Polycarbonate-polyorganosiloxane copolymer and resin composition containing said copolymer

Abstract

To provide a polycarbonate-polyorganosiloxane copolymer having high transparency.SOLUTION: Provided is a method for producing a polycarbonate-polyorganosiloxane copolymer, using a specific diol monomer (a1) and a specific polyorganosiloxane (a2) as raw monomers.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, mechanical properties, and 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 of directly reacting an aromatic dihydroxy compound with phosgene (interfacial polycondensation method) and a method of subjecting an aromatic dihydroxy compound with a carbonate diester to a transesterification reaction in a molten state (melt polymerization method).

[0003] Interfacial polymerization is often used to produce polycarbonate-polyorganosiloxane copolymers. For example, a diaryldiol compound such as bisphenol is reacted with phosgene in the presence of an organic solvent to produce a polycarbonate oligomer having reactive chloroformate groups. Simultaneously with or subsequent 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, polymerization reactions can produce homo-coupled products in which the same raw material components are bonded together, or unreacted raw material components, resulting from some raw materials not participating in the polymerization reaction. These components remain in the polymer without being uniformly incorporated into the polymer backbone, significantly reducing the transparency and mechanical properties of the polymer. The interfacial polymerization method described above rarely causes these problems and produces polycarbonate-polyorganosiloxane copolymers with excellent transparency and mechanical properties.

[0004] On the other hand, the interfacial polymerization method requires the use of highly toxic phosgene as a carbonate source. Additionally, the polymerization reaction system requires the use of methylene chloride as a solvent, which places a heavy burden on the environment. Its removal requires large degassing equipment and a large amount of energy, making it economically disadvantageous. To avoid this problem, other manufacturing methods, such as melt polymerization, for producing polycarbonate-polyorganosiloxane copolymers have been considered.

[0005] Patent Document 2 discloses the production 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 producing 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 producing polysiloxane / polycarbonate block cocondensation products, which comprises reacting a hydroxyaryloxy-terminated dimethylsiloxane with an oligocarbonate having a specific weight-average molecular weight and a specific terminal ratio (OH terminal groups to aryl terminal groups) in the melt 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 Si-free diphenol, and a diaryl carbonate ester in the presence of a specific catalyst. Patent Document 6 discloses a method for producing a modified polycarbonate resin by solid-state 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 a transesterification method. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-189953 [Patent Document 2] U.S. Patent 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] Japanese Patent Application Laid-Open No. 2008-248262 [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 methods for producing polycarbonate-polyorganosiloxane copolymers by melt polymerization, but these methods are still insufficient in terms of obtaining polycarbonate-polyorganosiloxane copolymers with good transparency and mechanical properties. Patent Document 2 does not teach anything about the transparency of polymers obtained using silanol-terminated siloxanes, and it is known that the lower the molecular weight of silanol-terminated dimethylsiloxanes, the more likely they are to undergo intramolecular condensation. The cyclic siloxanes produced as a result of intramolecular condensation remain in the resulting polycarbonate-polysiloxane copolymer, adversely affecting its transparency and mechanical properties, and raising concerns about adverse effects such as relay contact failure in electrical and electronic applications.

[0009] Although Patent Document 3 indicates that the amount of polydimethylsiloxane incorporated into the polymer main chain increases, it does not teach anything about the transparency of the resulting polymer. Furthermore, because it describes the appearance of the carbonate-terminated polysiloxane in a molten state with other raw materials as "milky white," it is presumed that the carbonate-terminated polysiloxane is separated from the other raw materials, and that components generated by homocoupling and unreacted carbonate-terminated polysiloxane remain in the copolymer. These components significantly reduce the transparency and mechanical properties of the polycarbonate-polysiloxane copolymer. Patent Document 3 also mentions 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) is used in an amount of 10 × 10 moles relative to the number of moles 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 the polycarbonate chain, and the resulting polymer does not have the heat resistance or weather resistance to withstand practical conditions.

[0010] In the method disclosed in Patent Document 4, the appearance of the obtained polymer is described as "white," and as such, the uniformity during polymerization of siloxane and other raw materials is still insufficient, and there is still room for improvement in the transparency and mechanical properties.

[0011] The copolymer disclosed in Patent Document 5 has a large domain structure, which is thought to have a negative effect on transparency. Patent Document 6 generally discusses the transparency of polycarbonate resins, but does not demonstrate that polycarbonate-polyorganosiloxane copolymers have high transparency. Patent Documents 7 to 9 produce copolymers having polysiloxane blocks with the same structure by a transesterification method (melt polymerization method), but as described in Patent Document 8, the resulting resin is an opaque white powder.

[0012] Although attempts have been made to obtain polycarbonate-polyorganosiloxane copolymers by methods other than interfacial polymerization, no effective means for obtaining polycarbonate-polyorganosiloxane copolymers with high transparency has yet been demonstrated. An object of the present invention is to obtain polycarbonate-polyorganosiloxane copolymers with high transparency. [Means for solving the problem]

[0013] As a result of extensive research, the present inventors have found that a polycarbonate-polyorganosiloxane copolymer having a specific structure has high transparency.

[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): [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. 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, and the functional group may be -O-, -COO-, -CO-, -S-, -NH-, or -NR 111 - may contain multiple R 8may 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, 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. z represents 0 or 1. a represents an integer of 2 to 500, and b represents an integer of 2 to 200. 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 with 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 oxygen atoms, nitrogen atoms, and sulfur atoms, or at least one halogen atom selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. y represents an integer of 10 to 500. [2] The polycarbonate-polyorganosiloxane copolymer according to [1] above, wherein the polycarbonate block (A-2) 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-, -SO2-, -O-, or -CO-. R 100 R represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, which may have a branched structure or a cyclic structure. 100may contain at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, and at least one halogen atom selected from fluorine, chlorine, bromine, and iodine atoms. y represents an integer of 10 to 500. s and t each independently represent an integer of 0 to 4.] [3] The polycarbonate block (A-2) is 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 [1] or [2] above, which contains structural units derived from an aromatic bisphenol 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.

