Polycarbonate-polyorganosiloxane copolymer

Abstract

A polycarbonate-polyorganosiloxane copolymer including a polycarbonate block (A-1) formed of a repeating unit having a specific structure and a polyorganosiloxane block (A-2) formed of a repeating unit having a specific structure, wherein a difference Δhaze between a haze value (haze A) and a haze value (haze B), which are respectively obtained when the polycarbonate-polyorganosiloxane copolymer or a resin composition thereof is kept at 300°C or 340°C for 3 minutes and 20 minutes, is less than 0.4.

Description

[Technical field]

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, and more particularly to a polycarbonate-polyorganosiloxane copolymer that has excellent thermal stability even when molded at high temperatures and can give molded articles with excellent transparency. [Background technology]

[0002] Polycarbonate resin (hereinafter sometimes abbreviated as PC resin) produced from bisphenol A etc. is known as a resin that has extremely high impact resistance and excellent heat resistance among engineering plastics. Meanwhile, attempts have been made to further improve impact resistance and heat resistance by using polyorganosiloxane as a copolymerization monomer together with dihydric phenols such as bisphenol A to form polycarbonate-polyorganosiloxane copolymers.

[0003] Polycarbonate-polyorganosiloxane copolymers (hereinafter sometimes abbreviated as PC-POS copolymers) are known as polycarbonate resins with excellent flame retardancy and impact resistance (for example, Patent Document 1). Due to their excellent properties such as high impact resistance, chemical resistance, and flame retardancy, PC-POS copolymers are expected to be widely used in various fields such as the electrical and electronic equipment field and the automotive field. Patent Document 2 discloses a polycarbonate-polyorganosiloxane copolymer with improved transparency, and evaluates the total light transmittance, haze value, and the like. Patent Documents 3 to 5 disclose molded articles having improved lubricity, abrasion resistance, and the like, by using a PC-POS copolymer. Patent Document 6 describes a method for producing a PC-POS copolymer, which has specific steps. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 2662310 [Patent Document 2] JP 2011-046911 A [Patent Document 3] Japanese Patent Application Publication No. 05-202181 [Patent Document 4] Japanese Patent Application Publication No. 05-202182 [Patent Document 5] Japanese Patent Application Publication No. 05-200761 [Patent Document 6] Patent No. 5919294 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, materials with the properties of PC-POS copolymers have come to be desired in many applications, and there has been a need to mold them into a variety of shapes. This has led to the need to ensure the fluidity of the resin, and the temperature during molding tends to be higher. However, PC-POS copolymers have the problem that their transparency is more likely to decrease than that of general polycarbonates when molded at high temperatures. Although Patent Document 2 reports that a PC-POS copolymer having a specific average domain size and normalized dispersion has improved total light transmittance (88% or more), such a total light transmittance has been achievable in the past. Patent Documents 3 to 5 show improvements in the mechanical strength of PC-POS copolymers, but do not consider improvements in thermal stability such as transparency during molding at high temperatures. Patent Document 6 discloses a method for producing a PC-POS copolymer with excellent impact resistance and transparency, but the thermal stability such as transparency during molding at high temperatures is still insufficient.

[0006] In view of the above, an object of the present invention is to provide a polycarbonate-polyorganosiloxane copolymer that has excellent mechanical properties such as impact resistance and also has excellent transparency even after molding at high temperatures. [Means for solving the problem]

[0007] As a result of extensive research, the present inventors have found that a polycarbonate-polyorganosiloxane copolymer in which the polyorganosiloxane block has a specific structure and satisfies specific haze conditions has high transparency.

[0008] [1] A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A-1) having a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) having a repeating unit represented by the following general formula (II): The polycarbonate-polyorganosiloxane copolymer has a difference Δhaze between the haze value (haze A) after retention for 3 minutes at 300°C or 340°C and the haze value (haze B) after retention for 20 minutes, which is less than 0.4. [ka] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 Each of a and b independently represents an integer of 0 to 4. 3 ~R 6each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n represents the average chain length of the polyorganosiloxane, and n-1 is an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit. Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In these divalent hydrocarbon groups or monovalent hydrocarbon groups, at least one of the carbon atoms may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. k represents an integer of 2 or 3.] [2] The polycarbonate-polyorganosiloxane copolymer according to [1] above, having a platinum content of 0.05 ppb by mass or more and less than 0.5 ppm by mass. [3] The polycarbonate-polyorganosiloxane copolymer according to the above [1] or [2], wherein Z in the formula (II) is represented by the following general formula (II-a): [ka] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. w represents an integer of 0 to 4, and the wavy line represents a bonding site.] [4] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [3], wherein the average chain length n of the polyorganosiloxane block (A-2) is 10 or more and 300 or less. [5] A polycarbonate-polyorganosiloxane copolymer according to any one of the above [1] to [4], comprising a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), in which the ratio of [total number of hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] is less than 0.01. [ka] [In the formula, Z is as defined above. k is 2 or 3.] [ka] [In the formula, R 3 ~R 6 , n, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , n is as defined above.] [6] A polycarbonate-polyorganosiloxane copolymer obtained by continuously supplying an organohydrogensiloxane represented by the following general formula (2), a compound represented by the following general formula (3), and a platinum catalyst to a reactor and passing them through the reactor to cause a hydrosilylation reaction, and then copolymerizing the resulting carbinol-modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or by copolymerizing the carbinol-modified polyorganosiloxane with an oligomer having a repeating unit represented by the following general formula (I). [ka] [In the formula, R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different, and f is an integer of 0 to 500. [ka] [In the formula, R 22represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.] [ka] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O- or -CO-; and a and b each independently represent an integer of 0 to 4. [7] The polycarbonate-polyorganosiloxane copolymer according to [6] above, wherein the platinum catalyst is used in an amount of 0.005 ppm by mass or more and less than 1.0 ppm by mass, calculated as platinum metal, based on the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst. [8] The polycarbonate-polyorganosiloxane copolymer according to [6] or [7] above, wherein the platinum catalyst is used in an amount of 0.005 ppm by mass or more and 0.2 ppm by mass or less, calculated as platinum metal, based on the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst. [9] The polycarbonate-polyorganosiloxane copolymer according to any one of the above [6] to [8], wherein the compound represented by the general formula (3) is a compound represented by the following general formula (33): [ka] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.]

