 3) was produced under the following production conditions 2, and the obtained PC-POS 3 was evaluated by the above-mentioned method. The results are shown in Table 1.

[0662] (Manufacturing condition 2)

[0663] In a 10L stainless steel reactor equipped with a stirring device, a trap for capturing distilled phenol, and a decompression device, the diol monomers shown in Table 1, diphenyl carbonate (2,500.0 g / 11.7 mol) having a molar fraction shown in Table 1 when the total amount of the diol monomers is 100, and polyether-modified polyorganosiloxane PDMS-1 in an amount shown in Table 1 to give a mass (theoretical value) of the PC-POS copolymer obtained in Table 1 were added, and these were completely melted at a reactor temperature of 100°C, and the inside of the reactor was replaced with nitrogen. 1.64 mL of 0.01N sodium hydroxide was added to start polymerization, and the reactor temperature was raised to 180°C over about 50 to 100 minutes, and the pressure in the reactor was reduced to 2.66×10 4 Pa, and maintain this condition until the phenol distillation volume reaches 0.2L.

[0664] Next, the temperature in the reactor was raised to 200°C over about 150 minutes, and the pressure in the reactor was reduced to 1.33×10 3 Pa, and this condition was maintained until 1.8 L of phenol was distilled off.

[0665] Next, the temperature in the reactor was raised to the final polymerization temperature shown in Table 1 over about 60 minutes, and then the pressure in the reactor was reduced to 1.33×10 2 Pa, phenol was distilled off by more than 2 L, and the reaction was continued until a predetermined stirring torque was reached. Then, nitrogen was introduced to raise the pressure to normal pressure, and butyl p-toluenesulfonate as a polymerization deactivator in an amount shown in Table 1 was added as required.

[0666] Furthermore, Irganox 1010 and Irgafos 168 were added respectively so that the content in the obtained polymer became 1,000 ppm, and stirred for more than 10 minutes. Then, high-pressure nitrogen was introduced into the reactor to extrude resin strands from the bottom of the reactor. The obtained strands were cut with a pelletizer, thereby obtaining pellets containing the polycarbonate-polyorganosiloxane copolymer PC-POS 3.

[0667] In the above-mentioned production condition 2, the “mass (theoretical value) of the obtained PC-POS copolymer” is the same as that in the production condition 1.

[0668] Examples 4 and 6: Manufacturing of PC-POS 4 and 6

[0669] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 1, pellets containing PC-POS 4 and 6 were obtained by the same method as in Example 3. The obtained pellets containing PC-POS 4 and 6 were evaluated by the above methods. The results are shown in Table 1.

[0670] [Table 1]

[0671]

[0672] As shown in Table 1, the molded articles of PC-POS 1 to 6 in which the content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0 mass % or more and 25.0 mass % or less, and the content of the structural unit (A-1) represented by the general formula (1) is 73.0 mass % or more, satisfy conditions (I) and (II), and the content of the structural unit represented by the general formula (XX) and the weight average molecular weight are of the same degree, surprisingly, the greater the content of the structural unit (A-1), the better the impact resistance. It should be noted that PC-POS 6 is a polycarbonate-polyorganosiloxane copolymer satisfying condition (C1), and PC-POS 2 to 5 are polycarbonate-polyorganosiloxane copolymers satisfying condition (D1).

[0673] On the other hand, the molded body of the PC-POS 31 that does not satisfy the condition (C1) does not satisfy the conditions (I) and (II).

[0674] Examples 7 to 10 and 12 to 15, and Comparative Examples 2 and 4: Production of PC-POS 7 to 10, 12 to 15, 32 and 34

[0675] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 2, pellets containing PC-POS 7 to 10, 12 to 15, 32, and 34 were obtained by the same method as in Example 1. The obtained pellets containing PC-POS 7 to 10, 12 to 15, 32, and 34 were evaluated by the above method. The results are shown in Table 2.

[0676] Example 11, and Comparative Examples 3 and 5: Production of PC-POS 11 and 33, and PC 35

[0677] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 2, pellets containing PC-POS 11 and 33, and PC 35 were obtained by the same method as in Example 3. The obtained pellets containing PC-POS 11 and 33, and PC 35 were evaluated by the above method. The results are shown in Table 2.