[0015] [4] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [3] above, 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 formulae (ai) to (av): [ka] [5] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [4], wherein in the general formula (1), a is an integer of 2 or more and 300 or less. [6] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [5], wherein the polyorganosiloxane block (A-1) contains at least one structural unit 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, b are as described above. R 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 1 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.] [7] In the general formula (1), R 1 ~R 4 The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [6], wherein all of are methyl groups. [8] In the general formula (1), R 6 The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [7], wherein is a trimethylene group (-(CH2)3-).

[0016] [9] In the general formula (1), R 8is any one structure selected from the group consisting of a dimethylene group (-(CH2)2-), a methyl-substituted dimethylene group (-CH2CHMe-), a trimethylene group (-(CH2)3-), and a tetramethylene group (-(CH2)4-).

[10] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [9] above, wherein the content of the polyorganosiloxane block represented by general formula (1) in the polycarbonate-polyorganosiloxane copolymer is 0.1% by mass or more and 60% by mass or less.

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

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

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

[11] above, 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.

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

[12] , which is obtained by a melt polymerization method.

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

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

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

[14] .

[16] The polycarbonate resin composition according to

[15] above, further comprising an inorganic filler.

[17] The polycarbonate resin composition according to

[16] above, which contains 1 to 150 parts by mass of the inorganic filler per 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer.

[18] The polycarbonate resin composition according to the above

[16] or

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

[19] A molded article made of the polycarbonate resin composition according to any one of the above

[15] to

[18] . [Effects of the Invention]

[0017] According to the present invention, a polycarbonate-polyorganosiloxane copolymer having high transparency can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0018] The polycarbonate-polyorganosiloxane copolymer of the present invention and the polycarbonate-based resin composition containing the copolymer are described in detail below. In this specification, the preferred definitions can be adopted arbitrarily, and it can be said that a combination of preferred definitions is more preferable. In this specification, the expression "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):

[0020] [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. 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, and the functional group may be -O-, -COO-, -CO-, -S-, -NH-, or -NR 111- may contain multiple R 8 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, 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. z represents 0 or 1. a represents an integer of 2 to 500, and b represents an integer of 2 to 200. 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 with 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 oxygen atoms, nitrogen atoms, and sulfur atoms, or at least one halogen atom selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. y represents an integer of 10 to 500.

[0021] R 6 When is an alkylene group, it preferably has 1 to 5 carbon atoms.

[0022] The polycarbonate-polyorganosiloxane copolymer has high transparency because the polyorganosiloxane block constituting the polycarbonate-polyorganosiloxane copolymer contains the structural unit represented by the general formula (1). 10 Depending on the selection of the material, even higher transparency can be obtained. The polyorganosiloxane blocks constituting the polycarbonate-polyorganosiloxane copolymer contain structural units represented by the general formula (1) above, resulting in highly transparent polycarbonate-polyorganosiloxane copolymers. This is presumably because the structural units represented by the general formula (1) improve the compatibility of the polyorganosiloxane with other raw material components such as diol monomers and carbonate esters, increase the reactivity of the polyorganosiloxane, and exhibit the effect of incorporating the polyorganosiloxane into the polymer with high randomness. More specifically, the above-mentioned effect of the structural units represented by the general formula (1) reduces the amount of unreacted polyorganosiloxane and polymers containing extremely large amounts of polyorganosiloxane, thereby reducing the interfaces between components that arise when these components separate within the polymer. This is presumably why highly transparent polycarbonate-polyorganosiloxane copolymers are obtained. As will be described later, the polycarbonate-polyorganosiloxane copolymer of the present invention can also be obtained by melt polymerization. Melt polymerization does not require a solvent such as methylene chloride, which is environmentally and economically advantageous. In addition, it does not use highly toxic phosgene as a carbonate source, which is advantageous in terms of production.

[0023] The polyorganosiloxane block (A-1) containing the 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 formulae (1-1) to (1-3). [ka] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, b are as described above. R 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 7represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 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.]

[0024] R 5 When is an alkylene group, it preferably has 1 to 5 carbon atoms.

[0025] 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 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 one 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 (I) includes a group in which the alkyl group moiety is the above-mentioned alkyl group and the aryl group moiety 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.

[0026] R in general formula (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 R include a phenylene group and a naphthylene group. 5 and R 6 Examples of the alkylene group having 1 to 10 carbon atoms represented by R 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). 5 and R 6 The alkylarylene group represented by the formula (I) includes a group in which the alkyl group moiety is the above-mentioned alkyl group and the arylene group moiety is the above-mentioned arylene group. R 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 particularly preferably a trimethylene group (-(CH2)3-).

[0027] 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 1 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 8 The alkylarylene group represented by the formula (I) includes a group in which the alkyl group moiety is the above-mentioned alkyl group and the arylene group moiety is the above-mentioned arylene group. R in the above general formula (1) 8or 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 more preferably any structure selected from the group consisting of a dimethylene group (-(CH2)2-), a methyl-substituted dimethylene group (-CH2CHMe-), a trimethylene group (-(CH2)3-), and a tetramethylene group (-(CH2)4-).

[0028] In the above general formula (1) or general formulas (1-1) to (1-3), R 1 ~R 4 are both methyl groups, R 5 and R 6 are both trimethylene groups, R 7 and R 8 In particular, polyorganosiloxanes in which each of the groups is an ethyl group are preferred.