[10] The carbinol-modified polyorganosiloxane is represented by the following general formula (222), in which R a The polycarbonate-polyorganosiloxane copolymer according to any one of the above [6] to [9], wherein a carbinol-modified polyorganosiloxane having a ratio of [the number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and groups represented by formula (vi)] of less than 0.01 is used. [ka] {where, R 3 ~R 6 , f is as described above. R a are each independently a group represented by the following general formula (v) or (vi): [ka] [In the formula, Z is as defined above. k is 2 or 3.] [ka] [In the formula, Z is as defined above. 33 is a vinyl group, an allyl group, or a -(CH 2 ) k -SiR 5 R 6 represents an end group having O-, and k is 2 or 3. [ka] [In the formula, R3 ~R 6 , f is as defined above.]}

[11] A polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane unit represented by the following general formula (222-i), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (b), and a compound represented by the following general formula (c), 33 The number of groups represented by formula (vi) and the number of groups represented by formula (b) and formula (c) 33 The polycarbonate-polyorganosiloxane copolymer according to the above item

[10] , wherein the ratio of the number of groups represented by the formula (I) to the number of groups represented by the formula (I) is less than 0.01. [ka] {where, R 3 ~R 6 , f is as described above. R a are each independently a group represented by the following general formula (vi): [ka] [wherein Z is as defined above; the oxygen atom of formula (vi) is bonded to the polycarbonate unit; and k is 2 or 3.] [ka] [In the formula, R 3 ~R 6 , Z, R 33 , f, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , Z, R 33 , f is as defined above.]

[12] The carbinol-modified polyorganosiloxane is represented by the following general formula (223), in which R b The polycarbonate-polyorganosiloxane copolymer according to any one of the above [6] to [9], wherein a carbinol-modified polyorganosiloxane having a ratio of [number of hydroxy groups] / [total number of hydroxy groups and groups represented by formula (v)] of less than 0.01 is used. [ka] {where, R 3 ~R 6 , f is as described above. R a are each independently a hydroxy group or a group represented by the following general formula (v): [ka] [In the formula, Z is as defined above, and k is 2 or 3.]

[13] A polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane unit represented by the following general formula (223-i), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (d), and a compound represented by the following general formula (e), in which the ratio of [total number of hydroxy groups in formulas (d) and (e)] / [total number of groups represented by formula (vi) and hydroxy groups in formulas (d) and (e)] is less than 0.01, as described in

[12] above. [ka] {where, R 3 ~R 6 , f is as described above. R b-i are each independently a group represented by the following general formula (vi): [ka] [wherein Z is as defined above; the oxygen atom of formula (vi) is bonded to the polycarbonate unit; and k is 2 or 3.] [ka] [In the formula, R 3 ~R 6 , f, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , f is as defined above.]

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

[13] .

[15] A molded article made of the polycarbonate resin composition described in

[14] above.

[0009] The present invention also relates to the following:

[0101] (X1) a step of continuously supplying an organohydrogensiloxane represented by the following general formula (2), a compound represented by the following general formula (3), and a platinum catalyst to a reactor and causing a hydrosilylation reaction while passing through the reactor to obtain a carbinol-modified polyorganosiloxane; and (X2) A method for producing a polycarbonate-polyorganosiloxane copolymer, comprising a step of copolymerizing the carbinol-modified polyorganosiloxane obtained in the step (X1) with a dihydric phenol and a carbonate precursor, or with an oligomer having a repeating unit represented by the following general formula (I): [ka] [In the formula, R 3 ~R 6each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different, and f is an integer of 0 to 500. [ka] [In the formula, R 22 represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.] [ka] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O- or -CO-; and a and b each independently represent an integer of 0 to 4.

[0102] The method for producing a polycarbonate-polyorganosiloxane copolymer according to the above-mentioned

[0101] , wherein in the step (X1), a platinum catalyst is used in an amount of 0.005 ppm by mass or more and less than 1.0 ppm by mass, calculated as platinum metal, based on the total amount of the organohydrogensiloxane represented by the above-mentioned general formula (2), the compound represented by the above-mentioned general formula (3), and the platinum catalyst.

[0103] The method for producing a polycarbonate-polyorganosiloxane copolymer according to the above

[0101] or

[0102] , wherein in the step (X1), a platinum catalyst is used in an amount of 0.005 ppm by mass or more and 0.2 ppm by mass or less, calculated as platinum metal, based on the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst.

[0104] The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of the above-mentioned

[0101] to

[0103] , wherein the compound represented by the general formula (3) is a compound represented by the following general formula (33): [ka] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.] Effect of the Invention

[0010] According to the present invention, it is possible to produce a polycarbonate-polyorganosiloxane copolymer that has excellent mechanical properties derived from the polyorganosiloxane blocks and maintains excellent transparency even after molding at high temperatures, i.e., has high thermal stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The polycarbonate-polyorganosiloxane copolymer of the present invention will be described in detail below. In this specification, the definitions that are considered to be preferable can be adopted arbitrarily, and it can be said that a combination of preferable ones is more preferable. In this specification, the description "XX to YY" means "XX or more and YY or less".

[0012] The polycarbonate-polyorganosiloxane copolymer of the present invention is a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A-1) consisting of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), characterized in that the difference Δhaze between the haze value (haze A) after retention of the polycarbonate-polyorganosiloxane copolymer or a resin composition thereof at 300°C or 340°C for 3 minutes and the haze value (haze B) after retention for 20 minutes is less than 0.4. [ka] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 Each of a and b independently represents an integer of 0 to 4. 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n represents the average chain length of the polyorganosiloxane, and n-1 is an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit. Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms of these divalent hydrocarbon groups or monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. k represents an integer of 2 or 3.]

[0013] <Polycarbonate-polyorganosiloxane copolymer> The polycarbonate-polyorganosiloxane copolymer of the present invention contains a polycarbonate block (A-1) consisting of repeating units represented by the above general formula (I) and a polyorganosiloxane block (A-2) containing repeating units represented by the above general formula (II).

[0014] The polycarbonate block (A-1) represented by the general formula (I) will be described in detail. 1 and R 2 The halogen atoms each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 1 and R 2 Examples of the alkyl groups each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups (the term "various" refers to both linear and branched butyl groups, and the same applies below), various pentyl groups, and various hexyl groups. 1 and R 2 The alkoxy groups each independently represent include those in which the alkyl moiety is the above-mentioned alkyl group.

[0015] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and an alkylene group having 5 to 10 carbon atoms is preferable. Examples of the arylene group represented by X include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group, and an alkylidene group having 5 to 10 carbon atoms is preferable, and an alkylidene group having 5 to 8 carbon atoms is more preferable. The aryl moiety of the aryl alkylene group represented by X includes aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. The aryl moiety of the aryl alkylidene group represented by X includes aryl groups having 6 to 14 ring carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group.

[0016] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, it is preferable that a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or that a and b are 0 and X is an alkylidene group, particularly an isopropylidene group.

[0017] In general formula (II), R 3 ~R 6 The halogen atoms each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 3 ~R 6 Examples of the alkyl groups each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 3 ~R 6The alkoxy group represented by each independently is exemplified by those in which the alkyl group moiety is the above-mentioned alkyl group. 3 ~R 6 Examples of the aryl group that each independently represents include a phenyl group and a naphthyl group.

