Polycarbonate-polyorganosiloxane copolymer and resin composition containing the 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 Art

[0002] Polycarbonate resin is an engineering plastic having excellent transparency and mechanical properties and very high impact resistance. A polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polysiloxane with polycarbonate is known to have excellent low-temperature impact resistance and chemical resistance while maintaining high transparency. Generally, as a method for producing polycarbonate resin, a method of directly reacting an aromatic dihydroxy compound with phosgene (interfacial polycondensation method) or a method of subjecting an aromatic dihydroxy compound and a carbonic acid diester to a transesterification reaction in a molten state (melt polycondensation method) is known.

[0003] In general, the interfacial polymerization method is often adopted to produce a polycarbonate-polyorganosiloxane copolymer. For example, a diaryl diol compound such as bisphenol is reacted with phosgene in the presence of an organic solvent to produce a polycarbonate oligomer having a reactive chloroformate group. Simultaneously with or sequentially to the production of the polycarbonate oligomer, the polycarbonate oligomer, bisphenols, and a polysiloxane having a hydroxyl group-containing aryl group at both ends are brought into contact in a methylene chloride / water medium to produce a polycarbonate-polyorganosiloxane copolymer (Patent Document 1). Generally, in a polymerization reaction, a homocoupling product in which the same raw material components are bonded to each other or an unreacted raw material component in which a part of the raw materials does not participate in the polymerization reaction may be generated. Since these components exist in the polymer without being uniformly incorporated into the polymer main chain, the transparency and mechanical properties of the polymer are significantly deteriorated. Such problems rarely occur in the above interfacial polymerization method, and a polycarbonate-polyorganosiloxane copolymer having excellent transparency and mechanical properties can be obtained.

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

[0005] Patent Document 2 discloses the production of polycarbonate-polyorganosiloxane copolymers by the melt polymerization method from bisphenol compounds, aromatic carbonic acid diesters, silanol-terminated polysiloxanes, and catalysts. Patent Document 3 discloses a method for producing block copolysiloxane carbonates in the presence of carbonate-terminated polyorganosiloxanes, dihydroxyaromatic compounds, diaryl carbonates, and carbonate transesterification catalysts. Patent Document 4 discloses a method for producing polysiloxane / polycarbonate block co-condensation products, including reacting hydroxyaryloxy-terminated dimethylsiloxane with an oligocarbonate having a specific weight average molecular weight and a specific terminal ratio (OH terminal groups and aryl terminal groups) in a molten state in the presence of a catalyst.

[0006] Patent Document 5 discloses a method for producing poly(diorganosiloxane) / polycarbonate block copolymers by melt polymerizing poly(diorganosiloxanes) containing poly(diorganosiloxane) components having specific terminal structures, Si-free diphenols, and diaryl carbonates in the presence of specific catalysts. Patent Document 6 discloses a method for producing modified polycarbonate resins by solid-phase polymerization, and describes the use of polysiloxane compounds as starting raw materials. Patent Documents 7 to 9 disclose methods for obtaining polysiloxane-polycarbonate block co-condensates by the 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 Specification [Patent Document 3] Japanese Patent Application Laid-Open No. 8-311206 [Patent Document 4] Japanese Patent Application Laid-Open No. 10-251408 [Patent Document 5] Japanese Patent Application Laid-Open No. 2008-248262 [Patent Document 6] Japanese Patent Application Laid-Open No. 2008-513594 [Patent Document 7] Japanese Patent Application Laid-Open No. 2017-505841 [Patent Document 8] Japanese Patent Application Laid-Open No. 2016-532734 [Patent Document 9] Japanese Patent Application Laid-Open No. 2016-532733 [Summary of the Invention] [Problems to be Solved by the Invention]

[0008] Patent Documents 2 to 7 disclose a production method by a melt polymerization method of a polycarbonate-polyorganosiloxane copolymer, but it is still insufficient in terms of obtaining a polycarbonate-polyorganosiloxane copolymer having good transparency and mechanical properties. Patent Document 2 has no teaching regarding the transparency of the polymer obtained using silanol-terminated siloxane, and it is known that silanol-terminated dimethylsiloxane tends to undergo intramolecular condensation as its molecular weight decreases. The cyclic siloxane generated as a result of intramolecular condensation remains in the obtained polycarbonate-polysiloxane copolymer, which not only has an adverse effect on its transparency and mechanical properties, but also raises concerns about having an adverse effect such as relay contact failure in applications in the electrical and electronic fields.

[0009] Although Patent Document 3 shows that the amount of polydimethylsiloxane incorporated into the polymer main chain increases, there is no teaching regarding the transparency of the resulting polymer. Also, since the appearance of the carbonate-terminated polysiloxane and other raw materials in the molten state is described as "milky white," it is inferred that the carbonate-terminated polysiloxane is separated from other raw materials and that components produced by homocoupling or unreacted carbonate-terminated polysiloxane still remain in the copolymer. These components significantly reduce the transparency and mechanical properties of the polycarbonate-polysiloxane copolymer. In Patent Document 3, even in a production example where a large amount of siloxane is incorporated into the polymer main chain, an alkali metal-based catalyst (sodium hydroxide) is used in an amount 10×10 -6 times the number of moles of bisphenol A. When an excessive amount of catalyst is used, an increase in the amount of residual catalyst components induces hydrolysis of the polycarbonate chain, and it is inferred that the resulting polymer does not have heat resistance and weather resistance that can withstand practical conditions.

[0010] As described in Patent Document 4 as "white" regarding the appearance of the resulting polymer, the uniformity during the polymerization of siloxane and other raw materials is still insufficient, and it can be said that there is room for improvement in its transparency and mechanical properties.

[0011] The copolymer disclosed in Patent Document 5 has a large domain structure and is considered to have an adverse effect on transparency. Patent Document 6 generally describes the transparency of polycarbonate resins, etc., but it has not been demonstrated that polycarbonate-polyorganosiloxane copolymers have high transparency. Patent Documents 7 to 9 produce copolymers having polysiloxane blocks with the same structure by the 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 the interfacial polymerization method, effective means for obtaining polycarbonate-polyorganosiloxane copolymers having high transparency have not yet been shown. The present invention aims to obtain a polycarbonate-polyorganosiloxane copolymer having high transparency.

Means for Solving the Problems

[0013] As a result of intensive studies, the present inventors have found that a polycarbonate-polyorganosiloxane copolymer having a specific structure has high transparency. That is, the present invention relates to the following.

[0014] [1] A polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) composed of a repeating unit represented by the following general formula (2).

Chemical formula

[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 selected from the group consisting of repeating units represented by the following general formulas (a-i) to (a-v). [Chemical formula] [5] In the general formula (1), a is an integer of 2 or more and 300 or less. The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [4] above. [6] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [5] above, wherein the polyorganosiloxane block (A-1) contains at least one selected from the group consisting of structural units represented by the following general formulas (1-1) to (1-3). [Chemical formula] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, and 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 moiety, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - as a functional group. 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 moiety, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - as a functional group. 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 halide of a dicarboxylic acid.] [7] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [6] above, wherein in the general formula (1), all of R 1 ~R 4 represent methyl groups. [8] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [7] above, wherein in the general formula (1), R 6 is a trimethylene group (-(CH2)3-).

[0016] [9] In the general formula (1), R 8The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [8] above, which has any structure selected from the group consisting of a dimethylene group (-(CH2)2-), a methyl-substituted dimethylene group (-(CH2)CHMe-), 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 the 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 [1] to

[10] above, having 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 the haze value measured in accordance with ISO 14782:1999 of a 1 mm thick plate obtained by molding the polycarbonate-polyorganosiloxane copolymer is 40 or less.