[0029] 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]

[0030] In the above general formula (1) or general formulas (1-1) to (1-3), a represents the chain length of the polyorganosiloxane and is an integer of 2 to 500, preferably 2 to 300, more preferably 10 to 100, even more preferably 15 to 70, and still more preferably 20 to 65. When a is within the above range, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance, which is preferable because it becomes a highly transparent copolymer. In the above general formula (1) or general formulas (1-1) to (1-3), b and b1 each independently represent 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. The above ranges are preferred because of the ease of availability of raw materials. When b and b1 are 100 or less, it is possible to suppress a decrease in handleability due to an increase in the viscosity or melting point of the polyorganosiloxane, so it is more preferable. When b and b1 are 50 or less, it is possible to maintain the polyorganosiloxane block content in the resin at an amount that can maintain the property-improving effect, so it is more preferable. In the above general formula (1) or general formulae (1-1) to (1-3), z and z1 each independently represent 0 or 1, and are preferably 0.

[0031] 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) 10 Examples of the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by the formula (I) include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, 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 divalent alicyclic hydrocarbon groups 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.

[0032] R in the above general formula (2) 10Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (I) include various groups. Particularly, examples include 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. Other examples include divalent aromatic hydrocarbon groups derived from at least one member selected from the group consisting of hydroquinone, resorcinol, and catechol.

[0033] 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-, -SO2-, -O-, or -CO-. R 100 R represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, which may have a branched structure or a cyclic structure. 100may contain at least one heteroatom selected from oxygen, nitrogen, and sulfur atoms, and at least one halogen atom selected from fluorine, chlorine, bromine, and iodine atoms. y represents an integer of 10 to 500. s and t each independently represent an integer of 0 to 4.]

[0034] In the above general formula (111), R 55 and R 56 The halogen atoms independently represented by each of the groups include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 55 and R 56 Examples of alkyl groups that R each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups ("various" means that both linear and branched groups are included, 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.

[0035] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and an alkylene group having 5 to 10 carbon atoms is preferred. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group, and an alkylidene group having 5 to 10 carbon atoms is preferred, and an alkylidene group having 5 to 8 carbon atoms is more preferred. Examples of the aryl moiety of the aryl alkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc. Examples of the aryl moiety of the aryl alkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc.

[0036] s and t each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, a compound in which s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a compound in which s and t are 0 and X is an alkylidene group, particularly an isopropylidene group, is preferred.

[0037] R 100 Specifically, the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by is preferably an alkylene group having 2 to 18 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms, a cycloalkylene group having 4 to 20 carbon atoms, and more preferably 5 to 20 carbon atoms, or a divalent oxygen- or nitrogen-containing saturated heterocyclic group having 4 to 20 carbon atoms, and more preferably 5 to 20 carbon atoms.

[0038] 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 groups. 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.

[0039] Specifically, the polycarbonate block (A-2) consisting of repeating units represented by the above general formula (2) preferably has at least one selected from the group consisting of 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 it has at least one selected from the group consisting of repeating units represented by (ai), (a-ii), and (av). [ka] [ka] [ka]

[0040] The polycarbonate block (A-2) represented by general formula (2) preferably contains structural units 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.

[0041] 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]

[0042] y, which indicates the number of units in the polycarbonate block (A-2) represented by general formula (2), is more preferably 20 to 200, and even more preferably 40 to 100. Setting y to 20 or more is preferable because it can suppress an increase in low-molecular-weight components in the copolymer. Setting y to 40 or more is preferable because it increases the toughness of the copolymer. Setting y to 200 or less is preferable because it provides appropriate fluidity during molding, and setting y to 100 or less is preferable because the reaction mixture during production has appropriate fluidity, thereby improving productivity.

[0043] The content of the polyorganosiloxane block represented by general formula (1) in the 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.

[0044] The polycarbonate-polyorganosiloxane copolymer of the present invention is characterized by its high transparency. Specifically, in one embodiment, the polycarbonate-polyorganosiloxane copolymer of the present invention can have a total light transmittance of 60% or more when made into a 1 mm plate. The total light transmittance is a value measured in accordance with ISO 13468-1:1996. 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, the total light transmittance is more preferably 70% or more, even more preferably 85% or more, and even more preferably 90% or more. When 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 is preferably 25% or more. In one embodiment, the haze value of a 1 mm plate obtained by molding the polycarbonate-polyorganosiloxane copolymer of the present invention, as measured in accordance with ISO 14782:1999, can be 40 or less. As described above, the polycarbonate-polyorganosiloxane copolymer of the present invention has a specific structure, which gives it high transparency. The haze value is more preferably 30 or less, even more preferably 15 or less, even more preferably 5 or less, and particularly preferably 2 or less.

[0045] 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. using the Schnell formula below. [η]=1.23×10 -5 Mv 0.83

[0046] The refractive index of the polycarbonate-polyorganosiloxane copolymer of the present invention is not particularly limited, but is preferably 1.430 or more and 1.590 or less, more preferably 1.450 or more and 1.570 or less, and even more preferably 1.470 or more and 1.550 or less, for light with a wavelength of 589.3 nm, for example. 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.

[0047] 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.

[0048] <<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]

[0049] R in the above general formula (a1) 10 are as described above, and the preferred ones are also the same.

[0050] Examples of the aliphatic dihydroxy compound 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-dioxan-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.

[0051] Specific examples of the aliphatic dihydroxy compound 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.

[0052] Examples of aromatic dihydroxy compounds include aromatic bisphenol compounds, and more specifically, particularly preferred examples include aromatic bisphenols selected from bisphenol A, bisphenol C, bisphenol Z, and compounds represented by the following general formula: [ka]

[0053] 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.

[0054] <<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. 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 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. 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 with 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 oxygen atoms, nitrogen atoms, and sulfur atoms, or at least one halogen atom selected from fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. 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.]

[0055] R 40’ It is preferable that the alkyl group contains 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. As a 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, a structure containing at least one structure selected from the group consisting of -OH, -O-, -(C=O)-, -O(C=O)-, -O(C=O)O-, -NH2, -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, and polyimide. Among these, 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 these, 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.