[0678] [Table 2]

[0679]

[0680] As shown in Table 2, the molded articles of PC-POS 7 to 10, 13 and 14, in which the content of the structural unit represented by the general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is 2.0 mass % or more and 25.0 mass % or less, and the content of the structural unit (A-1) represented by the general formula (1) is 73.0 mass % or more, satisfy conditions (I) and (II), and the content of the structural unit represented by the general formula (XX) and the weight average molecular weight are similar, surprisingly, the greater the content of the structural unit (A-1), the better the impact resistance. It should be noted that PC-POS 13 and 14 are polycarbonate-polyorganosiloxane copolymers satisfying condition (C2), and PC-POS 8 and 7 to 10 are polycarbonate-polyorganosiloxane copolymers satisfying condition (D2).

[0681] The molded body of PC-POS 15 having a content of the structural unit (A-1) represented by the general formula (1) of less than 73.0 and satisfying condition (C2) and the molded bodies of PC-POS 11 and 12 satisfying condition (D2) satisfy conditions (I) and (II).

[0682] In addition, when PC-POS 2 to 6 and PC-POS 7 to 15 are compared, it can be seen that the polycarbonate-polyorganosiloxane copolymer containing the structural unit (A-32) as the structural unit (A-3) has better impact resistance and scratch resistance than the polycarbonate-polyorganosiloxane copolymer containing the structural unit (A-31) as the structural unit (A-3).

[0683] On the other hand, the molded body of the PC-POS 34 that does not satisfy the condition (C2) and the molded bodies of the PC-POS 32 and 33 that do not satisfy the condition (D2) do not satisfy the condition (II).

[0684] In addition, the molded article of PC 35, which does not contain a polyorganosiloxane block and has a structural unit derived from isosorbide and 1,4-cyclohexanedimethanol, does not satisfy condition (I) as does the polycarbonate shown in the examples of Japanese Patent Application Laid-Open No. 2009-144013. It is noted that the impact resistance of the polycarbonate decreases as the content of the structural unit derived from isosorbide increases in the examples of Japanese Patent Application Laid-Open No. 2009-144013, but the comparison of Examples 2 and 3, Examples 4 and 5, Examples 8 to 10, and Examples 13 and 14, in which the content and weight average molecular weight of the structural unit represented by the general formula (XX) are similar to each other, clearly shows that the polycarbonate-polyorganosiloxane copolymer of the present invention containing a polyorganosiloxane block exhibits a surprising effect that the impact resistance becomes better as the content of the structural unit (A-1) represented by the general formula (1) corresponding to the structural unit derived from isosorbide increases.

[0686] Examples 16 to 18 and Comparative Example 6: Preparation of PC-POS 16 to 18 and 36

[0687] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 3, pellets containing PC-POS 16 to 18 and 36 were obtained by the same method as in Example 1. The obtained pellets containing PC-POS 16 to 18 and 36 were evaluated by the above method. The results are shown in Table 3.

[0688] Examples 19 and 20, and Comparative Examples 7 and 8: Preparation of PC-POS 19, 20 and 37, and PC 38

[0689] Except for changing the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature as shown in Table 3, pellets containing PC-POS 19, 20 and 37, and PC 38 were obtained by the same method as in Example 2. The obtained pellets containing PC-POS 19, 20 and 37, and PC 38 were evaluated by the above method. The results are shown in Table 3.

[0690] [Table 3]

[0691]

[0692] As shown in Table 3, the molded body of PC-POS 17 having a content of the structural unit (A-1) represented by the general formula (1) of less than 73.0 and satisfying condition (D41), the molded body of PC-POS 18 to 20 satisfying condition (D42), and the molded body of PC-POS 16 satisfying condition (D43) satisfy conditions (I) and (II).

[0693] On the other hand, the molded body of PC 38 not containing a polyorganosiloxane block does not satisfy condition (I). In addition, the molded body of PC-POS 38 not satisfying any of conditions (C41) to (C43) does not satisfy condition (II). Furthermore, the molded body of PC-POS 39 not satisfying any of conditions (D41) to (D43) does not satisfy condition (II).

[0694] Embodiment 21: Manufacturing of PC-POS 21

[0695] A pellet containing PC-POS 21 was obtained by the same method as in Example 3 except that the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature were changed as shown in Table 4. The obtained pellets containing PC-POS 21 were evaluated by the above methods. The results are shown in Table 4.