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

[12] above, obtained by a melt polymerization method.

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

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

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

[14] above.

[16] The polycarbonate-based resin composition according to

[15] above, further containing an inorganic filler.

[17] The polycarbonate-based resin composition according to

[16] above, containing 1 to 150 parts by mass of the inorganic filler with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer.

[18] The polycarbonate-based resin composition according to

[16] or

[17] above, 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

[15] to

[18] above.

Advantages of the Invention

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

Modes for Carrying Out the Invention

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

[0019] <Polycarbonate-Polyorganosiloxane Copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention includes a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) composed of repeating units represented by the following general formula (2).

[0020]

Chemical formula

[0021] R 6 When R is an alkylene group, the number of carbon atoms is preferably 1 to 5.

[0022] By including a structural unit represented by the above general formula (1) in the polyorganosiloxane block constituting the polycarbonate-polyorganosiloxane copolymer, the obtained polycarbonate-polyorganosiloxane copolymer has high transparency. Depending on the selection of R 10 in the formula of the polycarbonate block (A-2) composed of the repeating unit represented by the general formula (2), even higher transparency can be obtained. The polyorganosiloxane block constituting the polycarbonate-polyorganosiloxane copolymer contains a structural unit represented by the above general formula (1), and a highly transparent polycarbonate-polyorganosiloxane copolymer can be obtained because the structural unit represented by the above general formula (1) improves the compatibility of the polyorganosiloxane with other raw material components such as diol monomers and carbonates of polyorganosiloxane, increases the reaction rate of the polyorganosiloxane, and exhibits the effect of incorporating the polyorganosiloxane into the polymer with high randomness. More specifically, due to the above-described effects of the structural unit represented by the above general formula (1), the amount of unreacted polyorganosiloxane and polymers in which an extremely large amount of polyorganosiloxane is incorporated is reduced, and the interface between components caused by the separation of these components in the polymer is reduced. Therefore, it is presumed that a highly transparent polycarbonate-polyorganosiloxane copolymer is obtained. As will be described later, the polycarbonate-polyorganosiloxane copolymer of the present invention can also be obtained by a melt polymerization method. Since the melt polymerization method does not require a solvent such as methylene chloride, it is environmentally and economically advantageous. In addition, since highly toxic phosgene is not used as the carbonate source, it is also advantageous in terms of production.

[0023] The polyorganosiloxane block (A-1) containing the structural unit represented by the general formula (1) preferably contains at least one selected from the group consisting of structural units represented by the following general formulas (1-1) to (1-3). [Chemical formula] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, and 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 moiety, and may contain -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - as a functional group. 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 in which the alkyl group moiety has 1 to 10 carbon atoms, and as a functional group, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may be included. 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 halide of a dicarboxylic acid.]

[0024] R 5 When R is an alkylene group, the number of carbon atoms is preferably 1 to 5.

[0025] In the formula, the halogen atoms represented by R 1 ~R 4 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkyl groups having 1 to 10 carbon atoms represented by R 1 ~R 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. The alkoxy groups represented by R 1 ~R 4 include the case where the alkyl group moiety is the above alkyl group. The aryl groups represented by R 1 ~R 4 include a phenyl group, a naphthyl group, etc. The alkylarylene groups represented by R 1 ~R 4 include the case where the alkyl group moiety is the above alkyl group and the aryl group moiety is the above aryl group. R 1 ~R 4 are all 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 all are methyl groups.

[0026] R in the 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 5 and R 6 include a phenylene group, a naphthylene group, and the like. Examples of the alkylene group having 1 to 10 carbon atoms represented by R 5 and R 6 include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, a tetramethylene group (the tetramethylene group may have a branched structure), and the like. Examples of the alkylarylene group represented by R R 5 and R 6 are all preferably an alkylene group having 1 to 10 carbon atoms, more preferably a dimethylene group, a methyl-substituted dimethylene group or a trimethylene group. It is particularly preferable that R in the formula is a trimethylene group (-(CH2)3-). 6

[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 R 8 include a phenylene group, a naphthylene group, and the like. Examples of the alkylene group having 1 to 10 carbon atoms represented by R in the above general formula (1) 7 or R in general formulas (1-1) to (1-3) 8 and R 8 include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, a tetramethylene group (the tetramethylene group may have a branched structure), and the like. Examples of the alkylarylene group represented by R in the above general formula (1) 7 or R in general formulas (1-1) to (1-3) 8 include a case where the alkyl group moiety is the above alkyl group and the arylene group moiety is the above arylene group. R in the above general formula (1) 8 ​、 or R in general formulas (1-1) to (1-3) 7 and R 8 are both 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 (-(CH2)CHMe-), 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 all methyl groups, R 5 and R 6 are all trimethylene groups, R 7 and R 8 are all ethyl groups, and the polyorganosiloxane is particularly preferred.

[0029] β in general formulas (1-1) and (1-2) represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. For example, divalent groups represented by the following general formulas (iii) to (vii) can be mentioned.

Chemical formula

[0030] In the above general formula (1) or general formulas (1-1) to (1-3), a represents the chain length of the polyorganosiloxane, and represents an integer of 2 or more and 500 or less, preferably 2 or more and 300 or less, more preferably 10 or more and 100 or less, still more preferably 15 or more and 70 or less, and still more preferably 20 or more and 65 or less. When a is within the above range, the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and becomes a highly transparent copolymer, which is preferable. 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 still more preferably 8 or more and 25 or less. Being within the above range is preferable because of the easy availability of raw materials. When b and b1 are 100 or less, it is more preferable because it is possible to suppress a decrease in handleability due to an increase in the viscosity and melting point of the polyorganosiloxane. When b and b1 are 50 or less, it is more preferable because the content of the polyorganosiloxane block in the resin can be maintained at an amount capable of maintaining the physical property improvement effect. In the above general formula (1) or general formulas (1-1) to (1-3), z and z1 each independently represent 0 or 1, and are preferably 0.

[0031] The polycarbonate-polyorganosiloxane copolymer of the present invention contains a polycarbonate block (A-2) composed of a repeating unit 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 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, an n-octadecylene group, and the like. Examples of the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, a tricyclodecylene group, and the like.

[0032] R in the above general formula (2) 10Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms shown in include various ones. In particular, divalent aromatic hydrocarbon groups derived from 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane (bisphenol 3MZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol HTG), 1,1-bis(4-hydroxyphenyl)cyclododecene, etc. can be mentioned. In addition, divalent aromatic hydrocarbon groups derived from at least one selected from the group consisting of hydroquinone, resorcinol, and catechol can also be mentioned.

[0033] The polycarbonate block (A-2) having the structure represented by the general formula (2) preferably has the structure represented by the following general formula (111) and the structure represented by the following general formula (112). [Chemical formula] [In the formula, R 55 and R 56 each independently represent 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 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, which may contain a branched structure or a cyclic structure. R 100It may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. y represents an integer from 10 to 500. s and t each independently represent an integer from 0 to 4.]

[0034] In the general formula (111) above, R 55 and R 56 Examples of the halogen atom independently represented by each of them include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 55 and R 56 Examples of the alkyl group independently represented by each of them include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups (the term "various" means including linear and all branched-chain ones, and the same applies hereinafter), various pentyl groups, and various hexyl groups. Examples of the alkoxy group independently represented by each of R 55 and R 56 include the case where the alkyl group moiety is the above alkyl group.