[0056] 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]

[0057] 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 same applies to the preferred ones, and the combinations of the preferred ones are also preferred.

[0058] The polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by polymerizing raw material monomers using an interfacial polymerization method or a melt polymerization method (transesterification method). When producing by an interfacial polymerization method, reference can be made to the method described in, for example, JP 2014-80462 A. Preferably, the polycarbonate-polyorganosiloxane copolymer can be produced by reacting raw material monomers, polyorganosiloxane (a2), diol monomer (a1), and a carbonate ester compound, using a melt polymerization method in the presence of a basic catalyst, in the presence of a terminal terminator.

[0059] (carbonate diester) The carbonic acid diester 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 2Each of Ar represents an aryl group, and may be the same or different. 3 and Ar 4 each represents an aryl group, and may be the same or different; D 1 represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0060] 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 of R 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.]

[0061] 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 1 represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0062] 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 alkylaryl 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, but among these, it is preferable to use diphenyl carbonate.

[0063] (end terminator) When producing the polycarbonate-polyorganosiloxane copolymer of the present invention, a terminal terminator can be used as needed. The terminal terminator may be any known terminal terminator used in the production of polycarbonate resins. Specific examples of such a terminal terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0064] (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).

[0065] 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 ester compound are subjected to an ester exchange reaction. The amount of the carbonate ester compound relative to the amount of the diol monomer is preferably 0.9 to 1.2 times by mole, more preferably 0.98 to 1.02 times by mole. In the above transesterification reaction, it is preferable that the amount of the terminal terminator be in the range of 0.05 to 10 mol % relative to the diol monomer (a1) and polyorganosiloxane (a2), because this blocks the hydroxyl terminals of the resulting polycarbonate-polyorganosiloxane copolymer, resulting in a polycarbonate resin with sufficiently excellent heat resistance and water resistance. The amount of the terminal terminator relative to the diol monomer (a1) and 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 may be added to the reaction system in advance, with the remainder being added as the reaction progresses. It is preferred that the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound are simultaneously charged into a reactor together with an antioxidant, and the transesterification reaction is carried out in the presence of the antioxidant.

[0066] The reaction temperature for carrying out the transesterification reaction is not particularly limited and is usually selected from the range of 100 to 330°C, preferably 180 to 300°C, and more preferably 200 to 240°C, but a method in which the temperature is gradually increased to 180 to 300°C as the reaction progresses is particularly preferred. 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 discoloration of the produced polycarbonate-polyorganosiloxane copolymer are less likely to occur.

[0067] 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 it is set so that the reaction proceeds efficiently. Usually, in the early stage of the reaction, the pressure is set to atmospheric pressure (normal pressure) or a pressurized state of 1 to 50 atm (760 to 38,000 torr), and in the later stage of the reaction, the pressure is set to a reduced pressure, preferably 1.33 to 1.33 × 10 4 It is often set to Pa (0.01 to 100 torr). The reaction time may be such that the target molecular weight is reached, and is usually about 0.2 to 10 hours.

[0068] 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. If necessary, the reaction may be carried out in an inert gas atmosphere. Examples of the inert gas include argon, carbon dioxide, dinitrogen monoxide, nitrogen, and other gases; chlorofluorohydrocarbons; alkanes such as ethane and propane; and alkenes such as ethylene and propylene.

[0069] In the melt polymerization method, it is preferable to use a basic catalyst as a catalyst. The basic catalyst can 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 an aryl group, and metal compounds. These compounds can be used alone or in combination. Preferred basic catalysts include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing an aryl group. The basic catalysts can be used alone or in combination of two or more.

[0070] Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, and dilithium salt of bisphenol A, and sodium, potassium, cesium, and lithium salts of phenol. Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate.

[0071] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines, such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles, such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Further examples include bases or basic salts, such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0072] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0073] 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.

[0074] The amount of the basic catalyst used is preferably 1×10 -9 ~1×10 -2 mol, preferably 1 x 10 -8 ~1×10 -2 moles, more preferably 1 x 10 -7 ~1×10 -3 You can choose from a range of moles.

[0075] A catalyst deactivator can be added in the latter stage of the reaction. Known catalyst deactivators are effectively used as the catalyst deactivator, but among these, ammonium salts and phosphonium salts of sulfonic acid are preferred. Salts of dodecylbenzenesulfonic acid, such as tetrabutylphosphonium dodecylbenzenesulfonate, and salts of p-toluenesulfonic acid, such as tetrabutylammonium p-toluenesulfonate, are more preferred.

[0076] Preferred examples of sulfonic acid esters include methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate. Among these, tetrabutylphosphonium dodecylbenzenesulfonate or butyl p-toluenesulfonate is most preferably used.

[0077] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the amount of catalyst deactivator used is preferably 0.5 to 50 mol, more preferably 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, terminate the polymerization reaction, and then mix in an antioxidant.

[0078] The melt polymerization reaction may be carried out either continuously or batchwise. The reaction apparatus used for melt polymerization may be a vertical reaction apparatus equipped with an anchor-type impeller, a Maxblend impeller, or a helical ribbon impeller, or a horizontal reaction apparatus equipped with a paddle impeller, a lattice impeller, or a spectacle impeller. It may also be an extruder equipped with a screw. In the case of a continuous reaction, it is preferable to use an appropriate combination of such reaction apparatuses.

[0079] The polycarbonate-polyorganosiloxane copolymer of the present invention is preferably produced using raw materials that satisfy the following conditions. Condition (i): The haze value of a mixture obtained by contacting the raw material diol monomer (a1), the raw material polyorganosiloxane (a2), a carbonate diester, and a basic catalyst at 100 to 250°C for 0.5 to 5 hours, measured in accordance with ISO 14782:1999 at 23°C with an optical path length of 10 mm, is 30 or less.

[0080] 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.

