Polycarbonate-polyorganosiloxane copolymer and resin composition containing copolymer

Abstract

To provide a polycarbonate-polyorganosiloxane copolymer which can introduce a sufficient amount of a siloxane block to a polymer main chain by a method other than an interfacial polymerization method, and as a result, exhibits high mechanical properties.SOLUTION: A polycarbonate-polyorganosiloxane copolymer contains a polyorganosiloxane block (A-1) containing a specific structural unit, and a polycarbonate block (A-2) composed of a specific repeating unit, and satisfies the following condition (A) or (B). Condition (A): a hexane extract of the polycarbonate-polyorganosiloxane copolymer is 150 ppm or less. Condition (B): an average weight of the polyorganosiloxane block which is obtained by separating the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatograph and is contained in the polycarbonate-polyorganosiloxane copolymer satisfies a specific expression.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer and a resin composition containing the copolymer. [Background technology]

[0002] Polycarbonate resin is an engineering plastic that has excellent transparency and mechanical properties, as well as very high impact resistance. Polycarbonate-polyorganosiloxane copolymers, which are obtained by copolymerizing polycarbonate with polysiloxane, are known to have excellent low-temperature impact resistance and chemical resistance while maintaining high transparency. Generally, known methods for producing polycarbonate resins include a method in which an aromatic dihydroxy compound is directly reacted with phosgene (interfacial polycondensation method) and a method in which an aromatic dihydroxy compound is subjected to an ester exchange reaction with a carbonate diester in a molten state (melt polymerization method).

[0003] To produce a polycarbonate-polyorganosiloxane copolymer, an interfacial polymerization method is often adopted. For example, a diaryl diol compound such as bisphenol and phosgene are reacted in the presence of an organic solvent to produce a polycarbonate oligomer having a reactive chloroformate group, and simultaneously with or successively to the production of the polycarbonate oligomer, the polycarbonate oligomer, bisphenols, and a polysiloxane having hydroxyl-containing aryl groups at both ends are contacted in a methylene chloride / water medium to produce the copolymer (Patent Document 1). Generally, in a polymerization reaction, homo-coupling bodies in which the same raw material components are bonded together, or unreacted raw material components may be produced because some raw materials are not involved in the polymerization reaction. These components are present in the polymer without being uniformly incorporated into the polymer main chain, so the transparency and mechanical properties of the polymer are significantly reduced. The interfacial polymerization method described above rarely causes such problems, and a polycarbonate-polyorganosiloxane copolymer having excellent transparency and mechanical properties can be obtained.

[0004] On the other hand, the interfacial polymerization method requires the use of highly toxic phosgene as a carbonate source. In addition, the polymerization reaction system requires the use of methylene chloride, which has a large environmental impact, as a solvent, and its removal requires a large degassing device and a large amount of energy, making it economically disadvantageous. In order to avoid this problem, methods other than the interfacial polymerization method, such as the melt polymerization method, have been considered for producing polycarbonate-polyorganosiloxane copolymers.

[0005] Patent Document 2 discloses the preparation of polycarbonate-polyorganosiloxane copolymers by melt polymerization from bisphenol compounds, aromatic carbonate diesters, silanol-terminated polysiloxanes and catalysts. Patent Document 3 discloses a method for preparing block copolysiloxane carbonates in the presence of carbonate-terminated polyorganosiloxanes, dihydroxy aromatic compounds, diaryl carbonates and carbonate transesterification catalysts. Patent Document 4 discloses a method for preparing polysiloxane / polycarbonate block cocondensation products, which comprises reacting hydroxyaryloxy-terminated dimethylsiloxanes with oligocarbonates having specific weight average molecular weights and specific terminal ratios (OH terminal groups and aryl terminal groups) in the molten state in the presence of a catalyst.

[0006] Patent Document 5 discloses a method for producing a poly(diorganosiloxane) / polycarbonate block copolymer by melt-polymerizing a polydiorganosiloxane containing a polydiorganosiloxane component having a specific terminal structure, a diphenol not containing Si, and a diaryl carbonate in the presence of a specific catalyst. Patent Document 6 discloses a method for producing a modified polycarbonate resin by solid-phase polymerization, and describes the use of a polysiloxane compound as a starting material. Patent Documents 7 to 9 disclose methods for obtaining a polysiloxane-polycarbonate block co-condensate by an ester exchange method. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2015-189953 A [Patent Document 2] U.S. Pat. No. 5,227,449 [Patent Document 3] Japanese Patent Application Publication No. 8-311206 [Patent Document 4] Japanese Patent Application Publication No. 10-251408 [Patent Document 5] JP 2008-248262 A [Patent Document 6] Special Publication No. 2008-513594 [Patent Document 7] Special Publication No. 2017-505841 [Patent Document 8] Special Publication No. 2016-532734 [Patent Document 9] Special Publication No. 2016-532733 Summary of the Invention [Problem to be solved by the invention]

[0008] Patent Documents 2 to 7 disclose a method for producing a polycarbonate-polyorganosiloxane copolymer by melt polymerization, but it is still insufficient in terms of obtaining a polycarbonate-polyorganosiloxane copolymer having good mechanical properties. Patent Document 2 uses a silanol-terminated siloxane, but it is known that the lower the molecular weight of a silanol-terminated dimethylsiloxane, the more likely it is to undergo intramolecular condensation. The cyclic siloxane generated as a result of intramolecular condensation remains in the obtained polycarbonate-polysiloxane copolymer, and not only has an adverse effect on its mechanical properties, but also has a concern of having an adverse effect such as relay contact failure in electrical and electronic applications.

[0009] Although Patent Document 3 shows that the amount of polydimethylsiloxane incorporated into the polymer main chain increases, it also describes that the appearance of the carbonate-terminated polysiloxane in a molten state with other raw materials is "milky white," which suggests that the carbonate-terminated polysiloxane is separated from the other raw materials and that components generated by homo-coupling and unreacted carbonate-terminated polysiloxane still remain in the polymer. These components significantly reduce the mechanical properties of the polycarbonate-polysiloxane copolymer. Patent Document 3 also describes that even in a production example in which a large amount of siloxane is incorporated into the polymer main chain, an alkali metal catalyst (sodium hydroxide) was used in an amount of 10 x 10 moles per mole of bisphenol A. -6 It is presumed that when an excessive amount of catalyst is used, the increase in the amount of residual catalyst component induces hydrolysis of polycarbonate chains, and the obtained polymer does not have heat resistance or weather resistance that can withstand practical conditions. The present inventors have confirmed that the mechanical properties of the allylphenol-terminated polyorganosiloxane copolymer disclosed in Patent Document 3 are also deteriorated.

[0010] The method disclosed in Patent Document 4 requires the prior preparation of an oligocarbonate having a specific weight-average molecular weight and a specific terminal ratio (OH terminal group and aryl terminal group) in order to obtain a polycarbonate-polysiloxane copolymer, and therefore cannot be said to be a practical production method from an economical point of view.

[0011] The copolymer disclosed in Patent Document 5 has a large domain structure, and it cannot be said that siloxane is uniformly incorporated into the polymer main chain. Patent Document 6 shows a method for producing a polycarbonate-polyorganosiloxane copolymer by a solid-phase reaction, but does not mention the uniformity of the reaction or the physical properties of the polymer. Patent Documents 7 to 9 produce copolymers having polysiloxane blocks with the same structure by an ester exchange method (melt polymerization method), but these methods require the use of a polycarbonate with a specific structure, including a structure in which a carbonyl group is directly bonded to a benzene ring, as a raw material. In order to obtain a desired polycarbonate-polysiloxane copolymer, it is necessary to produce the polycarbonate with the specific structure in advance, which is economically disadvantageous.

[0012] As described in detail, attempts have been made to obtain a polycarbonate-polyorganosiloxane copolymer by a method other than the interfacial polymerization method, but the current situation is that the introduction of siloxane blocks into the polymer main chain is insufficient. The present invention aims to obtain a polycarbonate-polyorganosiloxane copolymer that can introduce a sufficient amount of siloxane blocks into the polymer main chain by a method other than the interfacial polymerization method, and as a result, exhibits high mechanical properties. [Means for solving the problem]

[0013] As a result of extensive research, the present inventors have found that by producing a polycarbonate-polyorganosiloxane copolymer having a specific structure and satisfying specific conditions, a sufficient amount of siloxane blocks can be introduced into the polymer main chain, resulting in a polycarbonate-polyorganosiloxane copolymer with high mechanical properties. That is, the present invention relates to the following.

[0014] [1] A polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) consisting of a repeating unit represented by the following general formula (2), and satisfying the following condition (A) or (B): Condition (A): the amount of hexane extractables from the polycarbonate-polyorganosiloxane copolymer is 150 ppm by mass or less; Condition (B): The average weight of polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by separating the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatography satisfies the following formula (B1).

number

[0015] [4] The polycarbonate block (A-2) is an aromatic bis(4-hydroxyphenyl)-substituted or unsubstituted cyclohexane selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-hydroxyphenyl)cyclododecene. The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [3], which contains a structural unit derived from phenol, or a structural unit derived from an aliphatic diol selected from the group consisting of isosorbide, cyclohexane-1,4-dimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol. [5] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [4], wherein the polycarbonate block (A-2) has one or more repeating units selected from the group consisting of repeating units represented by the following general formulas (ai) to (av): [ka] [6] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [5], wherein in the general formula (1), a is an integer of 2 or more and 300 or less.

[0016] [7] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [6], wherein the polyorganosiloxane block (A-1) contains at least one selected from the group consisting of structural units represented by the following general formulas (1-1) to (1-3): [ka] [In the formula, R 1 ~R 4, R 6 , R 8 , z, a, and b are as described above. 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 1 to 10 carbon atoms in the alkyl group portion, and the functional group is -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 7 represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion, and as a functional group, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z1 represents 0 or 1. b1 represents an integer of 2 to 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.] [8] In the general formula (1), R 1 ~R 4 The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [7], wherein all of [9] In the general formula (1), R 6 is a trimethylene group (-(CH 2 ) 3 The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [8],

[10] In the general formula (1'), R 8 is a dimethylene group (-(CH 2 ) 2 -), methyl-substituted dimethylene group (-CH 2 CHMe-), trimethylene group (-(CH 2 ) 3 -), and the tetramethylene group (-(CH 2 ) 4 The polycarbonate-polyorganosiloxane copolymer according to any one of the above [2] to [9], wherein the copolymer has a structure selected from the group consisting of:

[11] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[10] , wherein the content of the polyorganosiloxane block represented by general formula (1) in the polycarbonate-polyorganosiloxane copolymer is 0.1 mass % or more and 60 mass % or less.

[12] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[11] , having a viscosity average molecular weight (Mv) of 5,000 or more and 50,000 or less.

[13] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[12] , wherein a 1 mm thick plate obtained by molding the polycarbonate-polyorganosiloxane copolymer has a haze value of 40 or less as measured in accordance with ISO 14782:1999.