[0035] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, etc., and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X include an ethylidene group, an isopropylidene group, etc. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group, etc., and a cycloalkylene group having 5 to 10 carbon atoms is preferred. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, a biphenylene group, etc. Examples of the cycloalkylidene group represented by X include, for example, a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group, etc., and a cycloalkylidene group having 5 to 10 carbon atoms is preferred, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferred. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, etc. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring-forming 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, more preferably 0 or 1. Among them, those in which s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or those in which s and t are 0 and X is an alkylidene group, particularly an isopropylidene group, are preferred.

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

[0038] Examples of the alkylene group having 2 to 18 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a 2-ethylhexylene group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group, an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, an n-octadecylene group, and the like. 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, and the like. 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) composed of the repeating unit represented by the general formula (2) preferably has at least one selected from the group consisting of the repeating units represented by the following general formulas (a-i) to (a-xiii), more preferably has at least one selected from the group consisting of the following general formulas (a-i) to (a-v), and more preferably has one or more selected from the group consisting of the repeating units represented by (a-i), (a-ii), and (a-v) from the viewpoint of high transparency.

Chemical formula

Chemical formula

Chemical formula

[0040] The polycarbonate block (A-2) represented by the general formula (2) preferably contains a structural unit derived from an aromatic bisphenol selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 1,1-bis(4-hydroxyphenyl)cyclododecene, or an aliphatic diol selected from the group consisting of isosorbide, cyclohexane-1,4-dimethanol, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol.

[0041] Among them, it is more preferable that the polycarbonate block (A-2) composed of the repeating unit represented by the general formula (2) has one or more selected from the group consisting of the repeating units represented by the following general formulas (a-i) to (a-v).

Chemical formula

[0042] Y, which represents the number of units of the polycarbonate block (A-2) represented by the general formula (2), is more preferably 20 to 200, and even more preferably 40 to 100. It is preferable that y is 20 or more because it can suppress the increase of low molecular weight components in the copolymer. It is preferable that y is 40 or more because the toughness of the copolymer is enhanced. It is preferable that y is 200 or less because appropriate fluidity can be obtained during molding, and if it is 100 or less, the reaction mixture during production has appropriate fluidity, so the productivity is improved.

[0043] In the above polycarbonate-polyorganosiloxane copolymer, the content of the polyorganosiloxane block represented by the general formula (1) is preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass, still more preferably 1 to 30% by mass, and even more preferably 3 to 20% by mass. When the content of the polyorganosiloxane block in the above polycarbonate-polyorganosiloxane copolymer is within the above range, more excellent impact resistance and transparency can be obtained.

[0044] The polycarbonate-polyorganosiloxane copolymer of the present invention is characterized by having 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. The above total light transmittance is more preferably 70% or more, still more preferably 85% or more, and even more preferably 90% or more when the content of the polyorganosiloxane block represented by the 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. When the content of the polyorganosiloxane block represented by the formula (1) in the polycarbonate-polyorganosiloxane copolymer is 5% by mass or more, the above total light transmittance is preferably 25% or more. In one embodiment, the haze value measured in accordance with ISO 14782:1999 of a 1 mm plate obtained by molding the polycarbonate-polyorganosiloxane copolymer of the present invention can be 40 or less. As described above, the polycarbonate-polyorganosiloxane copolymer of the present invention has a specific structure and thus has high transparency. The above haze value is more preferably 30 or less, still 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, still more preferably 14,000 or more, particularly preferably 16,000 or more, and more preferably 30,000 or less, still more preferably 23,000 or less, particularly preferably 21,000 or less. The viscosity-average molecular weight (Mv) is a value calculated from the following Schnell's formula by measuring the intrinsic viscosity [η] of a methylene chloride solution (concentration: g / L) at 20°C. [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 for example, it is preferably 1.430 or more and 1.590 or less, more preferably 1.450 or more and 1.570 or less, and still more preferably 1.470 or more and 1.550 or less with respect to light having a wavelength of 589.3 nm. The difference (nF - nC) between the refractive index (nF) with respect to light having a wavelength of 486.1 nm and the refractive index (nC) with respect to light having a wavelength of 656.3 nm of the polycarbonate resin is preferably 0.015 or less, more preferably 0.013 or less, and still 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 monomers.

[0048] <<Diol monomer (a1)>> The above 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.

Chemical formula

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

[0050] Examples of the aliphatic dihydroxy compounds include dihydroxy compounds having a chain aliphatic hydrocarbon group such as ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 2,2-dimethylpropane-1,3-diol, diethylene glycol, triethylene glycol, tetraethylene glycol, octaethylene glycol, dipropylene glycol, N-methyldiethanolamine, p-xylylene glycol; dihydroxy compounds having an alicyclic hydrocarbon group such as 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, 2,6-decalindimethanol, 1,5-decalindimethanol, 2,3-decalindimethanol, 2,3-norbornanediol, 2,5-norbornanediol, 2,3-norbornanedimethanol, 2,5-norbornanedimethanol, 2,2-bis(4-hydroxycyclohexyl)-propane, 1,3-adamantandiol, 1,3-adamantanedimethanol, tricyclodecanedimethanol; 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 undecane, 1,4-anhydroerythritol, and cyclic ether diols; 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-pyrrolidine diol, 3,4-dimethylpiperidine diol, N-ethyl-3,4-piperidine diol, N-ethyl-3,5-piperidine diol; S-heterocyclic diols such as deoxythioglucose, etc. can be mentioned.

[0051] Specific examples of the aliphatic dihydroxy compounds 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, and particularly preferably these can be mentioned.

[0052] Examples of the aromatic dihydroxy compounds include aromatic bisphenol compounds. Specifically, aromatic bisphenols selected from bisphenol A, bisphenol C, bisphenol Z, and the compounds represented by the following general formula can be particularly preferably mentioned. [Chemical formula]

[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), bisphenol-CDE (1,1-bis(4-hydroxyphenyl)cyclododecene). Among them, it is preferable to use an aliphatic diol as the diol monomer (a1) because high transparency of the obtained polycarbonate-polyorganosiloxane copolymer can be achieved.

[0054] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably has a structure represented by the following general formula (a2-0). [Chemical formula] [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. R 5 and R 6 may be the same or different and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group moiety, and as a functional group, it may contain -O-, -COO-, -CO-, -S-, -NH-, -NR 111 -. 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, and may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one hetero atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 40’’represents a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and may be substituted by a substituent. e and u represent 0 or 1.

[0055] R 40’ is preferably a repeating chain structure in which at least two structures each containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom are linked. As the structure containing at least one hydrocarbon group selected from a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom, 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-, -S—S-, and -(S═O)- is preferable. 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, and these may be substituted by a substituent. Preferred examples of the repeating chain structure include polyether, polyacetal, polylactone, polyacrylate, polyester, polycarbonate, polyketone, polysulfide, polysulfone, polyamide, or polyimide. Among them, at least one selected from the group consisting of polyether, polyacrylate, and polycarbonate is preferable, and polyether is most preferable. As the polyether, polyalkylene ether is preferable, and among them, polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol are preferable. The above structure is preferable from the viewpoint of enhancing the 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.

Chemical formula

[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 preferred ones, and combinations of preferred ones are equally preferred.

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

[0059] (Carbonic acid diester) The carbonic acid diester is at least one compound selected from carbonic acid diaryl compounds, carbonic acid dialkyl compounds, and carbonic acid alkylaryl compounds. The carbonic acid diaryl compound is a compound represented by the following general formula (11) or a compound represented by the following general formula (12).