[0081] 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, even more preferably 10 or less, even more preferably 5 or less, and even more preferably 1 or less. The conditions for obtaining a mixture for measuring the haze value are as described in (i) above. Furthermore, the temperature condition in 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. Under condition (i), when the temperature condition and contact time are within the above-described preferred ranges and the resulting mixture has a haze value specified in condition (i), a polycarbonate-polyorganosiloxane copolymer with higher transparency can be obtained.

[0082] <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 they do not impair the properties of the polycarbonate-polyorganosiloxane copolymer (A).

[0083] (additives) The polycarbonate resin composition of the present invention may contain known additives depending on the intended use and 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.

[0084] [Filler] 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 spherical fillers 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 fibrous fillers 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.

[0085] As the glass fiber, any of those made from alkali-containing glass, low-alkali glass, and alkali-free glass can be suitably used. The form of these glass fibers is not particularly limited, and any form such as roving, milled fiber, and chopped strand can be used. Examples of 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.

[0086] The refractive index of the glass filler is not particularly limited, but for example, the refractive index at a wavelength of 589.3 nm is preferably 1.485 to 1.520. When the refractive index of the glass filler is within this range, the transparency of a molded article obtained using the polycarbonate resin composition of the present invention can be improved. Furthermore, from the viewpoint of improving the transparency of a molded article made from a polycarbonate-based resin composition, the refractive index of the glass filler at a wavelength of 589.3 nm is more preferably 1.490 or more, even more preferably 1.500 or more, and more preferably 1.515 or less, even more preferably 1.514 or less.

[0087] [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 adjusting the amount within the above range, various mechanical properties attributable to the inorganic filler, such as improvements in strength such as elastic modulus, can be achieved without impairing the properties of the polycarbonate-polyorganosiloxane copolymer (A).

[0088] The method for producing the polycarbonate-based resin composition of the present invention is not particularly limited as long as it includes a step of mixing a polycarbonate-polyorganosiloxane copolymer with optional additives. For example, the polycarbonate-polyorganosiloxane copolymer can be produced by mixing the polycarbonate-polyorganosiloxane copolymer with optional additives using a mixer or the like, followed by melt-kneading. Melt-kneading can be carried out by a commonly used method, such as a method using a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, or multi-screw extruder. The heating temperature during melt-kneading is typically selected from the range of 150°C to 300°C, preferably about 220°C to 300°C.

[0089] [Molded products] The molded article of the present invention contains the polycarbonate 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 resin composition or pellets obtained through melt-kneading as a raw material. It is particularly preferred to produce the molded article by injection molding or injection compression molding using the obtained pellets.

[0090] The thickness of the molded article can be set arbitrarily depending on the application, and when transparency of the molded article is particularly required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. If the thickness of the molded article is 0.2 mm or more, warping does not occur and good mechanical strength is obtained. Furthermore, if the thickness of the molded article is 4.0 mm or less, high transparency is obtained.

[0091] The molded article may be coated with a hard coat film, an anti-fogging film, an anti-static film, an anti-reflection film, or a composite film of two or more kinds, if necessary. Among these, it is particularly preferable to form a hard coating film because it has good weather resistance and can prevent wear of the surface of the molded article over time. The material of the hard coating film is not particularly limited, and known materials such as acrylate-based hard coating agents, silicone-based hard coating agents, and inorganic hard coating agents can be used.

[0092] 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 can increase the surface roughness of the molded article, increasing diffuse reflection on the surface of the molded article and, as a result, sometimes resulting in a deterioration in the transparency of the molded article. Therefore, one method for reducing the surface roughness of a molded article is to form a layer (skin layer) with a high resin content on the outermost surface of the molded article, thereby reducing the surface roughness of the molded article. In the case of injection molding, this skin layer can be formed by increasing the mold temperature above the general conditions, which facilitates the flow of the resin in contact with the mold and reduces the surface roughness of the outermost surface of the molded article. Furthermore, in the case of compression molding, the surface roughness of the outermost surface of the molded article can be reduced by increasing the molding pressure above the general conditions. By using these methods to reduce the surface roughness of a molded article, diffuse reflection on the surface of the molded article is reduced, reducing haze, and, as a result, improving the transparency of the molded article.

[0093] When the thus obtained molded article 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. 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, the haze during the flat plate molding is preferably 40 or less, more preferably 30 or less, even more preferably 15 or less, still more preferably 5 or less, and particularly preferably 2 or less. Molded articles having the above optical properties have excellent transparency and can be used in applications requiring high transparency. Total light transmittance for visible light can be measured in accordance with ISO 13468-1:1996, and haze can be measured in accordance with ISO 14782:1999.

[0094] 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 vehicles and ships; 4) electrical equipment parts such as various parts, outer panels, and housings for televisions, radio cassette players, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, cash registers, copiers, printers, and facsimiles; 5) precision equipment parts such as cases and covers for precision equipment such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as vinyl greenhouses and greenhouses; and 7) furniture parts such as lighting covers, blinds, and interior fixtures. [Example]

[0095] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0096] The characteristic values ​​in each example were determined according to the procedures shown below.