[14] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[13] , obtained by a melt polymerization method.

[15] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[14] , obtained by using a diol monomer (a1).

[16] A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to

[15] .

[17] The polycarbonate resin composition according to

[16] above, further comprising an inorganic filler.

[18] The polycarbonate resin composition according to the above

[17] , comprising 1 to 150 parts by mass of the inorganic filler per 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer.

[19] The polycarbonate resin composition according to the above

[17] or

[18] , wherein the inorganic filler is glass fiber or carbon fiber.

[20] A molded article comprising the polycarbonate resin composition according to any one of

[16] to

[19] above. Effect of the Invention

[0017] According to the present invention, a sufficient amount of siloxane blocks can be introduced into the polymer main chain, so that a polycarbonate-polyorganosiloxane copolymer having excellent mechanical properties can be obtained. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] The polycarbonate-polyorganosiloxane copolymer and the polycarbonate-based resin composition containing the copolymer of the present invention will be described in detail below. In this specification, the definitions that are considered to be preferable can be adopted arbitrarily, and it can be said that a combination of preferable ones is more preferable. In this specification, the description "XX to YY" means "XX or more and YY or less".

[0019] <Polycarbonate-polyorganosiloxane copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) consisting of a repeating unit represented by the following general formula (2), and is characterized in that it satisfies the following condition (A) or (B): Condition (A): the amount of hexane extractable components in the polycarbonate-polyorganosiloxane copolymer is 150 ppm by mass or less; Condition (B): The average weight of polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by separating the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatography satisfies the following formula (B1).

number

[0020] R 6 When is an alkylene group, it preferably has 1 to 5 carbon atoms.

[0021] In order to enhance the affinity with the diol monomer (a1) and perform uniform polymerization, R 40 It is preferable that the alkyl group has a repeating chain structure in which at least two structures containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom are linked together. Examples of the structure containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom include -OH, -O-, -(C=O)-, -O(C=O)-, -O(C=O)O-, -NH 2A structure containing at least one structure selected from the group consisting of -NRH, -NR-, -NR-(C=O)-, -N=CR-, -SH, -S-, -SS- and -(S=O)- is preferred. R represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted with a substituent. Preferred examples of the repeating chain structure include polyether, polyacetal, polylactone, polyacrylate, polyester, polycarbonate, polyketone, polysulfide, polysulfone, polyamide, polyimide, and the like. Among them, at least one selected from the group consisting of polyether, polyacrylate, and polycarbonate is preferable, and polyether is most preferable. As the polyether, polyalkylene ether is preferable, and among them, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol are preferable.

[0022] As described above, the polycarbonate-polyorganosiloxane copolymer of the present invention contains a polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) and a polycarbonate block (A-2) consisting of a repeating unit represented by general formula (2).

[0023] When the polyorganosiloxane block constituting the polycarbonate-polyorganosiloxane copolymer contains the structural unit represented by the above general formula (1) and satisfies the above specific condition (A) or (B), the obtained polycarbonate-polyorganosiloxane copolymer can have a sufficient amount of siloxane blocks introduced into the main chain. 6 , R 40 , the selection of a, and / or R in the formula of the polycarbonate block (A-2) consisting of a repeating unit represented by the general formula (2) 10 Depending on the selection, even higher transparency can be obtained. As will be described later, the polycarbonate-polyorganosiloxane copolymer of the present invention can also be obtained by a melt polymerization method. The melt polymerization method does not require a solvent such as methylene chloride, and is therefore advantageous from an environmental and economical perspective. In addition, it is advantageous in terms of production because it does not use highly toxic phosgene as a carbonate source.

[0024] The polyorganosiloxane block (A-1) containing the structural unit represented by general formula (1) preferably has a structure represented by the following general formula (1A). [ka]

[0025] In the above general formula (1A), R 1 ~R 4 , R 6 , a and u are as defined above. R 40’ represents a divalent aliphatic hydrocarbon group having 2 to 380 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 380 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 380 carbon atoms, which may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 40’’ represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted with a substituent. e represents 0 or 1.

[0026] R 40’It is preferable that the alkyl group has a repeating chain structure in which at least two structures containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom are linked together. Examples of the structure containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom include -OH, -O-, -(C=O)-, -O(C=O)-, -O(C=O)O-, -NH 2 A structure containing at least one structure selected from the group consisting of -NRH, -NR-, -NR-(C=O)-, -N=CR-, -SH, -S-, -SS- and -(S=O)- is preferred. R represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted with a substituent. Preferred examples of the repeating chain structure include polyether, polyacetal, polylactone, polyacrylate, polyester, polycarbonate, polyketone, polysulfide, polysulfone, polyamide, polyimide, and the like. Among them, at least one selected from the group consisting of polyether, polyacrylate, and polycarbonate is preferred, and polyether is most preferred. As the polyether, polyalkylene ether is preferred, and among them, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol are preferred. The above structure is preferred from the viewpoint of increasing affinity with the diol monomer (a1) and performing uniform polymerization.

[0027] The polyorganosiloxane block (A-1) containing the structural unit represented by general formula (1) more preferably has a structure represented by the following general formula (1'). [ka] [In the formula, R 1 ~R 4 , R 6 and a are as described above. 8 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as functional groups, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z represents 0 or 1. b represents an integer of 2 to 200.] R 8 Preferred ones will be described later.

[0028] The polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) preferably contains at least one selected from the group consisting of structural units represented by the following general formulas (1-1) to (1-3). [ka] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a and b are as defined above. 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 1 to 10 carbon atoms in the alkyl group portion, and the functional group is -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 7 represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion, and as a functional group, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 111represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z1 represents 0 or 1. b1 represents an integer of 2 to 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.]

[0029] R 5 When is an alkylene group, it preferably has 1 to 5 carbon atoms.

[0030] In the formula, R 1 ~R 4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 1 ~R 4 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (R) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. 1 ~R 4 The alkoxy group represented by the formula (I) may be an alkoxy group represented by the formula (I) in which the alkyl group moiety is the above-mentioned alkyl group. 1 ~R 4 Examples of the aryl group represented by R include a phenyl group and a naphthyl group. 1 ~R 4 The alkylaryl group represented by the formula: embedded image includes a group in which the alkyl group portion is the above-mentioned alkyl group and the aryl group portion is the above-mentioned aryl group. R 1 ~R 4 are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 1 to 10 carbon atoms, and more preferably a methyl group.

[0031] R in the general formula (1), (1A) or (1′) 6 or R in general formulas (1-1) to (1-3) 5 and R 6 Examples of the arylene group having 6 to 20 carbon atoms represented by the formula (1), (1A) or (1′) include a phenylene group and a naphthylene group. 6or R in general formulas (1-1) to (1-3) 5 and R 6 Examples of the alkylene group having 1 to 10 carbon atoms represented by the formula (1), (1A) or (1') include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and a tetramethylene group (the tetramethylene group may have a branched structure). 6 or R in general formulas (1-1) to (1-3) 5 and R 6 The alkylarylene group represented by the formula: embedded image has the alkyl group portion being the above-mentioned alkyl group and the arylene group portion being the above-mentioned arylene group. R in the above general formula (1), (1A) or (1′) 6 or R in general formulas (1-1) to (1-3) 5 and R 6 Each of R is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably a dimethylene group, a methyl-substituted dimethylene group, or a trimethylene group. 6 is a trimethylene group (-(CH 2 ) 3 It is particularly preferred that

[0032] R in the above general formula (1') 8 or R in general formulas (1-1) to (1-3) 7 and R 8 Examples of the arylene group having 6 to 20 carbon atoms represented by the formula (1') include a phenylene group and a naphthylene group. 8 or R in general formulas (1-1) to (1-3) 7 and R 8 Examples of the alkylene group having 2 to 10 carbon atoms represented by the formula (1') include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and a tetramethylene group (the tetramethylene group may have a branched structure). 8 or R in general formulas (1-1) to (1-3) 7 and R 8The alkylarylene group represented by the formula: embedded image has the alkyl group portion being the above-mentioned alkyl group and the arylene group portion being the above-mentioned arylene group. R in the above general formula (1') 8 or R in general formulas (1-1) to (1-3) 7 and R 8 are each preferably an alkylene group having 1 to 10 carbon atoms, and a dimethylene group (-(CH 2 ) 2 -), methyl-substituted dimethylene group (-CH 2 CHMe-), trimethylene group (-(CH 2 ) 3 -), and the tetramethylene group (-(CH 2 ) 4 The above structure is preferable from the viewpoint of increasing the affinity with the diol monomer (a1) and performing uniform polymerization.

[0033] In the above general formula (1), (1A) or (1′) or general formula (1-1) to (1-3), R 1 ~R 4 are all methyl groups, R 6 Or R in general formulas (1-1) to (1-3) 5 and R 6 are all trimethylene groups, R 8 Or R in general formulas (1-1) to (1-3) 7 and R 8 In particular, polyorganosiloxanes in which each of the groups is a dimethylene group are preferred.

[0034] In general formulas (1-1) and (1-2), β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples thereof include divalent groups represented by the following general formulas (iii) to (vii). [ka]

[0035] In the above general formula (1), (1A) or (1'), or general formula (1-1) to (1-3), a represents the chain length of polyorganosiloxane, and represents an integer of 2 to 500, preferably 2 to 300, more preferably 10 to 120, even more preferably 15 to 100, and even more preferably 20 to 90. When a is within the above range, it is preferable because a polycarbonate-polyorganosiloxane copolymer having excellent mechanical properties can be obtained. When a represents an integer of, for example, 20 to 65, it is more preferable because the transparency is excellent in addition to the excellent mechanical properties.

[0036] In the above general formula (1') or general formulas (1-1) to (1-3), b and b1 each independently represent an integer of preferably 0 to 200, more preferably 2 to 100, even more preferably 5 to 50, and even more preferably 8 to 25. The above ranges are preferable for the ease of availability of raw materials. It is more preferable that b and b1 are 100 or less, because the deterioration of handleability due to an increase in the viscosity or melting point of the polyorganosiloxane can be suppressed, and it is more preferable that b and b1 are 50 or less, because the polyorganosiloxane block content in the resin can be maintained at an amount that can maintain the physical property improving effect. In the above general formula (1′) or general formulas (1-1) to (1-3), z and z1 each independently represent 0 or 1, and are preferably 0.

[0037] The polycarbonate-polyorganosiloxane copolymer of the present invention contains a polycarbonate block (A-2) consisting of repeating units represented by the above general formula (2). R in the above general formula (2) 10Examples of the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a 2-ethylhexylene group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group, an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, and an n-octadecylene group. Examples of the alicyclic hydrocarbon group having 3 to 40 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, and a tricyclodecylene group.