Chemical formula

[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).

Chemical formula

[0061] The alkyl aryl carbonate compound is a compound represented by the following general formula (15) or a compound represented by the following general formula (16).

Chemical formula

[0062] Examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, bisphenol A bisphenyl carbonate, and the like. Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A bismethyl carbonate, and the like. Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A methyl phenyl carbonate, and the like. In the production of the polycarbonate-polyorganosiloxane copolymer of the present invention, as the carbonic acid diester, one or more of the above compounds can be appropriately selected and used. Among these, it is preferable to use diphenyl carbonate.

[0063] (Terminal terminator) In the production of the polycarbonate-polyorganosiloxane copolymer of the present invention, a terminal terminator can be used as necessary. As the terminal terminator, a known terminal terminator in the production of polycarbonate resin may be used. For example, specific compounds thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0064] (Branching agent) In the production of the polycarbonate-polyorganosiloxane copolymer of the present invention, a branching agent can also be used. Examples of the branching agent 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; isatin bis(o-cresol); and the like.

[0065] Specifically, for example, the polycarbonate-polyorganosiloxane copolymer of the present invention can be produced by a melt polymerization method according to the following procedure. A transesterification reaction is carried out between the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound. The carbonate ester compound is preferably 0.9 to 1.2 times the molar amount of the diol monomer, more preferably 0.98 to 1.02 times the molar amount. In the above transesterification reaction, when the amount of the end-capping agent present is in the range of 0.05 to 10 mol% with respect to the diol monomer (a1) and the polyorganosiloxane (a2), the hydroxyl terminals of the resulting polycarbonate-polyorganosiloxane copolymer are capped, so that a polycarbonate resin having sufficiently excellent heat resistance and water resistance can be obtained, which is preferable. The amount of the end-capping agent present with respect to the diol monomer (a1) and the polyorganosiloxane (a2) is more preferably 1 to 6 mol%. The end-capping agent may be added in its entirety to the reaction system in advance, or a part of it may be added to the reaction system in advance and the remainder may be added as the reaction proceeds. It is preferable to simultaneously charge an antioxidant into the reactor together with the diol monomer (a1), the polyorganosiloxane (a2), and the carbonate ester compound, and carry out the transesterification reaction in the presence of the antioxidant.

[0066] In carrying out the transesterification reaction, the reaction temperature is not particularly limited and is usually selected in the range of 100 to 330 °C, preferably in the range of 180 to 300 °C, more preferably in the range of 200 to 240 °C. However, a method of gradually raising the temperature to 180 to 300 °C as the reaction proceeds is particularly preferred. If the temperature of this transesterification reaction is 100 °C or higher, the reaction rate will increase. On the other hand, if it is 330 °C or lower, side reactions will not occur, and problems such as coloring of the resulting polycarbonate-polyorganosiloxane copolymer are less likely to occur.

[0067] The reaction pressure is set according to the vapor pressure of the monomers used and the reaction temperature. It is not particularly limited as long as it is set so that the reaction can be carried out efficiently. Usually, at the initial stage of the reaction, the atmospheric pressure (normal pressure) or a pressurized state up to 1 to 50 atm (760 to 38,000 torr) is used, and in the later stage of the reaction, a reduced pressure state, preferably finally 1.33 to 1.33×10 4 Pa (0.01 to 100 torr) is often used. The reaction time may be carried out until 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 if necessary, it may be carried out in the presence of 1 to 150 parts by mass of an inert solvent based on 100 parts by mass of the resulting polycarbonate resin. 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 decane, cycloalkanes such as cyclooctane and cyclodecane, etc. If necessary, it may be carried out under an inert gas atmosphere. Examples of the inert gas include gases such as argon, carbon dioxide, nitrous oxide, and nitrogen, chlorofluorocarbons, alkanes such as ethane and propane, alkenes such as ethylene and propylene, and various others.

[0069] In the melt polymerization method, it is preferable to use a basic catalyst as the catalyst. Examples of the basic catalyst include at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing an aryl group, and metal compounds. These compounds can be used alone or in combination. As the basic catalyst, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; quaternary phosphonium salts containing an aryl group, etc. are preferably used. The basic catalyst can be used alone or in combination of two or more.

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

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

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

[0073] Specific examples of the quaternary phosphonium salt containing an aryl group include, for example, 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, tetrabutylphosphonium hydroxide, etc., tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-t-butylphenyl)phosphonium diphenyl phosphate, triphenylbutylphosphonium phenolate, triphenylbutylphosphonium tetraphenylborate, and the like. The quaternary phosphonium salt containing an aryl group is preferably combined with a nitrogen-containing organic basic compound. For example, the combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0074] The amount of the basic catalyst used can preferably be selected in the range of 1×10 -9 ~1×10 -2 mol, preferably 1×10 -8 ~1×10 -2 mol, more preferably 1×10 -7 ~1×10 -3 mol per 1 mol of the diol monomer.

[0075] A catalyst deactivator can also be added in the later stage of the reaction. As the catalyst deactivator to be used, known catalyst deactivators are effectively used, among which ammonium salts and phosphonium salts of sulfonic acid are preferable. Further, salts of dodecylbenzenesulfonic acid such as tetrabutylphosphonium dodecylbenzenesulfonate and salts of p-toluenesulfonic acid such as tetrabutylammonium p-toluenesulfonate are preferable.

[0076] As esters of sulfonic acid, methyl benzenesulfonate, ethyl benzenesulfonate, butyl benzenesulfonate, octyl benzenesulfonate, phenyl benzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate, etc. are also preferably used. Among them, tetrabutylphosphonium dodecylbenzenesulfonate or butyl p-toluenesulfonate is most preferably used.

[0077] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the amount of the catalyst deactivator used is preferably in a ratio of 0.5 to 50 mol, more preferably in a ratio of 0.5 to 10 mol, and still more preferably in a ratio of 0.8 to 5 mol per mole of the catalyst. After adding the catalyst deactivator and terminating the polymerization reaction, it is preferable to mix an antioxidant.

[0078] The reaction in the melt polymerization method may be carried out either continuously or batchwise. The reaction apparatus used for melt polymerization may be any of a vertical reaction apparatus equipped with an anchor type stirring blade, a max blend stirring blade, or a helical ribbon type stirring blade, or a horizontal reaction apparatus equipped with a paddle blade, a grid blade, or a glasses blade. Further, an extruder type equipped with a screw may also be used. In the case of continuous operation, it is preferable to use such reaction apparatuses in appropriate combination.

[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 bringing a raw material diol monomer (a1), a raw material polyorganosiloxane (a2), a carbonic acid diester, and a basic catalyst into contact at 100 to 250°C for 0.5 to 5 hours is 30 or less under the conditions of 23°C and an optical path length of 10 mm, as measured in accordance with ISO 14782:1999.

[0080] The above haze value is the value measured with a haze measuring device at 23°C using a glass cell with an optical path length of 10 mm filled with the above mixture in accordance with ISO 14782:1999. Note that the haze value measurement conditions for the above 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 above heat treatment is within the above range, it is preferable because the resulting polycarbonate-polyorganosiloxane copolymer has high transparency. The haze value of the raw material mixture after the above heat treatment is more preferably 20 or less, still more preferably 10 or less, still more preferably 5 or less, and still more preferably 1 or less. The conditions for obtaining the mixture for measuring the haze value are as described in (i) above. Further, among the temperature conditions in (i), it is preferably 150 to 250°C, more preferably 180 to 250°C, and the contact time is preferably 0.7 to 4 hours, more preferably 0.7 to 2 hours. In condition (i), when the temperature condition and the contact time are within the above preferred ranges and the resulting mixture has the haze value specified in condition (i), a polycarbonate-polyorganosiloxane copolymer having higher transparency can be obtained.