[0018] R 3 ~R 6 are preferably all hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or aryl groups having 6 to 12 carbon atoms, and more preferably all methyl groups.

[0019] Z represents a divalent hydrocarbon group. The number of carbon atoms in the divalent hydrocarbon group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10. The divalent hydrocarbon group may be linear, branched or cyclic, and specific examples thereof include linear, branched or cyclic alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, cyclohexylene and octamethylene groups; arylene groups such as o-phenylene, m-phenylene, p-phenylene, methylphenylene, ethylphenylene, methoxyphenylene and naphthylene groups, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms or monovalent hydrocarbon groups having 1 to 20 carbon atoms. Some of the carbon atoms of these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with oxygen atoms, nitrogen atoms or sulfur atoms. The monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, may be linear, branched, or cyclic, and specific examples thereof include linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, and n-octyl groups; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl, phenylethyl, and phenylpropyl groups, and groups in which some or all of the hydrogen atoms of these groups have been substituted with halogen atoms or the like. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. When a part of the carbon atoms of a divalent hydrocarbon group or a monovalent hydrocarbon group is substituted with an oxygen atom, a nitrogen atom, or a sulfur atom, for example, -CH 2 - is replaced by -O-, -NH- or -S-.

[0020] k represents an integer of 2 or 3, with 3 being preferred.

[0021] Among these, Z is preferably a phenylene group which may be substituted with Q and which is represented by the following general formula (II-a). [ka] [In the formula, w is an integer of 0 to 4, and the wavy line indicates the bonding site.]

[0022] Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, some of the carbon atoms of which may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the monovalent hydrocarbon group in which some of the carbon atoms are substituted with an oxygen atom include alkoxy groups having 1 to 5 carbon atoms, such as methoxy, ethoxy, isopropoxy, n-butoxy and tert-butoxy groups. Q is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably a methyl group or a methoxy group. w is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0023] More specifically, Z in the above formula (II) is preferably one represented by the following formula: [ka] [In the formula, the wavy line indicates a bonding site. d, e and g each independently represent an integer of 0 to 50, preferably 0 to 10.] Among these, a group represented by formula (Z-1), a group represented by formula (Z-2), a group represented by formula (Z-8) (wherein d=6), or a group represented by formula (Z-9) (wherein e=1, g=0) is more preferred.

[0024] The polycarbonate-polyorganosiloxane copolymer of the present invention will now be described in more detail from another aspect. The polycarbonate-polyorganosiloxane copolymer of the present invention can be obtained by continuously supplying an organohydrogensiloxane represented by the following general formula (2), a compound represented by the following general formula (3), and a platinum catalyst to a reactor, and allowing the mixture to pass through the reactor while undergoing a hydrosilylation reaction to obtain a carbinol-modified polyorganosiloxane, which is then copolymerized with a dihydric phenol and a carbonate precursor, or by copolymerizing the carbinol-modified polyorganosiloxane with an oligomer having a repeating unit represented by the following general formula (I). The polycarbonate-polyorganosiloxane copolymer of the present invention may be obtained by purifying the carbinol-modified polyorganosiloxane by a known method as necessary, and then copolymerizing the purified carbinol-modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or by copolymerizing the purified carbinol-modified polyorganosiloxane with an oligomer having a repeating unit represented by the following general formula (I). Purification will be described later. [ka] [In the formula, R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different, and f is an integer of 0 to 500. [ka] [In the formula, R 22represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.] [ka] [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O- or -CO-; and a and b each independently represent an integer of 0 to 4.

[0025] R 3 ~R 6 The preferred examples of are as described above, and the combinations of the preferred ones are also preferred. f is an integer of 0 or more and 500 or less, more preferably 0 or more and 300 or less, and further preferably 30 or more and 200 or less. In another preferred embodiment, f is an integer of 8 to 298, more preferably 28 or more, even more preferably 33 or more, still more preferably 38 or more, more preferably 198 or less, even more preferably 148 or less, still more preferably 98 or less, and particularly preferably 93 or less. When f is 500 or less, the molecular weight of the resulting carbinol-modified polyorganosiloxane falls within a preferred range from the viewpoint of the transparency and mechanical properties of the copolymer.

[0026] R in Equation (3) 22 represents a vinyl group or an allyl group, and an allyl group is more preferable. Examples of Z are as described above, and the preferred examples and preferred combinations are also as described above.

[0027] As the compound represented by formula (3), a compound represented by the following general formula (33) is more preferable. [ka] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.]

[0028] The platinum catalyst is a catalyst for promoting hydrosilylation, and specific examples thereof include known ones such as platinum black, platinic chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohols, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. The platinum catalyst can be used in an amount of 0.005 mass ppm or more and less than 1.0 mass ppm in terms of platinum metal relative to the total of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst. If the amount of platinum catalyst is 0.005 mass ppm or more, the hydrosilylation reaction proceeds sufficiently. If the amount of platinum catalyst is less than 1.0 mass ppm, side reactions can be suppressed at the reaction sites of the organosiloxane terminals. The amount of the platinum catalyst is more preferably 0.005 ppm by mass or more and 0.5 ppm by mass or less, even more preferably 0.005 ppm by mass or more and 0.2 ppm by mass or less, and still more preferably 0.01 ppm by mass or more and 0.10 ppm by mass or less.

[0029] The carbinol-modified polyorganosiloxane can be produced by the following process: (i): A step of continuously supplying an organohydrogensiloxane represented by the above general formula (2), a compound represented by the above general formula (3), and a platinum catalyst to a reactor; (ii): A step of carrying out a hydrosilylation reaction while passing the above (2) and (3) and a platinum catalyst through the reactor; and (iii): Removal of reaction product It can be prepared by:

[0030] Process (i) In the above step (i), the above components (2), (3) and the platinum catalyst may be continuously supplied to the reactor through respective supply pipes, or a part or whole of the above components (2), (3) and the platinum catalyst may be premixed in a tank equipped with a stirrer or the like and then continuously supplied to the reactor. The reactor is preferably a tubular reactor. There are no particular limitations on the type of tubular reactor, and any known flow reactor capable of carrying out a reaction while passing (2) and (3) and a platinum catalyst therethrough may be appropriately selected for use.

[0031] In the above step (i), the temperature of the (2), (3) and the platinum catalyst supplied is not particularly limited. In order to smoothly proceed with the reaction in step (ii), the temperature is preferably 0°C or higher and 150°C or lower, more preferably 10°C or higher and 100°C or lower, and even more preferably 20°C or higher and 80°C or lower. In step (i), a solvent may be added in addition to (2), (3) and the platinum catalyst. Specific examples of the solvent include alkanes such as pentane, hexane, octane, decane, isododecane, cyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; ethers such as diethyl ether, ethyl propyl ether, glyme, and diglyme; and alcohols such as ethanol, 1-propanol, and 2-propanol.