[0038] R in the above general formula (2) 10 As the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, various ones can be mentioned. In particular, divalent aromatic hydrocarbon groups derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane (bisphenol 3MZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol HTG), and 1,1-bis(4-hydroxyphenyl)cyclododecene can be mentioned. In addition, divalent aromatic hydrocarbon groups derived from at least one selected from the group consisting of hydroquinone, resorcinol, and catechol can also be mentioned.

[0039] The polycarbonate block (A-2) having the structure represented by the above general formula (2) preferably has a structure represented by the following general formula (111) and a structure represented by the following general formula (112). [ka] [In the formula, R 55 and R 56 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-, -SO 2 R represents -, -O- or -CO-. 100 R represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, which may include a branched structure or a cyclic structure. 100 may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. y represents an integer of 10 to 500. s and t each independently represent an integer of 0 to 4.]

[0040] In the above general formula (111), R 55 and R 56 The halogen atoms each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 55 and R 56 Examples of the alkyl groups each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" refers to both linear and branched butyl groups, and the same applies below), various pentyl groups, and various hexyl groups. 55 and R 56 The alkoxy groups each independently represent include those in which the alkyl moiety is the above-mentioned alkyl group.

[0041] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and an alkylene group having 5 to 10 carbon atoms is preferable. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group, and an alkylidene group having 5 to 10 carbon atoms is preferable, and an alkylidene group having 5 to 8 carbon atoms is more preferable. The aryl moiety of the aryl alkylene group represented by X includes aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc. The aryl moiety of the aryl alkylidene group represented by X includes aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc.

[0042] Each of s and t independently represents an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among them, 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, is preferable.

[0043] R 100 Specifically, the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms is an alkylene group having preferably 2 to 18, more preferably 2 to 10, and even more preferably 3 to 6 carbon atoms, a cycloalkylene group having preferably 4 to 20, and more preferably 5 to 20 carbon atoms, or a divalent oxygen- or nitrogen-containing saturated heterocyclic group having preferably 4 to 20, and more preferably 5 to 20 carbon atoms.

[0044] Examples of alkylene groups having 2 to 18 carbon atoms include ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, 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. Examples of the cycloalkylene group having 4 to 20 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, a tricyclodecylene group, etc. Examples of the divalent oxygen- or nitrogen-containing heterocyclic group include those containing an oxygen or nitrogen atom in the cycloalkylene group skeleton.

[0045] The polycarbonate block (A-2) consisting of the repeating unit represented by the above general formula (2) specifically preferably has at least one selected from the group consisting of the repeating units represented by the following general formulae (ai) to (a-xiii), more preferably has at least one selected from the group consisting of the following general formulae (ai) to (av), and from the viewpoint of high transparency, it is even more preferable that the polycarbonate block (A-2) consists of at least one selected from the group consisting of the repeating units represented by (ai), (a-ii) and (av). [ka] [ka] [ka]

[0046] The polycarbonate block (A-2) represented by general formula (2) preferably contains a structural unit derived from an aromatic bisphenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-hydroxyphenyl)cyclododecene, or an aliphatic diol selected from the group consisting of isosorbide, cyclohexane-1,4-dimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol.

[0047] In particular, it is more preferable that the polycarbonate block (A-2) consisting of the repeating unit represented by general formula (2) has one or more repeating units selected from the group consisting of the repeating units represented by the following general formulae (ai) to (av). [ka]

[0048] y, which indicates the number of units of the polycarbonate block (A-2) represented by the general formula (2), is more preferably 20 to 200, and even more preferably 40 to 100. By making y 20 or more, an increase in low molecular weight components in the copolymer can be suppressed, which is preferable. By making y 40 or more, the toughness of the copolymer is increased, which is preferable. By making y 200 or less, appropriate fluidity can be obtained during molding, which is preferable, and by making y 100 or less, the reaction mixture during production has appropriate fluidity, which is preferable since productivity is improved.

[0049] The content of the polyorganosiloxane block represented by general formula (1) in the above polycarbonate-polyorganosiloxane copolymer is preferably 0.1 to 60 mass%, more preferably 0.5 to 50 mass%, even more preferably 1 to 30 mass%, and still more preferably 3 to 20 mass%. When the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer is within the above range, better impact resistance and transparency can be obtained.

[0050] The polycarbonate-polyorganosiloxane copolymer of the present invention must have the above specific structure and satisfy either condition (A) or condition (B). It is also possible for the polycarbonate-polyorganosiloxane copolymer to satisfy both conditions (A) and (B). A polycarbonate-polyorganosiloxane copolymer satisfying condition (A) or condition (B) can be obtained, for example, by introducing a substituent having a repeating chain structure containing a polar functional group, which is a substituent having high affinity for the hydroxyl group of a diol monomer, into the terminal of a polyorganosiloxane. The substituent having the above-mentioned repeating chain structure can contact more diol monomer than the substituent having no repeating chain structure, so it is presumed that it can be strongly compatible with diol monomer.Therefore, it is presumed that when the above-mentioned repeating chain substituent is introduced to the end of polyorganosiloxane, the affinity between polyorganosiloxane and diol monomer can be increased more than when the substituent having the repeating chain structure is not introduced to the end.

[0051] <Condition (A)> This condition requires that the hexane extractable amount of the polycarbonate-polyorganosiloxane copolymer is 150 ppm by mass or less. "The hexane extractable amount is 150 ppm by mass or less" means that the amount of homocoupling components formed by bonding the same raw materials during the production of the polycarbonate-polyorganosiloxane copolymer, cyclic components formed by the reaction of unreacted raw materials and oligomers within the molecule, unreacted diol monomers, and unreacted terminal-modified polyorganosiloxanes is low, and polyorganosiloxane blocks are sufficiently introduced.

[0052] The hexane extraction amount of the polycarbonate-polyorganosiloxane copolymer under condition (A) is preferably 100 mass ppm or less, more preferably 80 mass ppm or less, even more preferably 70 mass ppm or less, and even more preferably 60 mass ppm or less. When condition (A) is satisfied, the lower limit of the hexane extraction amount is not particularly limited, but for synthesis reasons, it is, for example, 10 mass ppm or more, and in one embodiment, 20 mass ppm or more. When the polycarbonate-polyorganosiloxane copolymer is produced by the interfacial polymerization method, the hexane extraction amount can be relatively reduced compared to the melt polymerization method. The reason is that the interfacial polymerization method using methylene chloride and water as solvents allows the raw materials and polymer growth ends to be contacted more efficiently than the melt polymerization method performed without a solvent, so that the conversion rate of the raw materials to polymer is high, and unreacted raw materials and low molecular weight by-products that are extracted with hexane are less likely to be generated. However, when the melt polymerization method is selected, it is usually difficult to set the hexane extraction amount as condition (A). In the present invention, by using a polycarbonate-polyorganosiloxane copolymer having a specific structure, the above conditions can be satisfied even when the copolymer is produced by melt polymerization. The above hexane extraction conditions will be described in detail in the Examples.

[0053] <Condition (B)> The condition (B) requires that the average weight of polyorganosiloxane blocks contained in a polycarbonate-polyorganosiloxane copolymer obtained by separating the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatography satisfies the following formula (B1).

number

[0054] In formula (B1), [POS-Mh] represents the average weight of the polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by fractionating the components corresponding to the retention time range T1 to T2 using gel permeation chromatography, and [POS-Ml] represents the average weight of the polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by fractionating the components corresponding to the retention times T2 to T3 using gel permeation chromatography. T1: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene with Mw / Mn=1.01 and Mw=98,900 T2: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene with Mw / Mn=1.01 and Mw=13,700 T3: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene with Mw / Mn=1.03 and Mw=3,120

[0055] Measurement by gel permeation chromatography (GPC) can be carried out under the conditions described in the Examples. If the [POS-Mh] / [POS-Ml] value is outside the range of the above formula (B1), it indicates that the siloxane is not uniformly incorporated into the polymer main chain. The lower limit of the above [POS-Mh] / [POS-Ml] is preferably 0.35 or more, more preferably 0.5 or more, and even more preferably 0.8 or more, and the upper limit is preferably 2.8 or less, more preferably 2 or less, even more preferably 1.4 or less, even more preferably 1.25 or less, and particularly preferably 1.2 or less.

[0056] The viscosity average molecular weight of the polycarbonate-polyorganosiloxane copolymer of the present invention is preferably 5,000 or more and 50,000 or less, more preferably 12,000 or more, even more preferably 14,000 or more, particularly preferably 16,000 or more, and more preferably 30,000 or less, even more preferably 23,000 or less, particularly preferably 21,000 or less. The viscosity average molecular weight (Mv) is a value calculated from the intrinsic viscosity [η] of a methylene chloride solution (concentration: g / L) at 20° C. by the Schnell formula below. [η]=1.23×10 -5 Mv 0.83

[0057] The refractive index of the polycarbonate-polyorganosiloxane copolymer of the present invention is not particularly limited, but is preferably from 1.430 to 1.590, more preferably from 1.450 to 1.570, and even more preferably from 1.470 to 1.550, for light with a wavelength of 589.3 nm. The difference (nF-nC) between the refractive index (nF) of the polycarbonate resin for light with a wavelength of 486.1 nm and the refractive index (nC) for light with a wavelength of 656.3 nm is preferably 0.015 or less, more preferably 0.013 or less, and even more preferably 0.011 or less.

[0058] <Production method of polycarbonate-polyorganosiloxane copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by using a diol monomer (a1) and a polyorganosiloxane (a2) as raw material monomers.

[0059] <<Diol monomer (a1)>> The diol monomer (a1) is not particularly limited as long as it has a structure represented by the following general formula (a1): As the diol monomer (a1), an aromatic dihydroxy compound or an aliphatic dihydroxy compound can be used. [ka] R in the above general formula (a1) 10 are as described above, and the preferred ones are the same.

[0060] Examples of the aliphatic dihydroxy compounds include dihydroxy compounds having a chain aliphatic hydrocarbon group such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N-methyldiethanolamine, and p-xylylene glycol; 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,6-decalindiol, 1,5-decalindiol, 2,3-decalindiol, and 2,6-decalindimethanol; Dihydroxy compounds having an alicyclic hydrocarbon group, such as 1,5-decalin dimethanol, 2,3-decalin dimethanol, 2,3-norbornanediol, 2,5-norbornanediol, 2,3-norbornane dimethanol, 2,5-norbornane dimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 1,3-adamantanediol, 1,3-adamantanedimethanol, and tricyclodecane dimethanol; condensed polycyclic ether diols, such as isosorbide; , 3,9-bis(2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-diethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 3,9-bis(2-hydroxy-1,1-dipropylethyl)-2,4,8,10-tetraoxaspiro[5.5] Heterocyclic spiro compounds such as cyclic ether diols such as undecane and 1,4-anhydroerythritol; cyclic acetal diols such as 2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropan-1-ol; N-heterocyclic diols such as 3,4-pyrrolidinediol, 3,4-dimethylpiperidinediol, N-ethyl-3,4-piperidinediol, and N-ethyl-3,5-piperidinediol; and S-heterocyclic diols such as deoxythiofructose.