[0082] <Polycarbonate resin composition> The polycarbonate resin composition of the present invention contains the above-described polycarbonate-polyorganosiloxane copolymer (polycarbonate-polyorganosiloxane copolymer (A)). In the polycarbonate resin composition of the present invention, well-known additives can be used as long as the properties of the above polycarbonate-polyorganosiloxane copolymer (A) are not impaired.

[0083] (Additive) In the polycarbonate resin composition of the present invention, known additives can be blended according to the use and necessity. Examples of the additives include various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymerization metal inactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, mold release agents, and the like. The antioxidant can suppress the decomposition of the resin during the production or molding of the thermoplastic resin composition.

[0084] [Filler] Examples of the filler that can be blended in the polycarbonate resin composition of the present invention include inorganic fillers such as spherical fillers, plate-like fillers, and fibrous fillers. Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, and amorphous zeolite. Examples of the plate-like filler include talc, mica, and wollastonite. Examples of the fibrous filler include glass fiber, carbon fiber, needle-like materials such as wollastonite, magnesium oxysulfate, potassium titanate fiber, and fibrous materials such as fibrous calcium carbonate. It is preferable that the inorganic filler is 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 preferably used as raw materials. The form of these glass fibers is not particularly limited, and for example, 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.), MA409C (manufactured by Asahi Fiber Glass Co., Ltd.), and the like. From the viewpoint of strengthening the resin composition, the polycarbonate-based resin composition of the present invention preferably contains a glass filler.

[0086] The refractive index of the glass filler is not particularly limited. 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 the molded body obtained using the polycarbonate-based resin composition of the present invention can be improved. Furthermore, from the viewpoint of improving the transparency of the molded body made of the 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, still more preferably 1.500 or more, more preferably 1.515 or less, and still more preferably 1.514 or less.

[0087] [Composition ratio] The polycarbonate-based resin composition of the present invention can contain an inorganic filler in an amount of preferably 1 to 150 parts by mass, more preferably 11 to 100 parts by mass, still more preferably 15 to 60 parts by mass, and still more preferably 15 to 40 parts by mass, based on 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A). By setting the amount within the above range, various mechanical property effects caused by the inorganic filler, such as an improvement 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 resin composition of the present invention is not particularly limited as long as it has a step of mixing a polycarbonate-polyorganosiloxane copolymer and an optional additive. For example, it can be produced by mixing a polycarbonate-polyorganosiloxane copolymer and an optional additive using a mixer or the like and performing melt-kneading. Melt-kneading can be carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a kneader, a multi-screw extruder, etc. The heating temperature during melt-kneading is usually appropriately selected in the range of 150°C to 300°C, preferably about 220 to 300°C.

[0089] [Molded article] The molded article of the present invention contains the polycarbonate resin composition of the present invention. The molded article can be produced by an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, a foam molding method, etc., using a melt-kneaded product of the polycarbonate resin composition or pellets obtained through melt-kneading as raw materials. In particular, it is preferable to produce a molded article by an injection molding method or an injection compression molding method using the obtained pellets.

[0090] The thickness of the molded article can be arbitrarily set according to the application. Particularly when transparency of the molded article is required, 0.2 to 4.0 mm is preferable, 0.3 to 3.0 mm is more preferable, and 0.3 to 2.0 mm is even more preferable. If the thickness of the molded article is 0.2 mm or more, warping will not occur and good mechanical strength can be obtained. Also, if the thickness of the molded article is 4.0 mm or less, high transparency can be obtained.

[0091] A hard coat film, an anti-fog film, an antistatic film, or an anti-reflection film coating may be formed on the molded article as needed, or a composite coating of two or more types may also be used. Among these, since it has good weather resistance and can prevent abrasion of the molded product surface over time, it is particularly preferable that a coating film of a hard coat film is formed. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic-based hard coat agents can be used.

[0092] In the case of a molded product containing a glass filler, at least a part of the glass filler exists on the outermost surface of the molded product, which may increase the surface roughness of the molded product, increase diffuse reflection on the molded product surface, and as a result, deteriorate the transparency of the molded product. Therefore, as a method of reducing the surface roughness of the molded product, there is a method of reducing the surface roughness of the molded product by forming a layer (skin layer) with a high resin presence ratio on the outermost surface of the molded product. As a method of forming this skin layer, in the case of injection molding, by setting the temperature of the mold higher than general conditions, the resin in contact with the mold can be made more fluid, and the surface roughness of the outermost surface of the molded product can be reduced. Also, in the case of compression molding, by setting the pressure during molding higher than general conditions, the surface roughness of the outermost surface of the molded product can be reduced. By using these methods to reduce the surface roughness of the molded product, diffuse reflection on the molded product surface is reduced, haze is reduced, and as a result, the transparency of the molded product can be improved.

[0093] When the molded article obtained in this manner is formed into a flat plate, when the content of the polyorganosiloxane block represented by the 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 with respect to visible light is preferably 60% or more. The total light transmittance is more preferably 70% or more, still more preferably 80% or more, still more preferably 85% or more, and still more preferably 90% or more. When the content of the polyorganosiloxane block represented by the formula (1) in the polycarbonate-polyorganosiloxane copolymer is 5% by mass or more, the total light transmittance with respect to visible light is preferably 25% or more. The haze during the flat plate forming is preferably 40 or less, more preferably 30 or less, still more preferably 15 or less, still more preferably 5 or less, and particularly preferably 2 or less when the content of the polyorganosiloxane block represented by the 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. Since the molded article having the above optical properties is excellent in transparency, it can be used in applications that require high transparency. The total light transmittance with respect to visible light can be measured according to ISO 13468-1:1996, and the haze can be measured according to ISO 14782:1999.

[0094] The molded article containing the polycarbonate resin according to the present invention is a member that requires transparency, rigidity, further scratch resistance and weather resistance, for example, 1) automotive parts such as sunroofs, door visors, rear windows, side windows, etc.; 2) building parts such as architectural glass, soundproof walls, carports, sunrooms and gratings; 3) windows for railway vehicles and ships; 4) various parts such as TVs, radio cassettes, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, registers, copiers, printers, facsimiles, etc., parts for electrical equipment such as outer plates and housings; 5) cases and covers for precision machinery such as mobile phones, PDAs, cameras, slide projectors, watches, calculators, measuring instruments, display devices, etc., parts for precision machinery; 6) agricultural parts such as greenhouses and hothouses; 7) furniture parts such as lighting covers, blinds, and interior fixtures, etc., and can be suitably used for these.

Example

[0095] Hereinafter, the present invention will be described in more detail 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 following procedures.