[0097] <Method for quantifying polydimethylsiloxane content> Example) Quantitative determination of polydimethylsiloxane contained in the polycarbonate-polyorganosiloxane copolymer obtained in Example 3 NMR device: JEOL RESONANCE ECA-500 Probe: Compatible with TH5 5φ NMR sample tubes 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 amount: 30-40mg Solvent: deuterated chloroform Measurement temperature: room temperature A: Integral value of meta position of 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 in the PEG moiety observed around δ3.3-3.8 E: Integral value of methine and methylene groups in the CHDM moiety observed around δ0.8 to 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

[0098] <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, and the intrinsic viscosity [η] was determined from this, and the viscosity average molecular weight (Mv) was calculated using the following formula (Schnell's formula). [η]=1.23×10 -5 Mv 0.83

[0099] [Evaluation test] <Total light transmittance of resin molded products: Tt (%), haze value> The evaluation pellets obtained in each example and comparative example were used in an injection molding machine (Niigata Machine Techno Co., Ltd., "MD50XB," screw diameter 30 mm) at a cylinder temperature of 240°C and a mold temperature of 80°C to produce a three-stage plate for transparency evaluation (90 mm x 50 mm, 3 mm thick portion 45 mm x 50 mm, 2 mm thick portion 22.5 mm x 50 mm, 1 mm thick portion 22.5 mm x 50 mm). Total light transmittance was measured for a 1 mm thick portion of the three-stage plate in accordance with ISO 13468-1:1996. Haze value was measured for a 1 mm thick portion of the same sample in accordance with ISO 14782:1999. Both values ​​were measured using an NDH5000 measuring device 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 is diffuse transmittance, Tt is total light transmittance)

[0100] <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 and zero-point correction was performed. 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 cell was filled with the liquid mixture obtained by the method described below, 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 is diffuse transmittance, Tt is total light transmittance)

[0101] Production Example 1: Production of PDMS-1 Under a nitrogen atmosphere, the following formula: [ka] To 100 g of a polyorganosiloxane 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 Figure 1, was added in a molar amount (82.3 g) twice that of the polyorganosiloxane. 455 g of isopropyl alcohol (2.5 parts based on the total mass of the polyorganosiloxane and polyethylene glycol) was added, and the mixture temperature was controlled at 80°C and thoroughly stirred. 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. The isopropyl alcohol and platinum catalyst were removed from the resulting mixture to obtain polyether-modified polyorganosiloxane PDMS-1.

[0102] Production Example 2: Production of PDMS-2 Production was carried out in the same manner as in Production Example 1, except that an α,ω-dihydrogenorganopolysiloxane with an average siloxane chain length of 61 was used.

[0103] Production Example 3: Production of PDMS-3 Production was carried out in the same manner as in Production Example 1, except that an α,ω-dihydrogenorganopolysiloxane with an average siloxane chain length of 88 was used.

[0104] 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.

[0105] Production Example 5: Production of PDMS-5 Under a nitrogen atmosphere, the following formula: [ka] To a polyorganosiloxane having an average siloxane chain length of 39, 2-allylphenol was added in an amount twice the molar amount of the polyorganosiloxane. The mixture was thoroughly stirred while controlling the temperature at 100°C. 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. Isopropyl alcohol and the platinum catalyst were removed from the resulting mixture, yielding an allylphenol-modified polyorganosiloxane PDMS-5.

[0106] 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.

[0107] Production Example 7: Production of PDMS-7 Production was carried out in the same manner as in Production Example 1, except that ethylene glycol monoallyl ether (CH2=CHCH2-O-CH2CH2-OH) was used instead of polyethylene glycol.

[0108] Production Example 8: Production of PDMS-8 The procedure of Production Example 1 was repeated 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.

[0109] Production Example 9: Production 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, the solvent was toluene, and the reaction temperature was 110°C.

[0110] 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, toluene was used as the solvent, and the reaction temperature was 110°C.

[0111] Production Example 11: Production of PDMS-11 Under a nitrogen atmosphere, 350 mL of methylene chloride was placed in a flask, and 21.5 g of 2,6-di-t-butylpyridine and 21 g of trifluoromethanesulfonic anhydride were added thereto. The mixture was cooled to below 15°C. 4.3 g of allyl alcohol was added dropwise to form a reaction initiator. After stirring for approximately 15 minutes, 1 L of dehydrated tetrahydrofuran was added and stirred at 20-23°C for 5 minutes, after which 30 mL of ion-exchanged water was added to stop the reaction. The mixture was extracted with heptane, washed with 10% hydrochloric acid, and the aqueous layer was separated. Subsequently, the mixture was washed twice with ion-exchanged water and the aqueous layer was separated. The solvent was then distilled off under reduced pressure, and the following reaction product was obtained: [ka] Thus, 120 g of one-terminal allyl-modified polytetramethylene glycol (tetramethylene glycol moiety chain length=20) shown in the formula: 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.

[0112] Production Example 12: Production of PDMS-12 A flask under nitrogen atmosphere was charged with polydimethylsiloxane (average number of SiMeO units: 40) bearing -C3H6OC2H4OH groups at both ends and trimethylene carbonate (25 times the molar amount relative to the hydroxyl groups of the polyorganosiloxane). Dehydrated dichloromethane was then added to the resulting clear reaction solution to a concentration of 10 wt%. Three equivalents of 1,8-diazabicycloundecene per terminal OH group of the polydimethylsiloxane were added as a catalyst, and the reaction was allowed to proceed at room temperature for 48 hours. Benzoic acid was then added to quench the reaction. The reaction mixture was then reprecipitated in a mixed solvent consisting of methanol, 2-propanol, and hexane (volume ratio: 10:1:10, respectively). The resulting precipitate was vacuum dried to obtain PDMS-12 (number of polytrimethylene carbonate units at each end: 18).

[0113] Production Example 13: Production of PDMS-13 Under a nitrogen atmosphere, 450 mL of methylene chloride was placed in a flask, 45.0 g of 3-iodo-1-propanol was added, and the mixture was cooled in an ice bath. 40.1 g of tert-butyldimethylchlorosilane was added, 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 on a silica gel column to obtain a TBS-protected 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 below -65°C. 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. 55 mL of 0.52 mol / L lithium chloride THF solution was then added and stirred for 10 minutes. 10.1 mL of methyl methacrylate was then added and stirred for 10 minutes. 3.36 mL of allyl bromide was added to quench the reaction, and the mixture was then stirred at room temperature for 12 hours. The resulting reaction mixture was concentrated under reduced pressure, reprecipitated with a THF / heptane system, and then purified using a silica gel column to remove the solvent, yielding a TBS-protected mono-terminal allyl-modified PMMA. This product was dissolved in THF and deprotected with a 2 mol / L aqueous hydrochloric acid solution. The resulting reaction mixture was poured into heptane to separate the target product (deprotected product). This deprotected product was purified by silica gel column chromatography and the solvent was removed to obtain the compound shown in the following formula: [ka] Thus, one-terminal allyl-modified PMMA (number of PMMA chains = 20) shown in the formula (1) was obtained. The same production method as in Production Example 8 was carried out, except that the above-mentioned one-terminal allyl-modified PMMA was used instead of polyethylene glycol.