[0061] Specific examples of the aliphatic dihydroxy compound that can be particularly preferably mentioned include aliphatic diols selected from isosorbide, cyclohexane-1,4-dimethanol, tricyclodecane dimethanol, 3,9-bis(2-hydroxy-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol.

[0062] The aromatic dihydroxy compound may be an aromatic bisphenol compound, and more specifically, may be an aromatic bisphenol selected from bisphenol A, bisphenol C, bisphenol Z, and the compounds represented by the following general formula: [ka]

[0063] Specifically, it is more preferable to use bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol C (2,2-bis(4-hydroxy-3-methylphenyl)propane), bisphenol Z (1,1-bis(4-hydroxyphenyl)cyclohexane), bisphenol 3MZ (1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane), bisphenol HTG (1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane), or bisphenol-CDE (1,1-bis(4-hydroxyphenyl)cyclododecene). Among these, it is preferable to use an aliphatic diol as the diol monomer (a1), since the resulting polycarbonate-polyorganosiloxane copolymer can have high transparency.

[0064] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably has a structure represented by the following general formula (a2-0). [ka] [In the formula, R 1 ~R 4 may be the same or different and 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 in which the alkyl group moiety has 1 to 10 carbon atoms. R 5 and R 6 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as the functional group, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain 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. R 40’ represents a divalent aliphatic hydrocarbon group having 2 to 380 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 380 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 380 carbon atoms, which may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 40’’represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted with a substituent. e and u represent 0 or 1.]

[0065] R 40’ It is preferable that the repeating chain structure has at least two structures each containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Preferred examples of the repeating chain structure include polyether, polyacetal, polylactone, polyacrylate, polyester, polycarbonate, polyketone, polysulfide, polysulfone, polyamide, polyimide, and the like. Among them, at least one selected from the group consisting of polyether, polyacrylate, and polycarbonate is preferred, and polyether is most preferred. As the polyether, polyalkylene ether is preferred, and among them, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol are preferred. The above structure is preferred from the viewpoint of increasing affinity with the diol monomer (a1) and performing uniform polymerization.

[0066] As the polyorganosiloxane (a2), a monomer having any of the structures represented by the following general formulas (a2-1) to (a2-3) can be used. [ka]

[0067] In the above formula, R 1 ~R 4 , R 5 and R 6 , R 7 and R 8, z, z1, β, a, b and b1 are as described above. The preferred ones are the same, and the combinations of the preferred ones are the same. In the above general formulae (a2-0) and (a2-1) to (a2-3), a represents the chain length of the polyorganosiloxane, and from the viewpoint of increasing the affinity with the diol monomer (a1) and performing uniform polymerization, represents an integer of 2 or more and 500 or less, preferably 2 or more and 300 or less, more preferably 10 or more and 100 or less, even more preferably 15 or more and 70 or less, and even more preferably 20 or more and 65 or less. In the above general formulae (a2-1) to (a2-3), b represents an integer of 2 or more and 200 or less, preferably 2 or more and 100 or less, more preferably 5 or more and 50 or less, and even more preferably 8 or more and 25 or less. From the viewpoint of increasing affinity with the diol monomer (a1) and performing uniform polymerization, the above range is preferable.

[0068] The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by polymerizing raw material monomers by interfacial polymerization or melt polymerization (ester exchange). When produced by interfacial polymerization, the method described in JP 2014-80462 A, for example, can be referred to. The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by reacting raw material monomers polyorganosiloxane (a2), diol monomer (a1), and a carbonate ester compound by melt polymerization in the presence of a base catalyst, preferably in the presence of a terminal terminator.

[0069] (carbonic acid diester) The diester carbonate is at least one compound selected from diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds. The diaryl carbonate compound is a compound represented by the following general formula (11) or a compound represented by the following general formula (12). [ka] [In formula (11), Ar 1 and Ar 2 Each of Ar represents an aryl group and may be the same or different. 3 and Ar 4 each represents an aryl group, which may be the same or different; D 1 represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0070] The dialkyl carbonate compound is a compound represented by the following general formula (13) or a compound represented by the following general formula (14). [ka] [In formula (13), R 21 and R 22 Each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and may be the same or different. 23 and R 24 each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same or different, D 2 represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0071] The alkylaryl carbonate compound is a compound represented by the following general formula (15) or a compound represented by the following general formula (16). [ka] [In formula (15), Ar 5 is an aryl group, R 25 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. 6 is an aryl group, R 26 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms; D 1represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0072] Examples of diaryl carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, and bisphenol A bisphenyl carbonate. Examples of dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. When producing the polycarbonate-polyorganosiloxane copolymer of the present invention, one or more of the above compounds can be appropriately selected and used as the carbonate diester, and among these, it is preferable to use diphenyl carbonate.

[0073] (Terminator) In the production of the polycarbonate-polyorganosiloxane copolymer of the present invention, a terminal terminator can be used as necessary. As the terminal terminator, a terminal terminator known in the production of polycarbonate resins can be used, and specific examples 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 in combination of two or more.

[0074] (Branching Agent) A branching agent can also be used in producing the polycarbonate-polyorganosiloxane copolymer of the present invention. Examples of branching agents include phloroglucin, trimellitic acid, 1,1,1-tris(4-hydroxyphenyl)ethane, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, and isatin bis(o-cresol).

[0075] Specifically, the polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by melt polymerization, for example, according to the following procedure. The diol monomer (a1), the polyorganosiloxane (a2), and the carbonate compound are subjected to an ester exchange reaction. The amount of the carbonate compound relative to the amount of the diol monomer is preferably 0.9 to 1.2 times by mol, and more preferably 0.98 to 1.02 times by mol.

[0076] In the above transesterification reaction, the amount of the terminal terminator is preferably in the range of 0.05 to 10 mol% relative to the diol monomer (a1) and the polyorganosiloxane (a2), since the hydroxyl group terminals of the resulting polycarbonate-polyorganosiloxane copolymer are blocked, and a polycarbonate resin having sufficiently excellent heat resistance and water resistance is obtained. The amount of the terminal terminator relative to the diol monomer (a1) and the polyorganosiloxane (a2) is more preferably 1 to 6 mol%. The entire amount of the terminal terminator may be added to the reaction system in advance, or a portion of the terminal terminator may be added to the reaction system in advance, and the remainder may be added as the reaction proceeds. It is preferable to simultaneously charge an antioxidant into a reactor together with the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate compound, and to carry out the transesterification reaction in the presence of the antioxidant.

[0077] The reaction temperature for carrying out the transesterification reaction is not particularly limited and is usually selected within the range of 100 to 330° C., preferably 180 to 300° C., and more preferably 200 to 240° C., but it is particularly preferred to gradually increase the temperature to 180 to 300° C. as the reaction proceeds. If the temperature of this transesterification reaction is 100° C. or higher, the reaction rate increases, while if it is 330° C. or lower, side reactions do not occur and problems such as coloration of the resulting polycarbonate-polyorganosiloxane copolymer are unlikely to occur.

[0078] The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. There are no particular limitations as long as the reaction is carried out efficiently. In general, the reaction pressure is set to atmospheric pressure (normal pressure) or pressurized state of 1 to 50 atm (760 to 38,000 torr) in the early stage of the reaction, and reduced pressure in the later stage of the reaction, preferably 1.33 to 1.33×10 4 It is often expressed as Pa (0.01 to 100 torr). The reaction time may be such that the reaction is continued until the target molecular weight is reached, and is usually about 0.2 to 10 hours.

[0079] The above transesterification reaction is usually carried out in the absence of an inert solvent, but may be carried out in the presence of 1 to 150 parts by mass of an inert solvent per 100 parts by mass of the resulting polycarbonate resin, if necessary. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; tricyclo[5.2.1.0 2,6 ] Cycloalkanes such as decane, cyclooctane, and cyclodecane are also included. If necessary, the reaction may be carried out in an inert gas atmosphere. Examples of the inert gas include argon, carbon dioxide, nitrous oxide, nitrogen, and other gases, chlorofluorohydrocarbons, alkanes such as ethane and propane, and alkenes such as ethylene and propylene.

[0080] In the melt polymerization method, it is preferable to use a basic catalyst as a catalyst. The basic catalyst may be at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing aryl groups, and metal compounds. These compounds may be used alone or in combination. As the basic catalyst, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals, quaternary ammonium hydroxides, quaternary phosphonium salts containing an aryl group, etc. are preferably used. The basic catalysts can be used alone or in combination of two or more kinds.

[0081] Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogen carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, and dilithium salt of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol. 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.

[0082] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having an alkyl or aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Other examples include bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0083] Examples of the metal compound include a zinc aluminum compound, a germanium compound, an organotin compound, an antimony compound, a manganese compound, a titanium compound, and a zirconium compound.

[0084] Specific examples of quaternary phosphonium salts containing an aryl group include tetra(aryl or alkyl)phosphonium hydroxides such as tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide; tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(pt-butylphenyl)phosphonium diphenylphosphate, triphenylbutylphosphonium phenolate, and triphenylbutylphosphonium tetraphenylborate. The quaternary phosphonium salt containing an aryl group is preferably combined with a nitrogen-containing organic basic compound, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0085] The amount of the basic catalyst used is preferably 1×10 -9 ~1×10 -2 Molar, preferably 1 x 10 -8 ~1×10 -2 mole, more preferably 1×10 -7 ~1×10 -3 can be chosen in the molar range.

[0086] A catalyst deactivator may be added in the later stage of the reaction. Known catalyst deactivators are effectively used as the catalyst deactivator, and among them, ammonium salts and phosphonium salts of sulfonic acid are preferred. Furthermore, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, and salts of p-toluenesulfonic acid such as tetrabutylammonium salt of p-toluenesulfonic acid are preferred.

[0087] As the ester of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, etc. are also preferably used. Among them, tetrabutylphosphonium dodecylbenzenesulfonate or butyl p-toluenesulfonate is most preferably used.

[0088] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the amount of the catalyst deactivator used is preferably 0.5 to 50 mol, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol, per mol of the catalyst. It is preferable to add a catalyst deactivator and mix an antioxidant after terminating the polymerization reaction.

[0089] The reaction in the melt polymerization method may be carried out either continuously or batchwise. The reaction apparatus used in the melt polymerization may be either a vertical reaction apparatus equipped with an anchor type impeller, a Max Blend impeller, or a helical ribbon type impeller, or a horizontal reaction apparatus equipped with a paddle impeller, a lattice impeller, or a spectacle impeller. It may also be an extruder type equipped with a screw. In the case of a continuous method, it is preferable to use such reaction apparatuses in appropriate combination.