[0097] <Quantification method of polydimethylsiloxane content> Example) Quantification method of polydimethylsiloxane contained in the polycarbonate - polyorganosiloxane copolymer obtained in Example 3 NMR apparatus: ECA - 500 manufactured by JEOL RESONANCE Co., Ltd. Probe: Compatible with TH5 5φ NMR sample tube Observation range: - 5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of integrations: 256 times NMR sample tube: 5φ Sample amount: 30 - 40 mg Solvent: Deuterated chloroform Measurement temperature: Room temperature A: Integral value of the meta-position of the phenyl group observed around δ 7.3 - 7.5 B: Integral value of the methyl group of the dimethylsiloxane part observed around δ -0.02 - 0.3 C: Integral value of the methine group of the ISB (isosorbide) part observed around δ 4.8 - 5.3 D: Integral value of the methylene group of the PEG part observed around δ 3.3 - 3.8 E: Integral values of the methine group and methylene group of the CHDM part observed around δ 0.8 - 2.0 F: Integral value of the methylene group at the end of the dimethylsiloxane part observed around δ 0.4 - 0.6 a = A / 2 b = B / 6 c = C / 3 d = D / 4 e = (E - F) / 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> Using an Ubbelohde viscometer, the viscosity of a methylene chloride solution (concentration: g / L) at 20°C was measured, and from this, the intrinsic viscosity [η] was determined, and the viscosity-average molecular weight (Mv) was calculated using the following equation (Schnell's equation). [η] = 1.23×10 -5 Mv 0.83

[0099] [Evaluation test] <Total light transmittance of resin molded product: Tt (%), haze value> The evaluation pellets obtained in each example and comparative example were processed using an injection molding machine (manufactured by Niigata Machine Technology Co., Ltd., "MD50XB", screw diameter 30 mmφ) at a cylinder temperature of 240 °C and a mold temperature of 80 °C to create a three-step plate for transparency evaluation (90 mm × 50 mm, 45 mm × 50 mm at 3 mm thickness, 22.5 mm × 50 mm at 2 mm thickness, 22.5 mm × 50 mm at 1 mm thickness). The total light transmittance was measured for the 1 mm thick portion of the above three-step plate in accordance with ISO 13468-1:1996. The haze value was measured for the 1 mm thick portion of the same sample in accordance with ISO 14782:1999. For both values, NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. was used as the measuring device. The smaller the haze value, the higher the transparency of the sample. Haze = Td / Tt × 100 (where Td: diffuse transmittance, Tt: total light transmittance)

[0100] <Total light transmittance of raw material mixture (%), haze value> 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: NDH5000 manufactured by Nippon Denshoku Industries Co., Ltd. Glass cell: Optical path length: 10 mm Dimensions: Outer dimensions 14 mm (depth) × 40 mm (width) × 55 mm (height) Glass thickness of each surface: 2 mm Before measuring the haze of the raw material mixture, the glass cell was filled with pure water for zero point correction. Specifically, the measured values in the state where the cell was filled with pure water were corrected to a state where the total light transmittance was 100% and the haze value was 0.00. Next, the pure water was removed from the glass cell, and the liquid mixture obtained by the method described below was filled therein for measurement, and the haze value at 23 °C was determined in accordance with ISO 14782:1999. Haze = Td / Tt × 100 (where Td: diffuse transmittance, Tt: total light transmittance)

[0101] Production Example 1: Production of PDMS-1 Under a nitrogen atmosphere, the following formula: [Chemical formula] To 100 g of a polyorganosiloxane in which the average siloxane chain length represented by the following is 24, the following formula: [Chemical formula] 82.3 g of polyethylene glycol having an average oxyethylene chain length of 15, represented by the following, was added in a molar amount twice that of the polyorganosiloxane. Here, 455 g of isopropyl alcohol (2.5 parts based on the total mass of the polyorganosiloxane and polyethylene glycol) was added, and then the temperature of the mixture was controlled to 80 °C and stirred well. 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 with respect to the siloxane, and the mixture was stirred for 10 hours. By removing isopropyl alcohol and the platinum catalyst from the obtained mixture, polyether-modified polyorganosiloxane PDMS-1 was obtained.

[0102] Production Example 2: Production of PDMS-2 It was produced in the same manner as in Production Example 1, except that an α,ω-dihydrogen organopolysiloxane having an average siloxane chain length of 61 was used.

[0103] Production Example 3: Production of PDMS-3 It was produced in the same manner as in Production Example 1, except that an α,ω-dihydrogen organopolysiloxane having an average siloxane chain length of 88 was used.

[0104] Production Example 4: Production of PDMS-4 It was produced 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: [Chemical formula] To a polyorganosiloxane having an average siloxane chain length of 39, as shown by , 2-allylphenol was added in a 2-fold molar amount relative to the polyorganosiloxane. The mixture was stirred well while controlling the mixture temperature at 100 °C. Subsequently, 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 to obtain 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 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 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] Production Example 10: Production 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, the solvent was toluene, 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 charged into a flask, and 21.5 g of 2,6-di-t-butylpyridine and 21 g of trifluoromethanesulfonic anhydride were charged therein, and this mixture was cooled to 15 °C or lower. 4.3 g of allyl alcohol was added dropwise thereto to form a reaction initiator. After stirring for about 15 minutes, 1 L of dehydrated tetrahydrofuran was added, and after stirring at 20 to 23 °C for 5 minutes, 30 mL of ion-exchanged water was added to stop the reaction. Extraction was performed with heptane, washing was performed with 10% hydrochloric acid, and after separating the aqueous layer, subsequently, washing was performed twice with ion-exchanged water and the aqueous layer was separated. Thereafter, the solvent was distilled off under reduced pressure conditions, and 120 g of a mono-terminal allyl-modified polytetramethylene glycol (chain length of the tetramethylene glycol moiety = 20) represented by the following formula: [Chemical formula] was obtained. The production was carried out in the same manner as in Production Example 8, except that the mono-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 the solvent used was 3 times the total volume of the polyorganosiloxane and the mono-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 a nitrogen atmosphere was charged with a polydimethylsiloxane having -C3H6OC2H4OH groups at both ends (average chain number of SiMe2O units: 40) and trimethylene carbonate in a molar amount 25 times that of the hydroxyl groups of the aforementioned polyorganosiloxane. Dehydrated dichloromethane was added so that the concentration of these raw materials became 10 wt%. To the obtained transparent reaction solution, 1,8-diazabicycloundecene in an amount of 3 equivalents relative to the terminal OH groups of the polydimethylsiloxane was added as a catalyst, and the mixture was reacted at room temperature for 48 hours. Thereafter, benzoic acid was added to stop the reaction, and the reaction mixture was reprecipitated in a mixed solvent composed of a methanol, 2-propanol, hexane mixture (volume ratio: 10:1:10), and the obtained precipitate was dried under vacuum to obtain PDMS-12 (chain number of polytrimethylene carbonate at each terminal: 18).

[0113] Production Example 13: Production of PDMS-13 Under a nitrogen atmosphere, 450 mL of methylene chloride was charged into a flask, 45.0 g of 3-iodo-1-propanol was added thereto, and the mixture was cooled in an ice bath. 40.1 g of tert-butyldimethylchlorosilane was added thereto, and the mixture was stirred at room temperature for 20 hours. The obtained mixture was quenched with a 5% aqueous sodium hydrogen carbonate solution, and the product was extracted with ethyl acetate / ion-exchanged water. The obtained product was produced by a silica gel column to obtain a TBS-protected product of 3-iodo-1-propanol (yield 67.7 g). Under a nitrogen atmosphere, 2.9 g of the TBS-protected form of 3-iodo-1-propanol and 270 mL of tetrahydrofuran were mixed in a flask and cooled to -65°C or lower. 12.5 mL of 1.6 mol / L tert-butyllithium (pentane solution) was added dropwise thereto, and the mixture was stirred as it was for 15 minutes. 2.5 mL of diphenylethylene was added dropwise thereto, and the mixture was stirred as it was for 30 minutes. Thereafter, 55 mL of a 0.52 mol / L lithium chloride THF solution was added, and the mixture was stirred for 10 minutes. Next, 10.1 mL of methyl methacrylate was added and stirred for 10 minutes. Next, 3.36 mL of allyl bromide was added to quench the reaction, and thereafter the mixture was mixed at room temperature for 12 hours. The obtained reaction mixture was concentrated under reduced pressure, reprecipitated in a THF / heptane system, and then subjected to silica gel column purification to remove the solvent, thereby obtaining the TBS-protected form of the one-end allyl-modified PMMA. This product was dissolved in THF, deprotected with a 2 mol / L hydrochloric acid aqueous solution, and the obtained reaction mixture was poured into heptane to separate the target product (deprotected form). This deprotected form was subjected to silica gel column purification, and the solvent was removed to obtain the following formula: [Chemical formula] Thereby, one-end allyl-modified PMMA (number of chains in the PMMA part = 20) shown by the following was obtained. It was produced in the same manner as in Production Example 8, except that the above one-end allyl-modified PMMA was used instead of polyethylene glycol.