[0696] Comparative Example 9: Production of PC-POS 39

[0697] A pellet containing PC-POS 39 was obtained by the same method as in Example 1 except that the diol monomer and its molar fraction, the mass ratio of PDMS-1, and the final polymerization temperature were changed as shown in Table 4. The obtained pellet containing PC-POS 39 was evaluated by the above method. The results are shown in Table 4.

[0698] [Table 4]

[0699]

[0700] As shown in Table 4, the molded body of PC-POS 21 having a content of the structural unit (A-1) represented by the general formula (1) of less than 73.0 and satisfying the condition (D3) satisfies the conditions (I) and (II).

[0701] On the other hand, the molded body of the PC-POS 39 that does not satisfy the condition (D3) does not satisfy the condition (I).

[0702] The polycarbonate-based resin composition containing the polycarbonate-polyorganosiloxane copolymer of the present invention can be suitably used for impact-resistant applications and scratch-resistant applications because the molded article thereof has excellent impact resistance and scratch resistance.

[0703] Examples of impact-resistant and damage-resistant applications include structures whose outer surfaces are formed of the polycarbonate resin composition, and more specifically, resin windows, touch panels, interior decoration products, exterior decoration products, interior or exterior parts of vehicles, housings, electrical components, building materials, OA equipment components, etc. The polycarbonate resin composition of the present invention can be suitably used to manufacture the above-mentioned articles.

[0704] The molded article comprising the polycarbonate resin composition of the present invention can be suitably used for 1) automotive parts such as sunroofs, door visors, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms, and grilles; 3) windows for railway vehicles and ships; 4) various parts for televisions, radio-recorders, cameras, video recorders, audio players, DVD players, telephones, monitors, computers, cash registers, copiers, printers, fax machines, and various parts for outer panels and housings, etc., for electrical equipment; 5) precision equipment parts such as shells and covers of precision machinery such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as plastic greenhouses and greenhouses; 7) furniture parts such as lighting covers, blinds, and indoor appliances, etc.

Claims

1. A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block containing a structural unit (A-1) represented by the following general formula (1) and a polyorganosiloxane block containing a structure (A-2) represented by the following general formula (2), and satisfying the following conditions (I) and (II), In general formula (2), R 1 and R 2 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms, and a represents an integer of 2 to 500, Condition (I): Charpy impact strength of the molded sheet measured at a temperature of 23°C in accordance with ISO 179-1:2010 is 15 kJ / m 2 The above-mentioned molded sheet is obtained by post-processing the polycarbonate-polyorganosiloxane copolymer to form a long strip-shaped molded sheet with a length of 80 mm, a width of 10 mm, and a thickness of 3 mm, and giving a notch of r = 0.25 mm ± 0.05 mm; Condition (II): The scratch hardness of the molded article of the polycarbonate-polyorganosiloxane copolymer by a pencil method measured in accordance with JIS K 5600-5-4:1999 is HB or more.

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

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1, further comprising at least one structural unit (A-3) selected from the structures represented by the following general formulas (3) and (4), In general formulas (3) and (4), R 11 represents a divalent linear or branched aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and R 12 It represents a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms.

4. The polycarbonate-polyorganosiloxane copolymer according to claim 3, wherein The structural unit (A-3) has at least one structure selected from the group consisting of the structures represented by the following general formulae (31) to (34), In the general formula (31), n ​​represents an integer of 2 to 18.

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

6. The polycarbonate-polyorganosiloxane copolymer according to claim 4, wherein The structural unit (A-3) has the structural unit (A-31) represented by the general formula (31), and when the content of the structural unit represented by the following general formula (XX) in the polycarbonate-polyorganosiloxane copolymer is x, The molar ratio A-31 / A-1 of the structural unit (A-31) to the structural unit (A-1) and the content x of the structural unit represented by the following general formula (XX) satisfy the following condition (C1) or (D1), Condition (C1): A-31 / A-1 is 1.0 / 99.0 or more and 25.0 / 75.0 or less, and x is 1.0 mass % or more and less than 4.0 mass %; Condition (D1): A-31 / A-1 is 1.0 / 99.0 or more and 30.0 / 70.0 or less, x is 4.0 mass % or more and 10.0 mass % or less, In the general formula (XX), R 1 and R 2 represents the same as R in the general formula (2) 1 and R 2 Same meaning.

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

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

9. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 8, wherein The R 1 and R 2 It is methyl. 10 . A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to claim 1 . 11 . A molded article comprising the polycarbonate resin composition according to claim 10 .

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