[0090] The polycarbonate-polyorganosiloxane copolymer of the present invention is preferably produced using raw materials that satisfy the following conditions. Condition (i): A mixture obtained by contacting a raw material diol monomer (a1), a raw material polyorganosiloxane (a2), a carbonic acid diester, and a basic catalyst at 100 to 250°C for 0.5 to 5 hours has a haze value of 30 or less, as measured in accordance with ISO 14782:1999 under conditions of 23°C and an optical path length of 10 mm.

[0091] The haze value is a value measured by a haze measuring device at 23° C. in accordance with ISO 14782:1999 using a glass cell filled with the mixture and having an optical path length of 10 mm. Note that the conditions for measuring the haze value of the raw material mixture are different from the polymerization conditions and are simply the conditions used when selecting raw materials.

[0092] If the haze value of the raw material mixture after the heat treatment is within the above range, the resulting polycarbonate-polyorganosiloxane copolymer will have high transparency, which is preferable. The haze value of the raw material mixture after the heat treatment is more preferably 20 or less, further preferably 10 or less, further preferably 5 or less, and further preferably 1 or less. The conditions for obtaining the mixture for measuring the haze value are as described in (i) above. Furthermore, the temperature condition in the condition (i) is preferably 150 to 250°C, more preferably 180 to 250°C, and the contact time is preferably 0.7 to 4 hours, more preferably 0.7 to 2 hours. In the condition (i), when the temperature condition and the contact time are within the above-mentioned preferred ranges and the obtained mixture has a haze value specified in the condition (i), a polycarbonate-polyorganosiloxane copolymer having higher transparency can be obtained.

[0093] <Polycarbonate Resin Composition> The polycarbonate resin composition of the present invention contains the above-mentioned polycarbonate-polyorganosiloxane copolymer (polycarbonate-polyorganosiloxane copolymer (A)). Well-known additives can be used in the polycarbonate resin composition of the present invention, as long as the additives do not impair the properties of the polycarbonate-polyorganosiloxane copolymer (A).

[0094] (Additives) The polycarbonate resin composition of the present invention may contain known additives depending on the intended use and the needs, such as various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, and mold release agents. The antioxidant can suppress decomposition of the resin during the production or molding of the thermoplastic resin composition.

[0095] [Filler] Examples of fillers that can be incorporated into the polycarbonate resin composition of the present invention include inorganic fillers such as spherical fillers, plate-like fillers, and fibrous fillers. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloons, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, and amorphous zeolite. Examples of the plate-like filler include talc, mica, and wollastonite. Examples of the fibrous filler include acicular fillers such as glass fiber, carbon fiber, and wollastonite, and fibrous fillers such as magnesium oxysulfate, potassium titanate fiber, and fibrous calcium carbonate. The inorganic filler is preferably glass fiber or carbon fiber.

[0096] As the glass fiber, any of those made from alkali-containing glass, low-alkali glass, non-alkali glass, etc. can be suitably used. The form of these glass fibers is not particularly limited, and any form such as roving, milled fiber, chopped strand, etc. can be used. Commercially available glass fibers include CSH-3PA (manufactured by Nitto Boseki Co., Ltd.), T511 (manufactured by Nippon Electric Glass Co., Ltd.), and MA409C (manufactured by Asahi Fiber Glass Co., Ltd.). The polycarbonate resin composition of the present invention preferably contains a glass filler from the viewpoint of strengthening the resin composition.

[0097] [Composition ratio] The polycarbonate resin composition of the present invention may contain an inorganic filler in an amount of preferably 1 to 150 parts by mass, more preferably 11 to 100 parts by mass, even more preferably 15 to 60 parts by mass, and even more preferably 15 to 40 parts by mass, per 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A). By setting the amount within the above range, various mechanical properties attributable to the inorganic filler, for example, strength such as elastic modulus, can be improved without impairing the characteristics of the polycarbonate-polyorganosiloxane copolymer (A).

[0098] The method for producing the polycarbonate-based resin composition of the present invention is not particularly limited as long as it has a step of mixing a polycarbonate-polyorganosiloxane copolymer with any additive. For example, the polycarbonate-polyorganosiloxane copolymer can be produced by mixing the polycarbonate-polyorganosiloxane copolymer with any additive using a mixer or the like and melt-kneading the mixture. The melt-kneading can be carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, or the like. The heating temperature during melt-kneading is appropriately selected usually within the range of 150°C to 300°C, preferably about 220°C to 300°C.

[0099] [Molded products] The molded article of the present invention contains the polycarbonate-based resin composition of the present invention. The molded article can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc., using a melt-kneaded product of the polycarbonate-based resin composition or pellets obtained through melt-kneading as a raw material. In particular, it is preferable to produce a molded article by injection molding or injection compression molding using the obtained pellets.

[0100] The thickness of the molded article can be set arbitrarily depending on the application, and is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm, particularly when the molded article is required to be transparent. When the thickness of the molded article is 0.2 mm or more and 4.0 mm or less, good mechanical strength can be obtained.

[0101] If necessary, the molded article may be coated with a hard coat film, an anti-fogging film, an antistatic film, or an anti-reflection film, or may be coated with a composite film of two or more kinds of films. Among them, it is particularly preferable that a hard coat film is formed, since it has good weather resistance and can prevent wear of the surface of the molded article over time. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic hard coat agents can be used.

[0102] In the case of a molded article containing a glass filler, the presence of at least a portion of the glass filler on the outermost surface of the molded article may increase the surface roughness of the molded article, increase the amount of diffuse reflection on the surface of the molded article, and as a result, the transparency of the molded article may be deteriorated. For this reason, as a method for reducing the surface roughness of a molded article, there is a method for reducing the surface roughness of the molded article by forming a layer (skin layer) with a high resin content on the outermost surface of the molded article. As a method for forming this skin layer, in the case of injection molding, the temperature of the mold is made higher than the general conditions, so that the resin in contact with the mold can flow easily, and the surface roughness of the outermost surface of the molded article can be reduced. In addition, in the case of compression molding, the pressure during molding is made higher than the general conditions, so that the surface roughness of the outermost surface of the molded article can be reduced. By using these methods to reduce the surface roughness of the molded article, diffuse reflection on the surface of the molded article is reduced, haze is reduced, and as a result, the transparency of the molded article can be improved.

[0103] When the molded article thus obtained is molded into a flat plate, if the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is less than 5% by mass and the average chain length a of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer is less than 70, the total light transmittance for visible light is preferably 60% or more. The total light transmittance is more preferably 70% or more, even more preferably 80% or more, even more preferably 85% or more, and even more preferably 90% or more. If the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is 5% by mass or more, the total light transmittance for visible light is preferably 25% or more. The haze during the above-mentioned flat plate molding is preferably 40 or less, more preferably 30 or less, even more preferably 15 or less, and even more preferably 5 or less, when the content of the polyorganosiloxane block represented by formula (1) in the polycarbonate-polyorganosiloxane copolymer is less than 5 mass% and the average chain length a of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer is less than 70. Molded articles having the above optical properties have excellent transparency and can be used in applications requiring high transparency. The total light transmittance for visible light can be measured in accordance with ISO 13468-1:1996, and the haze can be measured in accordance with ISO 14782:1999.

[0104] Molded articles containing the polycarbonate resin according to the present invention can be suitably used for components requiring transparency and rigidity, as well as scratch resistance and weather resistance, such as: 1) automobile parts such as sunroofs, door visors, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms, and gratings; 3) windows for railway cars and ships; 4) various parts for televisions, radio cassettes, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, cash registers, copiers, printers, facsimiles, and other electrical equipment parts, such as exterior panels and housing parts; 5) precision equipment parts such as cases and covers for precision equipment such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display instruments; 6) agricultural parts such as vinyl greenhouses and greenhouses; and 7) furniture parts such as lighting covers, blinds, and interior fixtures. EXAMPLES

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0106] The characteristic values ​​in each example were determined according to the procedures described below. <Method for measuring hexane extractables> The amount of hexane extractables was measured by the following method. The polycarbonate-polyorganosiloxane copolymer pellets obtained in the following Examples and Comparative Examples were crushed in a crusher to obtain a sample, which was passed through a 20 mesh (mesh opening 0.84 mm) to remove large lumps that were not crushed sufficiently, and then sieved on a 300 mesh (mesh opening 0.055 mm). The sample remaining on the mesh was collected as a sample for hexane extraction, thereby removing overly crushed fine powder. Next, about 15 g of the hexane extraction sample obtained by the above method was weighed out and placed in a cylindrical filter paper (No. 84, inner diameter 28 mm x total length 100 mm) and set in a Soxhlet extractor. Next, extraction was performed by refluxing for 8 hours using 300 mL of n-hexane at a reflux rate of 70 mL / time every 3 to 4 minutes. After that, the n-hexane was removed from the obtained n-hexane extract by contacting it with a 40°C water bath using an evaporator. After that, it was vacuum dried at room temperature for 2.5 hours, and the amount of hexane extraction (mass ppm) was calculated from the mass (g) of the components remaining in the eggplant flask using the following formula. Hexane extractable amount (mass ppm) = 1,000,000 x H / amount of sample used for extraction (H: mass of hexane extract remaining in the eggplant flask, unit: g)

[0107] <Method for quantifying polydimethylsiloxane content> Example) Quantitative analysis of polydimethylsiloxane contained in the polycarbonate-polyorganosiloxane copolymer obtained in Example 3 NMR device: JEOL RESONANCE ECA-500 Probe: TH5 5φ NMR sample tube compatible Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of times accumulated: 256 NMR sample tube: 5φ Sample size: 30-40mg Solvent: deuterated chloroform Measurement temperature: room temperature A: The integral value of the meta position of the phenyl part observed around δ7.3~7.5 B: The integral value of the methyl group of the dimethylsiloxane part observed around δ-0.02 to 0.3 C: Integral value of methine group of ISB (isosorbide) part observed around δ4.8-5.3 D: Integral value of methylene groups of PEG observed around δ3.3-3.8 E: integral value of methine and methylene groups in the CHDM moiety observed in the vicinity of δ0.8-2.0 F: The integral value of the methylene group at the terminal of dimethylsiloxane observed around δ0.4-0.6 a=A / 2 b=B / 6 c=C / 3 d=D / 4 e=(EF) / 10 T=a+b+c+d+e f=a / T×100 g=b / T×100 h=c / T×100 i=d / T×100 j=e / T×100 TW=f×93+g×74.1+h×172+i×44+j×170 PDMS (wt%) = g × 74.1 / TW × 100