[0032] Process (ii) Step (ii) is a step of causing a hydrosilylation reaction between components (2) and (3) while passing components (2), (3) and a platinum catalyst through a reactor. The temperature inside the reactor in this step is not particularly limited, but from the viewpoint of improving the reaction efficiency and suppressing side reactions, it is preferably from 20°C to 180°C, more preferably from 40°C to 150°C, and even more preferably from 50°C to 120°C.

[0033] The total time for steps (i) and (ii) is not particularly limited, but from the viewpoint of production efficiency, it is preferably from 1 minute to 60 minutes, more preferably from 3 minutes to 45 minutes, and even more preferably from 5 minutes to 30 minutes.

[0034] Process (iii) The step (iii) is a step of taking out the reaction product obtained in the above step (ii). The withdrawal rate depends on the supply rate in step (i) and is not particularly limited, but from the viewpoint of efficient production, it is preferably 100 kg / h or more, more preferably 200 kg / h or more, and even more preferably 300 kg / h or more. The reaction product thus extracted can be used as it is, but may be purified by a known method as necessary before use. For example, the method includes a step (iv) of removing the compound represented by the above general formula (3). As a specific example of the step (iv), for example, a thin film evaporator or the like is used to remove the excess compound represented by the above general formula (3) under heating, for example, at 160°C. By using the above-mentioned carbinol-modified polyorganosiloxane, the platinum content finally contained in the PC-POS copolymer can be adjusted to the above-mentioned value.

[0035] As a preferred embodiment of the carbinol-modified polyorganosiloxane, there is provided a carbinol-modified polyorganosiloxane represented by the following general formula (222): a Among these, carbinol-modified polyorganosiloxanes having a ratio of [the number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and groups represented by formula (vi)] of less than 0.01 are preferred. [ka] {where, R3 ~R 6 , f is as described above. R a are each independently a group represented by the following general formula (v) or (vi): [ka] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. k is 2 or 3.] [ka] [In the formula, Z has the same meaning as in formula (v) above. 33 is a vinyl group, an allyl group, or a -(CH 2 ) k -SiR 5 R 6 represents an end group having O-, and k is 2 or 3. [ka] [In the formula, R 3 ~R 6 , f is as defined above.]}

[0036] When the ratio of the number of groups represented by formula (vi) / the total number of groups represented by formula (v) and formula (vi) is less than 0.01, the amount of side reaction products can be suppressed, and the decrease in transparency and color tone caused by molding the copolymer obtained using the carbinol-modified polyorganosiloxane at high temperatures can be suppressed, and the appearance of the molded article using the copolymer can be favorably maintained. The ratio of [the number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and groups represented by formula (vi)] is more preferably 0.008 or less, even more preferably 0.006 or less, and even more preferably 0.005 or less. The carbinol-modified polyorganosiloxane having the ratio of [the number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and formula (vi)] can be obtained, for example, by continuously supplying an organohydrogensiloxane represented by the above general formula (2), a compound represented by the above general formula (3), and a platinum catalyst to a reactor and carrying out a hydrosilylation reaction while passing through the reactor. The above ratios in this specification are 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 The integral value derived from Si in the -O-Si(R 5 )(R 6 )-OZ-structure and the integral value derived from Si.

[0037] As another preferred embodiment of the carbinol-modified polyorganosiloxane, there is provided a carbinol-modified polyorganosiloxane represented by the following general formula (223), in which R b Among these, there can be mentioned a polycarbonate-polyorganosiloxane copolymer obtained by using a carbinol-modified polyorganosiloxane having a ratio of [number of hydroxy groups] / [total number of hydroxy groups and groups represented by formula (v)] of less than 0.01. [ka] {where, R 3 ~R 6 , f is as described above. R b are each independently a hydroxy group or a group represented by the following general formula (v): [ka] [In the formula, Z is as defined above, and k is 2 or 3.]

[0038] When the ratio of the number of hydroxyl groups to the total number of hydroxyl groups and groups represented by formula (v) is less than 0.01, the amount of side reaction products can be suppressed, and the deterioration of transparency and color tone caused by molding at high temperatures of the copolymer obtained using the carbinol-modified polyorganosiloxane can be suppressed, and the appearance of the molded article using the copolymer can be maintained in a good condition. The ratio of [the number of hydroxy groups] / [the total number of hydroxy groups and the group represented by formula (v)] is more preferably 0.008 or less, further preferably 0.006 or less, and even more preferably 0.005 or less. The carbinol-modified polyorganosiloxane having the above ratio of [number of hydroxyl groups] / [total number of hydroxyl groups and groups represented by formula (v)] can be obtained, for example, by continuously supplying an organohydrogensiloxane represented by the above general formula (2), a compound represented by the above general formula (3), and a platinum catalyst to a reactor and causing a hydrosilylation reaction while passing through the reactor. The above ratios in this specification are 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 -Si(R 5 )(R 6 The value is calculated from the integral value derived from Si in the —OH structure.

[0039] The polycarbonate-polyorganosiloxane copolymer can be produced by adding polyorganosiloxane to a reaction system in which a dihydric phenol and a carbonate precursor are polymerized, and by an interfacial polymerization method (phosgene method), an ester exchange method (melt method), or the like. In the case of the interfacial polymerization method, phosgene, triphosgene, or the like can be used as the carbonate precursor, and in the case of the ester exchange method, diphenyl carbonate can be used as the carbonate precursor. Alternatively, as described later, it is also preferable to adopt a method in which a dihydric phenol is reacted with phosgene in advance to prepare a bisphenol monomer or a bisphenol polycarbonate oligomer having a chloroformate structure at both ends, and then the bisphenol monomer or the bisphenol polycarbonate oligomer is reacted with a polyorganosiloxane. In particular, when the interfacial polymerization method is employed, the process of separating the organic phase containing the PC-POS copolymer from the aqueous phase containing unreacted materials, catalyst residues, etc. is easy, and the organic phase containing the PC-POS copolymer and the aqueous phase are easily separated in each washing process such as alkali washing, acid washing, and pure water washing. Therefore, the PC-POS copolymer can be obtained efficiently. As a method for producing the PC-POS copolymer, for example, the method described in JP 2014-80462 A can be referred to.

[0040] Specifically, the polycarbonate oligomer and carbinol-modified polyorganosiloxane, which are previously prepared as described below, are dissolved in a non-water-soluble organic solvent (such as methylene chloride), an aqueous alkaline compound solution (such as an aqueous sodium hydroxide solution) of a dihydric phenol compound (such as bisphenol A) is added, and an interfacial polycondensation reaction is carried out in the presence of a terminal terminator (monohydric phenol such as p-tert-butylphenol) using a tertiary amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) as a polymerization catalyst. The PC-POS copolymer can also be produced by copolymerizing a carbinol-modified polyorganosiloxane, a dihydric phenol, and phosgene, a carbonate ester, or a chloroformate.