[0114] Production Example 14: Production of PDMS-14 Instead of polyethylene glycol, [ka] The same production method as in Production Example 1 was used except that polypropylene glycol having an average oxypropylene chain length of 15, as shown in

[0115] PDMS-1 to PDMS-14 obtained in Production Examples 1 to 14 are shown in Table 1.

[0116] [Table 1]

[0117] [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, Inc.] 0.01N sodium hydroxide aqueous solution [Fujifilm Wako Pure Chemical Industries, Ltd.]

[0118] Example 1 <Transparency evaluation of raw material mixture after heat treatment> A 10 L stainless steel reactor equipped with a double helical impeller as a stirring device was charged with 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. After completely melting these raw material monomers at 150 °C, stirring was started at 70 rpm, and the inside of the reactor was purged with nitrogen. Next, 1.64 mL of 0.01 N sodium hydroxide (1.5 × 10 moles relative to the total number of diol monomer moles) was added as a catalyst. -6 The temperature of the mixture was raised to 200°C while maintaining a nitrogen pressure of 101 kPa, the same as atmospheric pressure, 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, demonstrating high transparency.

[0119] <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 transparency evaluation above, but the polymerization conditions were as follows: A 10 L stainless steel reactor equipped with a stirrer, a trap to capture distilled phenol, and a pressure reducing device was charged with 2,489.9 g of BisP-A and 2,500 g of DPC (molar ratio of each raw material: BisP-A / DPC = 100 / 107) as diol monomers, and 28.2 g of polyether-modified polyorganosiloxane PDMS-1. These raw material monomers were completely melted at 150 °C, and the inside of the reactor was purged with nitrogen. 1.64 mL of 0.01 N sodium hydroxide (1.5 × 10 relative to the total number of diol monomer moles) was added as a catalyst. -6 The reactor temperature was raised to 180°C and the pressure was reduced to 200 mmHg (26.6 kPa) 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 internal temperature was raised to 200°C and the pressure was reduced to 10 mmHg (1.3 kPa) over a period of about 60 minutes, and the conditions were maintained until 1.0 L of phenol was distilled. Next, the reactor's internal temperature was raised to 240°C over approximately 120 minutes, and these conditions were maintained until 1.5 L of phenol had been distilled. The reactor's internal temperature was then raised to 280°C and the vacuum level was adjusted to 1 mmHg (0.1 kPa) or less over approximately 120 minutes. More than 2 L of phenol was distilled, and the reaction was continued until the specified stirring torque was reached. The pressure was then restored with nitrogen, and 0.037 g of butyl p-toluenesulfonate (10 times the amount per mole of NaOH) was added as a deactivator. Irganox 1010 and Irgafos 168 were added so that their contents in the resulting polymer were 1,500 ppm, and the mixture was thoroughly stirred. Resin strands were then extracted from the bottom of the reactor under nitrogen pressure and cut using a pelletizer to obtain highly transparent pelletized polycarbonate-polyorganosiloxane copolymers. The evaluation results of the resulting polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0120] Example 2 As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2,500 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 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, the total light transmittance was 98.5%, and the haze value was 0.5. As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2,500 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 polymerization 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.

[0121] 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, 2,500 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, the total light transmittance was 99.5%, and the haze value was 0.4.

[0122] <Production of PC-POS copolymer> A 10 L stainless steel reactor equipped with a stirrer, a trap to capture distilled phenol, and a pressure reducing device was charged with diol monomers: ISB (1193.8 g), 1,4-CHDM (504.9 g), DPC (2,500 g) (molar ratio of each raw material: ISB / 1,4-CHDM / DPC = 70:30:100), and 20.2 g of polyether-modified polyorganosiloxane PDMS-1. These raw material monomers were completely melted at 100 °C, and the inside of the reactor was purged with nitrogen. 1.64 mL of 0.01 N sodium hydroxide (1.5 × 10 relative to the total number of diol monomer moles) was added as a catalyst. -6 The reactor was heated and depressurized to 180°C and 200 mmHg (26.6 kPa) over approximately 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 10 mmHg (1.3 kPa) over approximately 150 minutes, and these conditions were maintained until 1.8 L of phenol was distilled. Next, over approximately 60 minutes, the reactor's internal temperature was adjusted to 220°C and the vacuum level to 1 mmHg (0.1 kPa) or less. More than 2 L of phenol was distilled off, and the reaction was continued until the specified stirring torque was reached. The pressure was then restored with nitrogen, and 0.037 g of butyl p-toluenesulfonate (10 times the amount per mole of NaOH) was added as a deactivator. Irganox 1010 and Irgafos 168 were added so that their contents in the resulting polymer were 1,500 ppm, and the mixture was thoroughly stirred. Resin strands were then extracted from the bottom of the reactor under nitrogen pressure and cut with a pelletizer to obtain highly transparent pelletized polycarbonate-polyorganosiloxane copolymers. The evaluation results of the resulting polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] 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.

[0128] Example 9 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that the diol monomers used were 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. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.5% and a haze value of 0.4. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 3, except that the diol monomers used were ISB (1,193.8 g), TCDDM (687.2 g), and 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. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0129] Example 10 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that the diol monomers used were ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), and 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 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), 19.8 g of polyether-modified polyorganosiloxane PDMS-1 were used. Polymerization was carried out under the same conditions as in Example 3, except that a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0130] 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 calculated 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 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 98.3% 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 (2,500 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.