[0108] <Measurement method for [POS-Mh] and [POS-Ml]> For various polycarbonate-polyorganosiloxane copolymers shown in the following examples and comparative examples, the average weight (wt%) of the polyorganosiloxane block contained in the polycarbonate-polyorganosiloxane copolymer obtained by separating the components corresponding to the retention time range T1-T2 by gel permeation chromatography (GPC) was determined by the above-mentioned measurement method, and the value was defined as [POS-Mh]. Similarly, the average weight (wt%) of the polyorganosiloxane block contained in the polycarbonate-polyorganosiloxane copolymer obtained by separating the components corresponding to the retention time range T2-T3 was defined as [POS-Ml]. The GPC measurement method and the method for determining T1, T2, and T3 are described below. ·Preparation conditions for polycarbonate-polyorganosiloxane copolymer by GPC Test equipment: Shimadzu Corporation, Preparative GPC [SPD-M20A] Solvent: Chloroform Column: JAIGEL-4H, JAIGEL-2H Column temperature: room temperature Flow rate: 3.8mL / min Detector: RI Injection concentration: For polystyrene standards: 3 mg / mL Polycarbonate-polyorganosiloxane copolymer: 30 mg / mL Injection volume: 3mL T1 to T3 were determined from the peak tops of the chromatograms obtained by measuring polystyrene standards using the above GPC. Polystyrene standard: The following standard polystyrene manufactured by Tosoh Corporation was used. F-10: Mw / Mn=1.01, Mw=98,900 F-2: Mw / Mn=1.01, Mw=13,700 A-2500: Mw / Mn=1.03, Mw=3,120

[0109] <Viscosity average molecular weight of polycarbonate-polyorganosiloxane copolymer> The viscosity of a methylene chloride solution (concentration: g / L) at 20° C. was measured using an Ubbelohde viscometer, from which the limiting viscosity [η] was determined and the viscosity average molecular weight (Mv) was calculated using the following formula (Schnell formula). [η]=1.23×10 -5 Mv 0.83

[0110] [Evaluation test] <Total light transmittance of resin molded products: Tt(%), haze value> The pellets for evaluation obtained in each Example and Comparative Example were used to prepare a three-stage plate for evaluating transparency (90mm×50mm, 3mm thick part 45mm×50mm, 2mm thick part 22.5mm×50mm, 1mm thick part 22.5mm×50mm) at a cylinder temperature of 240° C. and a mold temperature of 80° C. using an injection molding machine (manufactured by Niigata Machine Techno Co., Ltd., screw diameter 30mmφ). The total light transmittance was measured for the 1mm thick part of the three-stage plate in accordance with ISO 13468-1:1996. The haze value was measured for the 1mm thick part of the same sample in accordance with ISO 14782:1999. For both values, the measuring device used was NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the haze value, the higher the transparency of the sample. Haze = Td / Tt x 100 (Wherein, Td: diffuse transmittance, Tt: total light transmittance)

[0111] <Total light transmittance (%) and haze value of raw material mixture> The total light transmittance and haze value of the raw material mixture were determined using the following measuring device, glass cell, and measuring method. Measuring device: Nippon Denshoku Industries Co., Ltd. NDH5000 Glass cell: Optical path length: 10 mm Dimensions: External dimensions 14mm (depth) x 40mm (width) x 55mm (height) Glass thickness on each side: 2mm Before measuring the haze of the raw material mixture, the glass cell was filled with pure water to perform zero point correction. Specifically, the measurement value when the cell was filled with pure water was corrected to a state where the total light transmittance was 100% and the haze value was 0.00. Next, the pure water was removed from the glass cell, and the liquid mixture obtained by the method described below was filled in the cell, and measurements were performed to determine the haze value at 23°C in accordance with ISO 14782:1999. Haze = Td / Tt x 100 (Wherein, Td: diffuse transmittance, Tt: total light transmittance)

[0112] Production Example 1: Production of PDMS-1 Under nitrogen atmosphere, the following formula: [ka] To a polyorganosiloxane (100 g) having an average siloxane chain length of 24 represented by the following formula: [ka] Polyethylene glycol with an average oxyethylene chain length of 15, as shown in the formula (1), was added in a molar amount (82.3 g) twice that of the polyorganosiloxane. 455 g of isopropyl alcohol (2.5 parts relative to the total mass of the polyorganosiloxane and the polyethylene glycol) was added thereto, and the mixture temperature was controlled to 80°C and thoroughly stirred. Next, a toluene solution of a platinum vinylsiloxane complex was added in an amount such that the mass of platinum atoms was 5 ppm by mass relative to the siloxane, and the mixture was stirred for 10 hours. The isopropyl alcohol and platinum catalyst were removed from the resulting mixture to obtain a polyether-modified polyorganosiloxane PDMS-1.

[0113] Manufacturing Example 2: Manufacturing of PDMS-2 Production was carried out in the same manner as in Production Example 1, except that an α,ω-dihydrogenorganopolysiloxane having an average siloxane chain length of 61 was used.

[0114] Manufacturing Example 3: Manufacturing of PDMS-3 Production was carried out in the same manner as in Production Example 1, except that an α,ω-dihydrogenorganopolysiloxane having an average siloxane chain length of 88 was used.

[0115] Production Example 4: Production of PDMS-4 Production was carried out in the same manner as in Production Example 1, except that the average oxyethylene chain length of the polyethylene glycol used was 12.

[0116] Manufacturing Example 5: Manufacturing of PDMS-5 Under nitrogen atmosphere, the following formula: [ka] 2-allylphenol was added to polyorganosiloxane having an average siloxane chain length of 39 in an amount twice as much as the polyorganosiloxane. The mixture was thoroughly stirred while controlling the temperature of the mixture at 100°C. Next, a toluene solution of platinum vinylsiloxane complex was added in an amount such that the mass of platinum atoms was 5 ppm by mass relative to the siloxane, and the mixture was stirred for 10 hours. Isopropyl alcohol and the platinum catalyst were removed from the resulting mixture to obtain allylphenol-modified polyorganosiloxane PDMS-5.

[0117] Production Example 6: Production of PDMS-6 Production was carried out in the same manner as in Production Example 5, except that eugenol was used instead of 2-allylphenol.

[0118] Production Example 7: Production of PDMS-7 Instead of polyethylene glycol, ethylene glycol monoallyl ether (CH 2 =CHCH 2 -O-CH 2 CH 2 —OH) was used.

[0119] Manufacturing Example 8: Manufacturing of PDMS-8 The same procedure as in Production Example 1 was followed, except that the average siloxane chain length of the polyorganosiloxane used was 45, the average oxyethylene chain length of the polyethylene glycol used was 8, the solvent was toluene, and the reaction temperature was 110°C.

[0120] Manufacturing Example 9: Manufacturing of PDMS-9 Production was carried out in the same manner as in Production Example 8, except that the average oxyethylene chain length of the polyethylene glycol used was 38, that the solvent was toluene, and that the reaction temperature was 110°C.

[0121] Manufacturing Example 10: Manufacturing of PDMS-10 Production was carried out in the same manner as in Production Example 1, except that the average siloxane chain length of the polyorganosiloxane used was 5, that toluene was used as the solvent, and that the reaction temperature was 110°C.

[0122] Production Example 11: Production of PDMS-11 In a nitrogen atmosphere, 350 mL of methylene chloride was added to a flask, 21.5 g of 2,6-di-t-butylpyridine and 21 g of trifluoromethanesulfonic anhydride were added thereto, and the mixture was cooled to 15°C or lower. 4.3 g of allyl alcohol was added dropwise to form a reaction initiator. After stirring for about 15 minutes, 1 L of dehydrated tetrahydrofuran was added and stirred at 20-23°C for 5 minutes, and then 30 mL of ion-exchanged water was added to stop the reaction. Extraction was performed with heptane, washing was performed with 10% hydrochloric acid, and the water layer was separated, followed by washing twice with ion-exchanged water to separate the water layer. Thereafter, the solvent was distilled off under reduced pressure, and the following formula: [ka] Thus, 120 g of one-terminal allyl-modified polytetramethylene glycol (chain length of the tetramethylene glycol moiety = 20) was obtained. The same production method as in Production Example 8 was used, except that the one-terminal allyl-modified polytetramethylene glycol obtained in the above reaction was used instead of polyethylene glycol, the solvent was changed to a 1:1 (mass ratio) mixture of toluene and isopropanol, the amount of solvent used was three times the total volume of the polyorganosiloxane and one-terminal allyl-modified polytetramethylene glycol, and the reaction temperature was controlled at 80 to 90°C.

[0123] Manufacturing Example 12: Manufacturing of PDMS-12 In a flask under nitrogen, -C 3 H 6 O.C. 2 H 4 Polydimethylsiloxane (SiMe 2The average number of chains of O units: 40) and trimethylene carbonate in a molar amount 25 times that of the hydroxyl group of the polyorganosiloxane mentioned above were charged, and dehydrated dichloromethane was added so that the concentration of these raw materials was 10 wt%. 1,8-diazabicycloundecene in an amount of 3 equivalents relative to the terminal OH group of polydimethylsiloxane was added as a catalyst to the obtained transparent reaction solution, and the reaction was allowed to proceed at room temperature for 48 hours. After that, the reaction mixture was stopped by adding benzoic acid, and the reaction mixture was reprecipitated in a mixed solvent consisting of a mixture of methanol, 2-propanol, and hexane (volume ratios of 10:1:10, respectively), and the resulting precipitate was dried in a vacuum to obtain PDMS-12 (number of polytrimethylene carbonate chains at each end: 18).

[0124] Manufacturing Example 13: Manufacturing of PDMS-13 Under a nitrogen atmosphere, 450 mL of methylene chloride was added to the flask, 45.0 g of 3-iodo-1-propanol was added thereto, and the mixture was cooled in an ice bath. 40.1 g of tert-butyldimethylchlorosilane was added thereto, and the mixture was stirred at room temperature for 20 hours. The resulting mixture was quenched with a 5% aqueous solution of sodium bicarbonate, and the product was extracted with ethyl acetate / ion-exchanged water. The resulting product was purified using a silica gel column to obtain a TBS-protected form of 3-iodo-1-propanol (yield: 67.7 g). Under a nitrogen atmosphere, 2.9 g of the TBS-protected 3-iodo-1-propanol and 270 mL of tetrahydrofuran were mixed in a flask and cooled to -65°C or lower. 12.5 mL of 1.6 mol / L tert-butyllithium (pentane solution) was added dropwise and stirred for 15 minutes. 2.5 mL of diphenylethylene was added dropwise and stirred for 30 minutes. Then, 55 mL of 0.52 mol / L lithium chloride THF solution was added and stirred for 10 minutes. Next, 10.1 mL of methyl methacrylate was added and stirred for 10 minutes. Next, 3.36 mL of allyl bromide was added to quench the reaction, and then the mixture was mixed at room temperature for 12 hours. The resulting reaction mixture was concentrated under reduced pressure, reprecipitated with a THF / heptane system, and then subjected to silica gel column purification to remove the solvent to obtain a TBS-protected PMMA with one end allyl modification. This product was dissolved in THF and deprotected with 2 mol / L aqueous hydrochloric acid. The reaction mixture was poured into heptane to separate the target product (deprotected product). This deprotected product was purified by a silica gel column and the solvent was removed to obtain the product represented by the following formula: [ka] Thus, one-terminal allyl-modified PMMA (number of PMMA units=20) was obtained. The same production method as in Production Example 8 was carried out, except that the above-mentioned one-terminated allyl-modified PMMA was used instead of polyethylene glycol.