[0041] Polycarbonate oligomers can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, chloroform, etc. When producing a polycarbonate oligomer by the transesterification method, it can also be produced by reacting a dihydric phenol with a carbonate precursor such as diphenyl carbonate.

[0042] As the dihydric phenol, it is preferable to use a dihydric phenol represented by the following general formula (viii). [ka] In the formula, R 1 , R 2 , a, b and X are as defined above.

[0043] Examples of the dihydric phenol represented by the general formula (viii) include bis(hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)oxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)ketone. These dihydric phenols may be used alone or in combination of two or more. Among these, bis(hydroxyphenyl)alkane dihydric phenols are preferred, and bisphenol A is more preferred. When bisphenol A is used as the dihydric phenol, the resulting copolymer is a PC-POS copolymer in which X is an isopropylidene group and a=b=0 in the above general formula (i).

[0044] Examples of dihydric phenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, and dihydroxydiaryladamantanes. These dihydric phenols may be used alone or in combination of two or more.

[0045] Examples of bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane.

[0046] Examples of bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, and 1,1-bis(4-hydroxyphenyl)cyclododecane. Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether.

[0047] Examples of dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide. Examples of dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide. Examples of dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone.

[0048] Examples of dihydroxydiphenyls include 4,4'-dihydroxydiphenyl, etc. Examples of dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, etc. Examples of dihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, etc.

[0049] Examples of dihydric phenols other than those mentioned above include 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, and 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.

[0050] In order to adjust the molecular weight of the resulting PC-POS copolymer, a terminal terminator (molecular weight regulator) can be used. Examples of the terminal terminator include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0051] In one embodiment of the present invention, the polycarbonate-polyorganosiloxane copolymer can be obtained by reacting the carbinol-modified polyorganosiloxane represented by the general formula (222) with a dihydric phenol and a carbonate precursor, or with a polycarbonate oligomer. Therefore, it can have the polyorganosiloxane unit represented by the following general formula (222-i). [ka] {where, R 3 ~R 6 , f is as described above. R a-i are each independently a group represented by the following general formula (vi): [ka] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. The oxygen atom in formula (vi) is bonded to a polycarbonate unit. k is 2 or 3.]}

[0052] In addition, in the polyorganosiloxane unit represented by the general formula (222-i), R represented by the general formula (vi) a-i The (CH 2 )k is directly bonded to a silicon atom (Si).

[0053] Incidentally, the carbinol-modified polyorganosiloxane represented by the general formula (222) has R a Among them, the group represented by formula (vi) may be included, and it is preferable that the ratio of [the total number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and formula (vi)] is less than 0.01, as described above. That is, the polycarbonate-polyorganosiloxane copolymer in one embodiment of the present invention may contain, in addition to the polycarbonate-polyorganosiloxane copolymer having the polyorganosiloxane unit represented by the above general formula (222-i), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (b) in which a compound represented by formula (vi) is incorporated at the end, and a compound represented by the following general formula (c) that remains without reacting with the carbonate precursor, dihydric phenol, polycarbonate oligomer, etc. [ka] [In the formula, R 3 ~R 6 , Z, R 33 , f, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , Z, R 33 , f is as defined above.]

[0054] The polycarbonate-polyorganosiloxane polymer represented by the above formula (b) and the compound represented by the above formula (c) are contained as so-called "impurities" in the polycarbonate-polyorganosiloxane copolymer of this embodiment. The ratio of these is determined by the formula (b) and formula (c) {-OZR 33The total number of groups represented by formula (vi) and the groups represented by formula (b) and formula (c) 33 When the ratio of the number of groups represented by the formula {total number of groups represented by the formula {R1, R2, R3, R4}} to the number of groups represented by the formula {R2, R3, R4} is less than 0.01. When the ratio is less than 0.01, the deterioration in transparency and color tone due to molding at high temperatures of the PC-POS copolymer is suppressed, the Δ haze value of the PC-POS copolymer can be set to the above-mentioned value, and the appearance of a molded article using the copolymer can be maintained favorably. In the above formula (b) and formula (c), {-OZR 33 The total number of groups represented by formula (vi) and the groups represented by formula (b) and formula (c) 33 The ratio of the number of groups represented by the formula (I) to the total number of groups represented by the formula (I) is more preferably 0.008 or less, further preferably 0.006 or less, and further preferably 0.005 or less. In the above formula (b) and formula (c), {-OZR 33 The total number of groups represented by formula (vi) and the groups represented by formula (b) and formula (c) 33 A PC-POS copolymer having a ratio of [total number of groups represented by formula (vi)] / [total number of groups represented by formula (v) and groups represented by formula (vi)] of less than 0.01 can be obtained, for example, by using a carbinol-modified polyorganosiloxane having a ratio of [total number of groups represented by formula (v)] / [total number of groups represented by formula (vi)] of less than 0.01. The above ratios in this specification are 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 The integral value derived from Si in the - structure and the -O-Si(R 5 )(R 6 )-OZ-structure and the integral value derived from Si.

[0055] In another embodiment of the present invention, the polycarbonate-polyorganosiloxane copolymer can be obtained by reacting the carbinol-modified polyorganosiloxane represented by the general formula (223) with a dihydric phenol and a carbonate precursor, or with a polycarbonate oligomer. Therefore, it can have the polyorganosiloxane unit represented by the following general formula (223-i). [ka] {where, R 3 ~R 6 , f is as described above. R b-i are each independently a group represented by the following general formula (vi): [ka] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom or a sulfur atom. The oxygen atom in formula (vi) is bonded to a polycarbonate unit. k is 2 or 3.]}

[0056] In addition, in the polyorganosiloxane unit represented by the general formula (223-i), R represented by the general formula (vi) b-i The (CH 2 ) k is directly bonded to a silicon atom (Si).

[0057] The carbinol-modified polyorganosiloxane represented by the general formula (223) includes R bAs mentioned above, the hydroxyl group may also be included as the hydroxyl group. That is, the polycarbonate-polyorganosiloxane copolymer in one embodiment of the present invention may contain, in addition to the polycarbonate-polyorganosiloxane copolymer having the polyorganosiloxane unit represented by the above general formula (223-i) and the impurities represented by the above general formulas (b) and (c), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (d) in which a hydroxyl group is incorporated at the end, and a compound represented by the following general formula (e) that remains without reacting with the carbonate precursor, dihydric phenol, polycarbonate oligomer, etc. [ka] [In the formula, R 3 ~R 6 , f, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , f is as defined above.]