[0114] Production Example 14: Production of PDMS-14 It was produced in the same manner as in Production Example 1, except that polypropylene glycol having an average oxypropylene chain length of 15 shown by the following formula: [Chemical formula] was used instead of polyethylene glycol.

[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 [manufactured by Idemitsu Kosan Co., Ltd.] 1,4-CHDM: 1,4-Cyclohexanedimethanol [manufactured by Tokyo Chemical Industry Co., Ltd.] TCDDM: Tricyclodecane dimethanol [manufactured by OXEA GmbH] 1,3-PG: 1,3-Propanediol [manufactured by 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 [manufactured by Mitsui Chemicals Fine Co., Ltd.] 0.01N aqueous sodium hydroxide solution [manufactured by Fujifilm Wako Pure Chemical Corporation]

[0118] Example 1 <Evaluation of transparency of the raw material mixture after heat treatment> Into a 10 L stainless steel reactor equipped with double helical blades as a stirring device, BisP-A (2,489.9 g) and DPC (2,500 g) (mol ratio of each raw material: BisP-A / DPC = 100 / 107), and 28.2 g of polyether-modified polyorganosiloxane PDMS-1 were charged. 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 0.01N sodium hydroxide (1.5 × 10 -6 times the amount based on the total number of moles of diol monomers) was added, and while maintaining a nitrogen pressure of 101 kPa, the same as atmospheric pressure, the temperature of the mixture was raised to 200 °C and maintained at this temperature for 60 minutes. Subsequently, the content was withdrawn from the valve at the bottom of the reactor, and a liquid and transparent raw material mixture was obtained. The total light transmittance of the liquid raw material mixture after heat treatment was 98.4, and the haze value was 0.5, indicating 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 for the above transparency evaluation, but the polymerization conditions were as follows. Into a 10 L stainless steel reactor equipped with a stirrer, a trap for capturing distilled phenol, and a decompression device, as diol monomers, BisP-A (2,489.9 g) and DPC (2,500 g) (mol ratio of each raw material: BisP-A / DPC = 100 / 107), and 28.2 g of polyether-modified polyorganosiloxane PDMS-1 were charged. These raw material monomers were completely melted at 150 °C, and the inside of the reactor was purged with nitrogen. As a catalyst, 1.64 mL of 0.01 N sodium hydroxide (1.5 times the amount relative to the total number of moles of diol monomers) was charged to initiate polymerization. The temperature of the reactor was raised and the pressure was reduced over about 60 minutes to 180 °C and 200 mmHg (26.6 kPa), and the reaction conditions were maintained until the amount of distilled phenol reached 0.2 L. Then, over about 60 minutes, the internal temperature of the reactor was raised and the pressure was reduced to 200 °C and 10 mmHg (1.3 kPa), and the conditions were maintained until 1.0 L of phenol was distilled. -6 Next, the internal temperature of the reactor was raised to 240 °C over about 120 minutes, and the conditions were maintained until 1.5 L of phenol was distilled. Subsequently, over about 120 minutes, the internal temperature of the reactor was adjusted to 280 °C and the pressure was reduced to 1 mmHg (0.1 kPa) or less, and more than 2 L of phenol was distilled, and the reaction was continued until a predetermined stirring torque was reached. Then, the pressure was restored with nitrogen, and 0.037 g of butyl p-toluenesulfonate (10 times the amount relative to the number of moles of NaOH) was charged as a deactivator. Irganox 1010 and Irgafos 168 were each charged so that the content in the resulting polymer was 1,500 ppm, and the mixture was stirred well. Then, resin strands were withdrawn from the bottom of the reactor by nitrogen pressure and cut with a pelletizer to obtain highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2. Example 2

[0120] Example 2 As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2500 g of DPC (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), except that 24.4 g of polyether-modified polyorganosiloxane PDMS-1 was used, the transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.5% and a haze value of 0.5. As the diol monomers, 1293.3 g of BisP-A, 817.0 g of 1,4-CHDM, and 2500 g of DPC (mol ratio of each raw material: BisP-A / 1,4-CHDM / DPC = 50 / 50 / 103), except that 24.4 g of polyether-modified polyorganosiloxane PDMS-1 was used, by polymerizing under the same conditions as in Example 1, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0121] Example 3 <Transparency evaluation of the raw material mixture after heat treatment> Except for using 1193.8 g of isosorbide (ISB), 504.9 g of 1,4-CHDM, 2500 g of DPC (mol ratio of each raw material: ISB / 1,4-CHDM / DPC = 70:30:100), and 20.2 g of polyether-modified polyorganosiloxane PDMS-1, the raw materials were heat-treated in the same manner as in Example 1. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 99.5% and a haze value of 0.4.

[0122] <Production of PC-POS copolymer> Into a 10 L stainless steel reactor equipped with a stirring device, a trap for capturing the residual phenol, and a decompression device, as diol monomers, ISB (1193.8 g), 1,4-CHDM (504.9 g), DPC (2500 g) (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 charged. These raw material monomers were completely melted at 100 °C, and the inside of the reactor was purged with nitrogen. As a catalyst, 1.64 mL of 0.01 N sodium hydroxide (1.5×10 -6 times the number of moles of the total diol monomers) was charged to initiate polymerization. The temperature of the reactor was raised and the pressure was reduced over about 50 - 100 minutes to 180 °C and 200 mmHg (26.6 kPa) of reduced pressure, and these conditions were maintained until the amount of distilled phenol reached 0.2 L. Then, over about 150 minutes, the internal temperature of the reactor was raised and the pressure was reduced to 200 °C and 10 mmHg (1.3 kPa) of reduced pressure, and these conditions were maintained until 1.8 L of phenol was distilled. Next, over about 60 minutes, the internal temperature of the reactor was adjusted to 220 °C and the reduced pressure was adjusted to 1 mmHg (0.1 kPa) or less, and more than 2 L of phenol was distilled, and the reaction was continued until a predetermined stirring torque was reached. Then, the pressure was restored with nitrogen, and 0.037 g of butyl p-toluenesulfonate (10 times the number of moles of NaOH) was charged as a deactivator. Irganox 1010 and Irgafos 168 were charged so that the content in the resulting polymer was 1500 ppm each, and they were stirred well. Then, resin strands were withdrawn from the bottom of the reactor by nitrogen pressure and cut with a pelletizer to obtain highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0123] Example 4 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-2 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.4% and a haze value of 0.8. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-3 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 1.3. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-4 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 0.7. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 105.4 g of PDMS-1 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 97.5% and a haze value of 0.9. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 222.5 g of PDMS-1 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 97.1% and a haze value of 1.1. A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 as the diol monomer, 1193.8 g of ISB, 687.2 g of TCDDM, 2500 g of DPC (mol ratio of each raw material: ISB / TCDDM / DPC = 70:30:100), and 22.1 g of polyether-modified polyorganosiloxane PDMS-1 were used. 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 polymerizing under the same conditions as in Example 3, except that as the diol monomer, 1193.8 g of ISB, 687.2 g of TCDDM, 2500 g of DPC (mol ratio of each raw material: ISB / TCDDM / DPC = 70:30:100), and 22.1 g of polyether-modified polyorganosiloxane PDMS-1 were used. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0129] Example 10 As the diol monomer, except for using ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2500 g) (mol 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 transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 3. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. As the diol monomer, except for using ISB (1193.8 g), 1,4-CHDM (420.7 g), 1,3-PG (44.4 g), DPC (2500 g) (mol 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, a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 3. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[0130] Example 11 As the diol monomer, except for using ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2500 g) [mol ratio of each raw material: ISB / 1,4-CHDM / PEG400 / DPC = 70:28:2:100 (the number of moles of PEG400 was the value obtained by dividing the used mass by the average molecular weight of 400)], and 21.3 g of polyether-modified polyorganosiloxane PDMS-1, the transparency evaluation of the raw material mixture after heat treatment was carried out in the same manner as in Example 3. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 98.3% and a haze value of 0.4. As diol monomers, ISB (1193.8 g), 1,4-CHDM (504.9 g), PEG400 (93.4 g), DPC (2500 g) [mol ratio of each raw material: ISB / 1,4-CHDM / PEG400 / DPC = 70:28:2:100 (the number of moles of PEG400 was the value obtained by dividing the used mass by the average molecular weight of 400)], except that 21.3 g of polyether-modified polyorganosiloxane PDMS-1 was used, polymerization was carried out under the same conditions as in Example 3 to obtain a highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 2.