[0125] Manufacturing Example 14: Manufacturing of PDMS-14 Instead of polyethylene glycol, [ka] The same procedure as in Production Example 1 was repeated except that polypropylene glycol having an average oxypropylene chain length of 15, as shown in

[0126] PDMS-1 to PDMS-14 obtained in Production Examples 1 to 14 are shown in Table 1.

[0127] [Table 1]

[0128] [others] BisP-A: Bisphenol A [Idemitsu Kosan Co., Ltd.] 1,4-CHDM: 1,4-cyclohexanedimethanol [Tokyo Chemical Industry Co., Ltd.] TCDDM: Tricyclodecane dimethanol [manufactured by OXEA GmbH] 1,3-PG: 1,3-propanediol [Tokyo Chemical Industry Co., Ltd.] PEG400: Polyethylene glycol 400 [average molecular weight 380-420 g / mol, manufactured by Tokyo Chemical Industry Co., Ltd.] DPC: Diphenyl carbonate [Mitsui Fine Chemicals Co., Ltd.] 0.01N sodium hydroxide solution [FUJIFILM Wako Pure Chemical Industries, Ltd.]

[0129] Example 1 <Transparency evaluation of raw material mixture after heat treatment> BisP-A (2,489.9 g), DPC (2,500 g) (molar ratio of each raw material: BisP-A / DPC = 100 / 107), and 28.2 g of polyether-modified polyorganosiloxane PDMS-1 were added to a 10 L stainless steel reactor equipped with a double helical blade as a stirring device. After these raw material monomers were completely melted at 150 °C, stirring was started at 70 rpm and the inside of the reactor was replaced with nitrogen. Next, 1.64 mL of 0.01 N sodium hydroxide was added as a catalyst (1.5 × 10 relative to the total diol monomer moles). -6 Then, while maintaining the nitrogen pressure at 101 kPa, the same as atmospheric pressure, the temperature of the mixture was raised to 200°C and maintained at that temperature for 60 minutes. The contents were then removed from the valve at the bottom of the reactor, yielding a liquid, transparent raw material mixture. The liquid raw material mixture after the heat treatment had a total light transmittance of 98.4 and a haze value of 0.5, indicating high transparency.

[0130] <Production of polycarbonate-polyorganosiloxane (PC-POS) copolymer> A polycarbonate-polyorganosiloxane copolymer was produced using the following raw materials and conditions. The raw materials used were the same as those used in the above transparency evaluation, but the polymerization conditions were as follows. In a 10 L stainless steel reactor equipped with a stirrer, a trap to capture distilled phenol, and a pressure reducing device, 2,489.9 g of BisP-A and 2,500 g of DPC (molar ratio of each raw material: BisP-A / DPC = 100 / 107) were added as diol monomers, and 28.2 g of polyether modified polyorganosiloxane PDMS-1 was added. These raw material monomers were completely melted at 150 °C, and the inside of the reactor was replaced with nitrogen. 1.64 mL of 0.01 N sodium hydroxide was used as a catalyst (1.5 × 10 relative to the total number of moles of diol monomers). -6 The reactor was heated to 180°C and the pressure reduced to 200mmHg (26.6kPa) over a period of about 60 minutes, and the reaction conditions were maintained until the amount of phenol distilled reached 0.2 L. Thereafter, the reactor was heated to 200°C inside temperature and the pressure reduced to 10mmHg (1.3kPa) over a period of about 60 minutes, and the conditions were maintained until 1.0 L of phenol was distilled. Next, the internal temperature of the reactor was raised to 240°C over about 120 minutes, and the conditions were maintained until 1.5L of phenol was distilled. Next, the internal temperature of the reactor was adjusted to 280°C and the degree of vacuum was adjusted to 1mmHg (0.1kPa) or less over about 120 minutes, phenol was distilled at least 2L, and the reaction was continued until a predetermined stirring torque was reached. Then, the pressure was restored with nitrogen, and 0.037g (10 times the amount of NaOH moles) of p-butyl toluenesulfonate was added as a deactivator. Irganox 1010 and Irgafos 168 were added so that the content in the obtained polymer was 1,500ppm, and the mixture was thoroughly stirred. Then, resin strands were extracted from the bottom of the reactor by nitrogen pressure and cut with a pelletizer to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0131] Example 2 As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2500 g of DPC (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), except that 24.4 g of polyether-modified polyorganosiloxane PDMS-1 was used, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.5% and a haze value of 0.5. As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2500 g of DPC (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), except that 24.4 g of polyether-modified polyorganosiloxane PDMS-1 was used, by polymerizing under the same conditions as in Example 1, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0132] Example 3 <Transparency evaluation of the raw material mixture after heat treatment> Except that 1193.8 g of isosorbide (ISB), 504.9 g of 1,4-CHDM, 2500 g of DPC (mol ratio of each raw material: ISB / 1,4-CHDM / DPC = 70:30:100), and 20.2 g of polyether-modified polyorganosiloxane PDMS-1 were used, the heat treatment of the raw materials was carried out in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 99.5% and a haze value of 0.4.

[0133] <Production of PC-POS copolymer> In a 10L stainless steel reactor equipped with a stirrer, a trap to capture distilled phenol, and a pressure reducing device, ISB (1193.8g), 1,4-CHDM (504.9g), DPC (2,500g) (molar ratio of each raw material: ISB / 1,4-CHDM / DPC = 70:30:100), and 20.2g of polyether modified polyorganosiloxane PDMS-1 were added as diol monomers, and these raw material monomers were completely melted at 100°C, and the inside of the reactor was replaced with nitrogen. 1.64mL of 0.01N sodium hydroxide was used as a catalyst (1.5 x 10 relative to the total number of diol monomer moles). -6 The reactor was heated and depressurized to 180°C and 200mmHg (26.6kPa) over a period of about 50 to 100 minutes, and these conditions were maintained until the amount of phenol distilled reached 0.2 L. Thereafter, the reactor was heated and depressurized to 200°C and 10mmHg (1.3kPa) over a period of about 150 minutes, and these conditions were maintained until 1.8 L of phenol was distilled. Next, the reactor internal temperature was adjusted to 220°C and the vacuum level to 1 mmHg (0.1 kPa) or less over about 60 minutes, phenol was distilled at 2 L or more, and the reaction was continued until a predetermined stirring torque was reached. Then, the pressure was restored with nitrogen, and 0.037 g (10 times the amount of NaOH moles) of p-butyl toluenesulfonate was added as a deactivator. Irganox 1010 and Irgafos 168 were added so that the content in the resulting polymer was 1,500 ppm, and the mixture was thoroughly stirred. Then, resin strands were extracted from the bottom of the reactor by nitrogen pressure and cut with a pelletizer to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0134] Example 4 Except for using 20.2 g of PDMS-2 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 98.4% and a haze value of 0.8. A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 3, except that 20.2 g of PDMS-2 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0135] Example 5 Except for using 20.2 g of PDMS-3 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 98.1% and a haze value of 1.3. A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 3, except that 20.2 g of PDMS-3 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0136] Example 6 Except for using 20.2 g of PDMS-4 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 97.9% and a haze value of 0.7. A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 3, except that 20.2 g of PDMS-4 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0137] Example 7 Except for using 105.4 g of PDMS-1 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 97.5% and a haze value of 0.9. A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 3, except that 105.4 g of PDMS-1 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0138] Example 8 Except for using 222.5 g of PDMS-1 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 97.1% and a haze value of 1.1. A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 3, except that 222.5 g of PDMS-1 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0139] Example 9 The transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3, except that ISB (1193.8 g), TCDDM (687.2 g), DPC (2,500 g) (molar ratio of each raw material: ISB / TCDDM / DPC = 70:30:100), and 22.1 g of polyether-modified polyorganosiloxane PDMS-1 were used as diol monomers. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 98.5% and a haze value of 0.4. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 3, except that ISB (1193.8 g), TCDDM (687.2 g), DPC (2,500 g) (molar ratio of each raw material: ISB / TCDDM / DPC = 70:30:100) and 22.1 g of polyether-modified polyorganosiloxane PDMS-1 were used as diol monomers. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0140] Example 10 The transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3, except that the diol monomers were ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2,500 g) (molar ratio of each raw material: ISB / 1,4-CHDM / 1,3-PG / DPC = 70:25:5:100), and 19.8 g of polyether-modified polyorganosiloxane PDMS-1. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. As diol monomers, ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2,500 g) (molar ratio of each raw material: ISB / 1,4-CHDM / 1,3-PG / DPC = 70: 25: 5: 100), and 19.8 g of polyether-modified polyorganosiloxane PDMS-1 were used, but polymerization was performed under the same conditions as in Example 3 to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0141] Example 11 As diol monomers, ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2,500 g) [molar ratio of each raw material: ISB / 1,4-CHDM / PEG400 / DPC = 70: 28: 2: 100 (the number of moles of PEG400 was the value obtained by dividing the mass used by the average molecular weight of 400)], and 21.3 g of polyether-modified polyorganosiloxane PDMS-1 were used. The transparency evaluation of the raw material mixture after the heat treatment was performed in the same manner as in Example 3. The liquid raw material mixture after the heat treatment had high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. As the diol monomer, ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2500 g) [mol ratio of each raw material: ISB / 1,4-CHDM / PEG400 / DPC = 70:28:2:100 (the number of moles of PEG400 was the value obtained by dividing the used mass by the average molecular weight of 400)], except that 21.3 g of polyether-modified polyorganosiloxane PDMS-1 was used, polymerization was carried out under the same conditions as in Example 3 to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0142] Example 12 <Transparency evaluation of the raw material mixture after heat treatment> Except that 179.7 g of PDMS-8 was used as the polyorganosiloxane, the transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 90.8% and a haze value of 2.5. <Production of PC-POS copolymer> Except that 179.7 g of PDMS-8 was used as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20100, a polydimethylsiloxane content of 5.00% by mass, a total light transmittance of 33.7%, a haze value of 97.0, an amount of hexane extractable components of 653 ppm, [POS-Mh] / [POS-Ml] = 1.47, and a Charpy impact strength (with notch) of 81.0 kJ / m 2 It was.

[0143] Example 13 <Transparency evaluation of the raw material mixture after heat treatment> Except for using 312.8 g of PDMS-8 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 89.1% and a haze value of 2.6. <Production of PC-POS Copolymer> Except for using 312.8 g of PDMS-8 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,100, a polydimethylsiloxane content of 8.30% by mass, a total light transmittance of 28.3%, a haze value of 98.1, an amount of hexane extractable components of 714 ppm, [POS-Mh] / [POS-Ml] = 1.23, and a Charpy impact strength (with notch) of 85.0 kJ / m 2 It was.