[0131] 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, and a Charpy impact strength (with notch) of 81.0 kJ / m 2 It was.

[0132] Example 13 <Transparency evaluation of the raw material mixture after heat treatment> Except that 312.8 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 89.1% and a haze value of 2.6. <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 312.8 g of PDMS-8 was used as the polyorganosiloxane. 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, and a Charpy impact strength (with notch) of 85.0 kJ / m 2 It was.

[0133] Example 14 <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-9 was used as the polyorganosiloxane. 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> 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-9 was used as the polyorganosiloxane. 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, and a Charpy impact strength (with notch) of 75.0 kJ / m 2 It was.

[0134] 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 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, and a Charpy impact strength (with notch) of 76.0 kJ / m 2 was obtained.

[0135] Example 16 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out 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 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%, and a haze value of 83.5.

[0136] Example 17 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 1, except that 57.1 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 78.6% and a haze value of 12.0. <Production of PC-POS copolymer> A transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1, except that 57.1 g of PDMS-11 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,100, a polydimethylsiloxane content of 1.10% by mass, a total light transmittance of 48.1%, and a haze value of 87.5.

[0137] Example 18 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 1, except that 28.2 g of PDMS-12 was used as the polyorganosiloxane. 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> A 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-12 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 19,900, a polydimethylsiloxane content of 0.45% by mass, a total light transmittance of 81.0%, and a haze value of 11.3.

[0138] Example 19 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 1, except that 179.7 g of PDMS-12 was used as the polyorganosiloxane. 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> A 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-12 was used as the polyorganosiloxane. 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%, and a haze value of 82.1.

[0139] Example 20 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 1, except that 28.2 g of PDMS-13 was used as the polyorganosiloxane. 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> A 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-13 was used as the polyorganosiloxane. 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%, and a haze value of 81.2.

[0140] Example 21 <Transparency evaluation of the raw material mixture after heat treatment> The transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 3, except that 20.2 g of PDMS-14 was used as the polyorganosiloxane. 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> A highly transparent polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 2, except that 20.2 g of PDMS-14 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 15,000, a polydimethylsiloxane content of 0.68 mass%, a total light transmittance of 69.7%, and a haze value of 84.0.

[0141] Comparative Example 1 Except for using 28.2 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 1. The liquid raw material mixture after the heat treatment was cloudy, with a total light transmittance of 77.6% and a haze value of 95.4. Except for using 28.2 g of PDMS-5 as the polyorganosiloxane, polymerization was carried out under the same conditions as in Example 1 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.

[0142] Comparative Example 2 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. A highly opaque polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 2, except that 24.4 g of PDMS-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0143] Comparative Example 3 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. A highly opaque 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-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0144] Comparative Example 4 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. A highly opaque 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-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0145] Comparative Example 5 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. A highly opaque 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-6 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0146] Comparative Example 6 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. A highly opaque 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-7 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0147] Comparative Example 7 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. A highly opaque polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 9, except that 22.1 g of PDMS-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0148] Comparative Example 8 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. After the heat treatment, the liquid raw material mixture was cloudy, with a total light transmittance of 78.5% and a haze value of 89.9. A highly opaque polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 10, except that 19.8 g of PDMS-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0149] Comparative Example 9 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. After the heat treatment, the liquid raw material mixture was cloudy, with a total light transmittance of 79.9% and a haze value of 88.5. A highly opaque polycarbonate-polyorganosiloxane copolymer in pellet form was obtained by polymerization under the same conditions as in Example 11, except that 21.3 g of PDMS-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0150] 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. Polymerization was carried out under the same conditions as in Example 1, except that 179.7 g of PDMS-5 was used as the polyorganosiloxane, to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The resulting 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, and a Charpy impact strength (notched) of 61.0 kJ / m. 2 It was.

[0151] 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. Polymerization was carried out under the same conditions as in Example 1, except that 179.7 g of PDMS-7 was used as the polyorganosiloxane, to obtain a highly opaque polycarbonate-polyorganosiloxane copolymer in the form of pellets. The resulting 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, and a Charpy impact strength (notched) of 61.0 kJ / m. 2 It was.

[0152]

Table 2

[0153]

Table 3

Claims

1. A raw material monomer composition used in the production of a polycarbonate-polyorganosiloxane copolymer, comprising a polyorganosiloxane (a2) having any of the structures represented by the following general formulas (a2-1) to (a2-3): 【Chemical 1】 [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 having 1 to 10 carbon atoms in the alkyl group moiety. 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 moiety; and as a functional group, -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 1 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 multiple R ８ 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, 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. z represents 0 or 1. z1 represents 0 or 1. a represents an integer of 2 to 500, and b represents an integer of 5 to 200. b1 represents an integer of 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 with 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.]

2. 2. The raw material monomer composition according to claim 1, wherein in the general formulae (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 raw material monomer composition according to claim 1 or 2, wherein all of

4. In the general formulae (a2-1) to (a2-3), R ６ is a trimethylene group (-(CH ２ ) ３ The raw material monomer composition 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 tetramethylene group (-(CH ２ ) ４ 5. The raw material monomer composition according to claim 1, wherein the raw material monomer composition has a structure selected from the group consisting of:

6. The polycarbonate-polyorganosiloxane copolymer is produced by melt polymerization of the polyorganosiloxane (a2), the diol monomer (a1), and a carbonate ester compound in the presence of a basic catalyst. The raw material monomer composition according to any one of claims 1 to 5.

7. 7. The raw material monomer composition according to claim 6, wherein the diol monomer (a1) has a structure represented by the following general formula (a1): 【Chemistry 2】 [In the formula, 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 with 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.]

8. 8. The raw material monomer composition according to claim 6, wherein the diol monomer (a1) is 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.

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