[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 polymerizing 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 polymerizing 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 highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 1, except that 179.7 g of PDMS-10 was used as the polyorganosiloxane. The resulting polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,150, 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 <Evaluation of Transparency of Raw Material Mixture after Heat Treatment> The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1, except that 28.2 g of PDMS-11 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment had high transparency, with a total light transmittance of 89.9% and a haze value of 7.3. <Production of PC-POS Copolymer> A highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 1, except that 28.2 g of PDMS-11 was used as the polyorganosiloxane. The resulting polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 20,200, 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 <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 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 Raw Material Mixture after Heat Treatment> The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1, except that 28.2 g of PDMS-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 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-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 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-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 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 highly transparent pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerization under the same conditions as in Example 1, except that 28.2 g of PDMS-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 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 pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 2, except that 20.2 g of PDMS-14 was used as the polyorganosiloxane. The resulting polycarbonate-polyorganosiloxane copolymer had a viscosity-average molecular weight of 15,000, a polydimethylsiloxane content of 0.68% by mass, a total light transmittance of 69.7%, and a haze value of 84.0.

[0141] Comparative Example 1 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 1, except that 28.2 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 77.6% and a haze value of 95.4. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 1, except that 28.2 g of PDMS-5 was used as the polyorganosiloxane. The evaluation results of the obtained polycarbonate-polyorganosiloxane copolymer are shown in Table 3.

[0142] Comparative Example 2 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 2, except that 24.4 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 78.5% and a haze value of 93.2. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 79.1% and a haze value of 92.1. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 105.4 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 63.2% and a haze value of 95.5. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-6 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 79.5% and a haze value of 93.1. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 3, except that 20.2 g of PDMS-7 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, with a total light transmittance of 81.1% and a haze value of 88.9. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 9, except that 22.1 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, and the total light transmittance was 80.1% and the haze value was 90.1. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 10, except that 19.8 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, and the total light transmittance was 78.5% and the haze value was 89.9. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 The transparency of the raw material mixture after heat treatment was evaluated in the same manner as in Example 11, except that 21.3 g of PDMS-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, and the total light transmittance was 79.9% and the haze value was 88.5. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing 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 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-5 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, and the total light transmittance was 65.1% and the haze value was 97.5. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 1, except that 179.7 g of PDMS-5 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,000, a polydimethylsiloxane content of 5.30% by mass, a total light transmittance of 19.3%, a haze value of 99.6, and a Charpy impact strength (with notch) of 61.0 kJ / m 2 was obtained.

[0151] Comparative Example 11 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-7 was used as the polyorganosiloxane. The liquid raw material mixture after heat treatment was turbid, and the total light transmittance was 66.5% and the haze value was 96.2. A strongly turbid pellet-shaped polycarbonate-polyorganosiloxane copolymer was obtained by polymerizing under the same conditions as in Example 1, except that 179.7 g of PDMS-7 was used as the polyorganosiloxane. The obtained polycarbonate-polyorganosiloxane copolymer had a viscosity average molecular weight of 20,100, a polydimethylsiloxane content of 5.50% by mass, a total light transmittance of 17.5%, a haze value of 99.5, and a Charpy impact strength (with notch) of 61.0 kJ / m 2 was obtained.

[0152]

Table 2

[0153]

Table 3

Claims

1. A method for producing a polycarbonate-polyorganosiloxane copolymer using, as raw material monomers, a diol monomer (a1) represented by the following general formula (a1) and a polyorganosiloxane (a2) having any of the structures represented by the following general formulas (a2-1) to (a2-3): 【Chemistry 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 in which the alkyl group moiety has 1 to 10 carbon atoms. R 5 and R 6 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 1 to 10 carbon atoms in the alkyl group portion; and as functional groups, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 7 represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 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 be included. 8 may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 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 functional groups, -O-, -COO-, -CO-, -S-, -NH-, -NR 111 - may contain R 111 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z represents 0 or 1. z1 represents 0 or 1. a represents an integer from 2 to 500, and b represents an integer from 5 to 200. b1 represents an integer from 5 to 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. R 10 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may be substituted by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.]

2. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein 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.

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

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

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

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

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

8. The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 7, wherein the obtained polycarbonate-polyorganosiloxane copolymer comprises a polyorganosiloxane block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) consisting of a repeating unit represented by the following general formula (2). 【Chemistry 2】 [In the formula, R １ ~R ４ may be the same or different, and each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group in which the alkyl group moiety has 1 to 10 carbon atoms. R ６ represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having an alkyl moiety having 1 to 10 carbon atoms; １１１ - may be included. ８ may be the same or different, and each independently represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 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 functional groups, -O-, -COO-, -CO-, -S-, -NH-, -NR １１１ - may contain R １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z represents 0 or 1. a represents an integer of 2 to 500, and b represents an integer of 5 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 by a substituent. The divalent aliphatic hydrocarbon group, the divalent alicyclic hydrocarbon group, or the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, or at least one halogen atom selected from a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. y represents an integer of 10 to 500.]

9. The polycarbonate-polyorganosiloxane copolymer according to claim 8, wherein the content of the polyorganosiloxane block represented by the general formula (1) in the polycarbonate-polyorganosiloxane copolymer is 0.1% by mass or more and 60% by mass or less. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 8.

10. The method for producing a polycarbonate-polyorganosiloxane copolymer according to claim 8 or 9, wherein the viscosity average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer is 5,000 or more and 50,000 or less.

11. The polycarbonate-polyorganosiloxane copolymer is molded into a 1 mm thick plate, and the haze value measured according to ISO 14782:1999 of the resulting plate is 40 or less. The method for producing the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 10.

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