[0144] Example 14 <Evaluation of Transparency of Raw Material Mixture after Heat Treatment> Except for using 179.7 g of PDMS-9 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 90.1% and a haze value of 2.0. <Production of PC-POS Copolymer> Except for using 179.7 g of PDMS-9 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane content of 3.10% by mass, a total light transmittance of 62.0%, a haze value of 89.4, an amount of hexane extractable components of 663 ppm, [POS-Mh] / [POS-Ml] = 1.13, and a Charpy impact strength (with notch) of 75.0 kJ / m 2 It was.

[0145] Example 15 <Evaluation of transparency of raw material mixture after heat treatment> The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1, except that 179.7 g of PDMS-10 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 91.0% and a haze value of 1.3. <Production of PC-POS copolymer> A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1, except that 179.7 g of PDMS-10 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20150, a polydimethylsiloxane content of 0.90% by mass, a total light transmittance of 86.1%, a haze value of 6.8, an amount of hexane extractable components of 585 ppm, [POS-Mh] / [POS-Ml]=1.09, and a Charpy impact strength (with notch) of 76.0 kJ / m 2 It was.

[0146] Example 16 <Evaluation of transparency of raw material mixture after heat treatment> The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1, except that 28.2 g of PDMS-11 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 89.9% and a haze value of 7.3. <Production of PC-POS copolymer> A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1, except that 28.2 g of PDMS-11 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20200, a polydimethylsiloxane content of 0.53% by mass, a total light transmittance of 65.1%, a haze value of 83.5, an amount of hexane extractable components of 83 ppm, and [POS-Mh] / [POS-Ml]=1.20.

[0147] Example 17 <Evaluation of transparency of the raw material mixture after heat treatment> Except for using 57.1 g of PDMS-11 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 78.6% and a haze value of 12.0. <Production of PC-POS copolymer> Except for using 57.1 g of PDMS-11 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20100, a polydimethylsiloxane content of 1.10% by mass, a total light transmittance of 48.1%, a haze value of 87.5, an amount of hexane extractable components of 143 ppm, and [POS-Mh] / [POS-Ml] = 1.23.

[0148] Example 18 <Evaluation of transparency of the raw material mixture after heat treatment> Except for using 28.2 g of PDMS-12 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 97.9% and a haze value of 0.9. <Production of PC-POS copolymer> Except for using 28.2 g of PDMS-12 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 19900, a polydimethylsiloxane content of 0.45% by mass, a total light transmittance of 81.0%, a haze value of 11.3, an amount of hexane extractable components of 49 ppm, and [POS-Mh] / [POS-Ml] = 1.20.

[0149] Example 19 <Evaluation of transparency of the raw material mixture after heat treatment> Except for using 179.7 g of PDMS-12 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 91.3% and a haze value of 2.1. <Production of PC-POS Copolymer> Except for using 179.7 g of PDMS-12 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,100, a polydimethylsiloxane content of 2.70% by mass, a total light transmittance of 61.0%, a haze value of 82.1, an amount of hexane extractable components of 550 ppm, and [POS-Mh] / [POS-Ml] = 1.41.

[0150] Example 20 <Evaluation of Transparency of Raw Material Mixture after Heat Treatment> Except for using 28.2 g of PDMS-13 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 91.5% and a haze value of 8.5. <Production of PC-POS Copolymer> Except for using 28.2 g of PDMS-13 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,050, a polydimethylsiloxane content of 0.42% by mass, a total light transmittance of 63.5%, a haze value of 81.2, an amount of hexane extractable components of 75 ppm, and [POS-Mh] / [POS-Ml] = 1.22.

[0151] Example 21 <Evaluation of Transparency of Raw Material Mixture after Heat Treatment> Except for using 20.2 g of PDMS-14 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.1% and a haze value of 1.0. <Production of PC-POS Copolymer> Except for using 20.2 g of PDMS-14 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 2. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 15,000, a polydimethylsiloxane content of 0.68% by mass, a total light transmittance of 69.7%, a haze value of 84.0, an amount of hexane extractable components of 55 ppm, and [POS-Mh] / [POS-Ml] = 1.31.

[0152] Example 22 <Evaluation of Transparency of Raw Material Mixture after Heat Treatment> Except for using 19.7 g of PDMS-1 as the polyorganosiloxane, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 99.2% and a haze value of 0.4. <Production of PC-POS Copolymer> Except for using 19.7 g of PDMS-1 as the polyorganosiloxane, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 15,600, a polydimethylsiloxane content of 0.43% by mass, a total light transmittance of 86.8%, a haze value of 3.9, an amount of hexane extractable components of 55 ppm, [POS-Mh] / [POS-Ml] = 1.09, and a Charpy impact strength (with notch) of 19.5 kJ / m 2 It was. It was.

[0153] Comparative Example 1 Except for using 24.4 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 2. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 78.5% and a haze value of 93.2. Except for using 24.4 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 2 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0154] Comparative Example 2 Except for using 20.2 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 79.1% and a haze value of 92.1. Except for using 20.2 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 3 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0155] Comparative Example 3 Except for using 105.4 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 63.2% and a haze value of 95.5. Except for using 105.4 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 3 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0156] Comparative Example 4 Except for using 20.2 g of PDMS-6 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 79.5% and a haze value of 93.1. Except for using 20.2 g of PDMS-6 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 3 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0157] Comparative Example 5 Except for using 20.2 g of PDMS-7 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 3. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 81.1% and a haze value of 88.9. Except for using 20.2 g of PDMS-7 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 3 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0158] Comparative Example 6 Except for using 22.1 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 9. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 80.1% and a haze value of 90.1. Except for using 22.1 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 9 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0159] Comparative Example 7 Except for using 19.8 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 10. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 78.5% and a haze value of 89.9. Except for using 19.8 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 10 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0160] Comparative Example 8 Except for using 21.3 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 11. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 79.9% and a haze value of 88.5. Except for using 21.3 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 11 to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0161] Comparative Example 9 Except for using 19.8 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 78.1% and a haze value of 94.5. Except for using 19.8 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a polycarbonate-polyorganosiloxane copolymer in the form of pellets that were strongly opaque. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 15,100, a polydimethylsiloxane content of 0.62 mass%, a total light transmittance of 53.1%, a haze value of 98.5, a hexane extractable component amount of 175 ppm, [POS-Mh] / [POS-Ml]=1.1, and a Charpy impact strength (notched) of 15.8 kJ / m 2 It was.

[0162] Comparative Example 10 Except for using 179.7 g of PDMS-5 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 65.1% and a haze value of 97.5. A strongly opaque pellet-like polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1, except that 179.7 g of PDMS-5 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane content of 5.30 mass%, a total light transmittance of 19.3%, a haze value of 99.6, a hexane extractable component amount of 1,351 ppm, [POS-Mh] / [POS-Ml]=1.4, and a Charpy impact strength (notched) of 61.0 kJ / m 2 It was.

[0163] Comparative Example 11 Except for using 179.7 g of PDMS-7 as the polyorganosiloxane, the transparency of the raw material mixture after the heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 66.5% and a haze value of 96.2. Except for using 179.7 g of PDMS-7 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 to obtain a polycarbonate-polyorganosiloxane copolymer in the form of pellets that were strongly opaque. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,100, a polydimethylsiloxane content of 5.50 mass%, a total light transmittance of 17.5%, a haze value of 99.5, a hexane extractable content of 1,416 ppm, [POS-Mh] / [POS-Ml]=1.3, and a Charpy impact strength (notched) of 61.0 kJ / m 2 It was.

[0164] [Table 2]

[0165] [Table 3]

Claims

1. A method for producing a polycarbonate-polyorganosiloxane copolymer using, as raw material monomers, a diol monomer (a1) represented by the following general formula (a1) and a polyorganosiloxane (a2) having any of the structures represented by the following general formulas (a2-1) to (a2-3), which satisfies the following condition (A) or (B): Condition (A): the hexane extractable amount of the polycarbonate-polyorganosiloxane copolymer is 150 ppm by mass or less; Condition (B): The average weight of polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by separating the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatography satisfies the following formula (B1): [0010] [In formula (B1), [POS-Mh] represents the average weight of polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by fractionating the components corresponding to the retention time range T1 to T2 using gel permeation chromatography. [POS-Ml] represents the average weight of polyorganosiloxane blocks contained in the polycarbonate-polyorganosiloxane copolymer obtained by fractionating the components corresponding to the retention time range T2 to T3 using gel permeation chromatography. T1: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene having Mw / Mn=1.01 and Mw=98,900 T2: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene having Mw / Mn=1.01 and Mw=13,700 T3: retention time at which the peak top is located in the gel permeation chromatogram of standard polystyrene having Mw / Mn=1.03 and Mw=3,120. 【number】 [In the formula, R 1 ~R 4 may be the same or different, and 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 in which the alkyl group moiety has 1 to 10 carbon atoms. R 5 and R 6 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as functional groups, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 7 represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; 111 - may be included. 8 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as a functional group, -O-, -CO-, -S-, -NH-, -NR 111 - may contain R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z represents 1. z1 represents 1. a represents an integer from 2 to 500, and b represents an integer from 5 to 200. b1 represents an integer from 5 to 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. R 10 represents a divalent 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, which may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.]

2. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein in the general formulas (a2-1) to (a2-3), a is an integer of 2 or more and 300 or less.

3. In the general formulae (a2-1) to (a2-3), R １ ~R ４ The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein all of the groups represent a methyl group.

4. In the general formulae (a2-1) to (a2-3), R ６ is a trimethylene group (-(CH ２ ) ３ The method for producing the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3, wherein

5. In the general formulae (a2-1) to (a2-3), R ８ is a dimethylene group (-(CH ２ ) ２ -), methyl-substituted dimethylene group (-CH ２ CHMe-), trimethylene group (-(CH ２ ) ３ -), and the tetramethylene group (-(CH ２ ) ４ The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 4, wherein the copolymer has a structure selected from the group consisting of:

6. The polyorganosiloxane (a2), the diol monomer (a1), and a carbonate ester compound are reacted by melt polymerization under a basic catalyst. The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 5.

7. The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 6, wherein the obtained polycarbonate-polyorganosiloxane copolymer comprises a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1') and a polycarbonate block (A-2) consisting of a repeating unit represented by the following general formula (2): 【Chemistry 2】 [In the formula, R 1 ~R 4 may be the same or different, and 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 in which the alkyl group moiety has 1 to 10 carbon atoms. R 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 1 to 10 carbon atoms in the alkyl group portion; 111 - may be included. 8 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 2 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as a functional group, -O-, -CO-, -S-, -NH-, -NR 111 - may contain R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z represents 1. b represents an integer of 5 to 200. a represents an integer of 2 to 500. R 10 represents a divalent 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, which may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, or at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. y represents an integer of 10 to 500.]

8. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 7, wherein the viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer is 5,000 or more and 50,000 or less.

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