[0058] The polycarbonate-polyorganosiloxane copolymer represented by the above formula (d) and the compound represented by the above formula (e) are also contained in the polycarbonate-polyorganosiloxane copolymer of this embodiment as so-called "impurities". The ratio of these is preferably less than 0.01, i.e., the ratio of [total number of hydroxy groups in formula (d) and formula (e)] / [total number of groups represented by formula (vi) and hydroxy groups in formula (d) and formula (e)]. If it is less than 0.01, the PC-POS copolymer is prevented from losing transparency and color tone due to molding at high temperatures, and the Δ haze value of the PC-POS copolymer can be set to the above-mentioned value, and the appearance of the molded product using the copolymer can be favorably maintained. The ratio of the total number of hydroxy groups in formula (d) and formula (e) to the total number of the group represented by formula (vi) and the hydroxy groups in formula (d) and formula (e) is more preferably 0.008 or less, even more preferably 0.006 or less, and even more preferably 0.005 or less. The PC-POS copolymer having the above ratio of [total number of hydroxy groups in formula (d) and formula (e)] / [total number of groups represented by formula (vi) and hydroxy groups in formula (d) and formula (e)] is, for example, represented by the above general formula (223), b The carbinol-modified polyorganosiloxane can be obtained by using a carbinol-modified polyorganosiloxane having a ratio of [number of hydroxy groups] / [total number of hydroxy groups and groups represented by formula (v)] of less than 0.01. The above ratios in this specification are 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 The integral value derived from Si in the - structure and the -O-Si(R 5 )(R 6 The ratio of the above [total number of hydroxy groups in formula (d) and formula (e)] / [total number of groups represented by formula (vi) and hydroxy groups in formula (d) and formula (e)] is calculated from the integral value derived from Si in the -O-Si(R 5 )(R 6 )-CH 2 This can be expressed as the ratio of the number of groups represented by - to the total number of hydroxy groups in formula (d) and formula (e).

[0059] In another embodiment of the present invention, the polycarbonate-polyorganosiloxane copolymer is a polycarbonate-polyorganosiloxane copolymer including a polycarbonate block (A-1) composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) including a repeating unit represented by the following general formula (II): the difference Δhaze between the haze value (haze A) after the polycarbonate-polyorganosiloxane copolymer is allowed to reside for 3 minutes at 300° C. or 340° C. and the haze value (haze B) after the polycarbonate-polyorganosiloxane copolymer is allowed to reside for 20 minutes is less than 0.4; The composition contains a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), and has a ratio of [total number of hydroxy groups in formulas (f) and (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formulas (f) and (g)] of less than 0.01. [ka] [In the formula, R 1 ~R 6 , X, Z, a, b, n, and k are as defined above.] [ka] [In the formula, Z is as defined above. k is 2 or 3.] [ka] [In the formula, R 3 ~R 6 , n, and k are as defined above. In the formula, (PC) represents a bond to the polycarbonate block.] [ka] [In the formula, R 3 ~R 6 , n is as defined above.]

[0060] The polycarbonate-polyorganosiloxane copolymer represented by the above formula (f) and the compound represented by the above formula (g) are contained in the polycarbonate-polyorganosiloxane copolymer in this embodiment as so-called "impurities". The ratio of these is preferably less than 0.01, i.e., the ratio of [total number of hydroxyl groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxyl groups in formula (f) and formula (g)]. If it is less than 0.01, the PC-POS copolymer is prevented from losing transparency and color tone due to molding at high temperatures, and the Δ haze value of the PC-POS copolymer can be set to the above-mentioned value, and the appearance of the molded product using the copolymer can be favorably maintained. The group represented by formula (v-ii) is included in the polycarbonate-polyorganosiloxane copolymer containing the polycarbonate block (A-1) and the polyorganosiloxane block (A-2) and the polycarbonate-polyorganosiloxane copolymer represented by the above formula (f). The ratio of the total number of hydroxy groups in formula (f) and formula (g) to the total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g) is more preferably 0.008 or less, even more preferably 0.006 or less, and even more preferably 0.005 or less. The PC-POS copolymer having the above ratio of [total number of hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] is, for example, represented by the above general formula (223), b The carbinol-modified polyorganosiloxane can be obtained by using a carbinol-modified polyorganosiloxane having a ratio of [number of hydroxy groups] / [total number of hydroxy groups and groups represented by formula (v)] of less than 0.01. The above ratios in this specification are 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 The integral value derived from Si in the - structure and the -O-Si(R 5 )(R6 The ratio of the above [total number of hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] is calculated from the integral value derived from Si in the -O-Si(R 5 )(R 6 )-CH 2 - the total number of hydroxy groups in formula (f) and formula (g).

[0061] After the above-mentioned interfacial polycondensation reaction, the mixture is left to stand for an appropriate period to separate into an aqueous phase and an organic solvent phase [separation step], the organic solvent phase is washed (preferably with a basic aqueous solution, an acidic aqueous solution, and water, in that order) [washing step], and the obtained organic phase is concentrated [concentration step] and dried [drying step], thereby obtaining a PC-POS copolymer.

[0062] The PC-POS copolymer of the present invention is characterized in that the difference Δhaze between the haze value (haze A) after the copolymer or a composition thereof is retained at 300°C or 340°C for 3 minutes and the haze value (haze B) after the copolymer or a composition thereof is retained for 20 minutes is less than 0.4. When no haze difference is observed at a retention temperature of 300°C, a retention temperature of 340°C is used. In general, when the average chain length of the polyorganosiloxane is long, the haze difference may not be apparent at 300°C, and in that case, the haze difference is measured at a retention temperature of 340°C, but is not limited to this description. This characteristic indicates that the PC-POS copolymer of the present invention is excellent in transparency and thermal stability.

[0063] Without being bound by theory, after the above-mentioned retention test, the siloxane portion generally decomposes and becomes less compatible with the polycarbonate block portion, so that the product tends to become cloudy and have a large haze value. The present inventors have surprisingly found that a PC-POS copolymer having a polycarbonate block having a specific structure and a polyorganosiloxane block having a specific structure has excellent transparency and thermal stability as described above. The Δ haze value is preferably 0.3 or less, and more preferably 0.2 or less.

[0064] The platinum content of the polycarbonate-polyorganosiloxane copolymer of the present invention is, specifically, 0.05 mass ppb or more and less than 0.5 mass ppm. If the platinum content of the PC-POS copolymer of the present invention is within the above range, coloration of the PC-POS copolymer caused by platinum can be suppressed, which is preferable. The upper limit of the platinum content in the PC-POS copolymer of the present invention is more preferably 0.4 mass ppm or less, even more preferably 0.3 mass ppm or less, even more preferably 0.1 mass ppm or less, even more preferably 50 mass ppb or less, even more preferably 10 mass ppb or less, and particularly preferably 1.0 mass ppb or less.

[0065] The platinum content in the polyorganosiloxane in the PC-POS copolymer of the present invention is measured using an ICP emission spectrometer. Specifically, the organic matter in the PC-POS copolymer is subjected to a sulfate ashing treatment, and the residue is dissolved in hydrofluoric acid and aqua regia. The platinum content in the copolymer can be measured using the solution in an ICP emission spectrometer (e.g., Hitachi High-Tech Science Corporation, product name: "SPS5100") under the measurement conditions of the calibration curve method.

[0066] The average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer is preferably 10 or more and 300 or less. The average chain length is calculated by nuclear magnetic resonance (NMR) measurement. If the average chain length of the polycarbonate-polyorganosiloxane copolymer is 10 or more and 300 or less, the finally obtained polycarbonate resin composition is superior in impact resistance, etc. Although the reason is not clear, it has been found that the polycarbonate resin composition of the present invention has extremely excellent impact resistance.

[0067] The average chain length n of the polyorganosiloxane block (A-2) is more preferably 30 or more, even more preferably 35 or more, even more preferably 40 or more, and more preferably 200 or less, even more preferably 150 or less, even more preferably 100 or less, and particularly preferably 95 or less.

[0068] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer is preferably 1% by mass or more and 50% by mass or less. If the content of polyorganosiloxane in the PC-POS copolymer is within the above range, better impact resistance can be obtained. In addition, it is possible to avoid a decrease in handleability due to a high content of polyorganosiloxane. If the content of polyorganosiloxane is equal to or less than the above upper limit, the resulting copolymer can be sufficiently pulverized, and powder aggregation and the like can be avoided, which is preferable.

[0069] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer is more preferably 2% by mass or more, even more preferably 3% by mass or more, particularly preferably 4% by mass or more, and is preferably 45% by mass or less, more preferably 30% by mass or less, even more preferably 15% by mass or less, particularly preferably 7% by mass or less.

[0070] The viscosity average molecular weight (Mv) of the PC-POS copolymer can be appropriately adjusted by using a molecular weight regulator (terminal terminator) or the like to obtain a target molecular weight depending on the application or product to be used. The viscosity average molecular weight of the PC-POS copolymer is preferably 9,000 or more and 50,000 or less. If the viscosity average molecular weight is 9,000 or more, a molded product with higher strength can be obtained. If the viscosity average molecular weight is 50,000 or less, injection molding or extrusion molding can be more easily performed at a temperature that does not cause thermal degradation.

[0071] The viscosity average molecular weight of the PC-POS copolymer is more preferably 12,000 or more, even more preferably 14,000 or more, particularly preferably 16,000 or more, and more preferably 30,000 or less, even more preferably 23,000 or less, particularly preferably 22,000 or less, and most preferably 20,000 or less. The viscosity average molecular weight (Mv) is a value calculated from the intrinsic viscosity [η] of a methylene chloride solution at 20° C. using the Schnell formula below.

[0072]

number

[0073] <Polycarbonate resin composition> According to one embodiment of the present invention, there can be provided a polycarbonate resin composition containing the above PC-POS copolymer. The polycarbonate resin composition may contain other PC-POS copolymers and other additives within the range that does not impair the effects of the present invention.

[0074] Other PC-POS copolymers include, for example, those having the structures shown below. [ka]

[0075] The PC-POS copolymer has a structure other than that of a PC-POS copolymer and is not particularly limited. 111 , R 112 , X', a1 and b1 are each R as detailed in formula (I). 1 , R 2 , X, a and b are the same as those in the formula (i-II), and the preferred values ​​and combinations of the preferred values ​​are also the same. 333 , R 444 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0076] In the above general formula (i-II), R 333 or R 444 The halogen atoms each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 333 or R 444 Examples of the alkyl groups each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 333 or R 444 The alkoxy group represented by each independently is exemplified by those in which the alkyl group moiety is the above-mentioned alkyl group. 333 or R 444 Examples of the aryl group that each independently represents include a phenyl group and a naphthyl group. R 333 and R 444 are preferably all hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or aryl groups having 6 to 12 carbon atoms, and more preferably all methyl groups.

[0077] The polyorganosiloxane block (A-2) containing the repeating unit represented by general formula (i-II) preferably has units represented by the following general formulas (II-i) to (II-iii). [ka] [In the formula, R 333 ~R 666 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 333 ~R 666 may be the same or different. Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R9 -O- or -R 7 OR 10 The R represents —O—, and a plurality of Y's may be the same or different. 7 R represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 R represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 R represents a diarylene group. 10 represents a linear, branched or cyclic alkylene group, or a diarylene group; β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide; m represents the average chain length of the polyorganosiloxane, m-1, and p and q are each an integer of 1 or more indicating the number of repetitions of the polyorganosiloxane unit, and the sum of p and q is m-2.]

[0078] R 333 ~R 666 The halogen atoms each independently represent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 333 ~R 666 Examples of the alkyl groups each independently represent include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 333 ~R 666 The alkoxy group represented by each independently is exemplified by those in which the alkyl group moiety is the above-mentioned alkyl group. 333 ~R 666 Examples of the aryl group that each independently represents include a phenyl group and a naphthyl group. R 333 ~R 666 are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R in general formula (II-i), (II-ii) and / or (II-iii) 3 ~R 6 are preferably all methyl groups.

[0079] Y indicates -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R 9 -O- or -R 7 OR 10 R in -O- 7 The linear or branched alkylene group represented by the formula (I) is an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and the cyclic alkylene group is a cycloalkylene group having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

[0080] R 7 The aryl-substituted alkylene group represented by may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring, and its specific structure can be, for example, the structure of the following general formula (i) or (ii). When the aryl-substituted alkylene group is present, the alkylene group is bonded to Si. [ka] (In the formula, c represents a positive integer, and is usually an integer of 1 to 6.)

[0081] R 7 , R 9 and R 10 The diarylene group represented by the formula (I) is a group in which two arylene groups are linked directly or via a divalent organic group, and specifically, -Ar 1 -W-Ar 2 - is a group having a structure represented by Ar 1 and Ar 2 represents an arylene group, and W represents a single bond or a divalent organic group. The divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group, or a trimethylene group. R 7 , Ar 1 and Ar 2Examples of the arylene group represented by the formula (1) include arylene groups having 6 to 14 ring carbon atoms, such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may have any substituent, such as an alkoxy group or an alkyl group. R 8 The alkyl group represented by the formula (I) is a straight or branched group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. The alkenyl group is a straight or branched group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. The aryl group is a phenyl group, a naphthyl group, etc. The aralkyl group is a phenylmethyl group, a phenylethyl group, etc. R 10 The linear, branched or cyclic alkylene group represented by R 7 is the same as:

[0082] Y is preferably -R 7 O- and R 7 is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, and more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol. With respect to p and q in formula (II-ii), it is preferable that p=q. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide, and examples thereof include divalent groups represented by the following general formulas (iii) to (vii). [ka] In the other PC-POS copolymers, the repeat number of the polyorganosiloxane block (A'-2) is preferably 10 or more and 500 or less, more preferably 20 or more and 300 or less, and further preferably 30 to 150. The repeating number is calculated by nuclear magnetic resonance (NMR) measurement. By setting the repeating number of the polyorganosiloxane block (A-2) within the above range, it is possible to achieve both excellent transparency and flexibility, and to suppress peeling after production of a molded product.

[0083] The content of the polyorganosiloxane block (A'-2) in the other PC-POS copolymer is preferably 1 mass% or more and 50 mass% or less, more preferably 2 mass% or more and 45 mass% or less, even more preferably 3 mass% or more and 30 mass% or less, and even more preferably 3 mass% or more and less than 20 mass%.

[0084] The viscosity average molecular weight (Mv) of the other PC-POS copolymers can be appropriately adjusted to the desired molecular weight by using a molecular weight regulator (terminal terminator) or the like depending on the application or product to be used. The viscosity average molecular weight of the other PC-POS copolymers is preferably 9,000 or more and 50,000 or less. If the viscosity average molecular weight is 9,000 or more, a molded product with higher strength can be obtained. If the viscosity average molecular weight is 50,000 or less, injection molding or extrusion molding can be more easily performed at a temperature that does not cause thermal degradation.

[0085] The viscosity average molecular weight of the other PC-POS copolymers is more preferably 12,000 or more, even more preferably 14,000 or more, particularly preferably 16,000 or more, and more preferably 30,000 or less, even more preferably 23,000 or less, particularly preferably 22,000 or less, and most preferably 20,000 or less. The viscosity average molecular weight (Mv) is a value calculated from the intrinsic viscosity [η] of a methylene chloride solution at 20° C. using the Schnell formula below.

[0086]

number

[0087] The above other polycarbonate-polyorganosiloxane copolymers can be produced by known production methods such as interfacial polymerization (phosgene method), pyridine method, and transesterification method. In particular, when the interfacial polymerization method is adopted, the separation process of the organic phase containing the PC-POS copolymer and the aqueous phase containing unreacted materials and catalyst residues is easy, and the organic phase containing the PC-POS copolymer and the aqueous phase are easily separated in each washing process such as alkali washing, acid washing, and pure water washing. Therefore, the PC-POS copolymer can be obtained efficiently. As a method for producing the PC-POS copolymer, for example, the method described in JP-A-2014-80462 can be referred to.

[0088] Examples of other additives include antioxidants, alicyclic epoxy compounds, ultraviolet absorbers, release agents, reinforcing materials, fillers, elastomers for improving impact resistance, dyes, pigments, antistatic agents, resins other than polycarbonate, and the like.

[0089] The blending and kneading can be carried out by premixing using commonly used equipment such as a ribbon blender or drum tumbler, followed by using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder, a co-kneader, etc. The heating temperature during kneading is usually appropriately selected within the range of 240° C. to 320° C. For this melt kneading, it is preferable to use an extruder, particularly a vent-type extruder.

[0090] [Molded products] Using the above-mentioned melt-kneaded polycarbonate resin composition of the present invention or the obtained pellets as a raw material, various molded articles can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, 3D printers, etc. In particular, the pellets obtained by melt kneading can be suitably used for producing injection molded articles by injection molding and injection compression molding.

[0091] The PC-POS copolymer of the present invention and molded articles made of a polycarbonate resin composition containing the copolymer can be suitably used as exterior and internal parts of electric and electronic equipment parts such as televisions, radios, cameras, video cameras, audio players, DVD players, air conditioners, mobile phones, smartphones, transceivers, displays, computers, tablet terminals, portable game devices, stationary game devices, wearable electronic devices, cash registers, calculators, copiers, printers, facsimiles, communication base stations, batteries, and robots; exterior and internal parts of automobiles, railways, ships, aircraft, space industry equipment, and medical equipment; and building material parts. EXAMPLES

[0092] The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The characteristic values ​​and evaluation results in each example were determined according to the following procedures.

[0093] (1) Polydimethylsiloxane chain length and content The ratio was calculated from the integral ratio of the methyl groups of polydimethylsiloxane measured by NMR. In this specification, polydimethylsiloxane may be abbreviated as PDMS. <Quantitative method for determining the chain length of polydimethylsiloxane> 1 H-NMR measurement conditions NMR device: JEOL RESONANCE ECA-500 Probe: 50TH5AT / FG2 Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5φ Sample size: 30-40mg Solvent: deuterated chloroform Measurement temperature: room temperature Number of times accumulated: 256 In the case of allylphenol-terminated polydimethylsiloxane A: The integral value of the methyl group of the dimethylsiloxane part observed around δ-0.02 to 0.5 B: Integral value of methylene group of allylphenol observed around δ2.50~2.75 Polydimethylsiloxane chain length = (A / 6) / (B / 4) In the case of eugenol-terminated polydimethylsiloxane A: The integral value of the methyl group of the dimethylsiloxane part observed around δ-0.02 to 0.5 B: Integral value of methylene group of eugenol observed around δ2.40~2.70 Polydimethylsiloxane chain length = (A / 6) / (B / 4)

[0094] <Method for quantifying polydimethylsiloxane content> Quantitative method for determining the amount of polydimethylsiloxane copolymerized in PTBP-terminated polycarbonate copolymerized with allylphenol-terminated polydimethylsiloxane NMR device: JEOL RESONANCE ECA-500 Probe: 50TH5AT / FG2 Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of times accumulated: 256 NMR sample tube: 5φ Sample size: 30-40mg Solvent: deuterated chloroform Measurement temperature: room temperature A: Integral value of the methyl group of the BPA part observed around δ1.5-1.9 B: The integral value of the methyl group of the dimethylsiloxane part observed around δ-0.02 to 0.3 C: Integral value of the butyl group in the p-tert-butylphenyl moiety observed around δ1.2~1.4 a=A / 6 b=B / 6 c=C / 9 T=a+b+c f=a / T×100 g=b / T×100 h=c / T×100 TW=f×254+g×74.1+h×149 PDMS (wt%) = g × 74.1 / TW × 100

[0095] (2) Viscosity average molecular weight The viscosity average molecular weight (Mv) was calculated by the following formula (Schnell formula) using the intrinsic viscosity [η] obtained by measuring the viscosity of a methylene chloride solution at 20° C. using an Ubbelohde viscometer.

number

[0096] (3) Ratio of [number of groups represented by formula (vi)] / [total number of groups represented by formula (v) and groups represented by formula (vi)] 29 In the Si-NMR spectrum, -O-Si(R 5 )(R 6 )-CH 2 The integral value derived from Si in the -O-Si(R 5 )(R 6 The value is calculated from the integral value derived from Si in the SiO2-OZ-structure. Hereinafter, this is also referred to as the "terminal impurity ratio."

[0097] (4) Ratio of [hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] In a 100 mL Erlenmeyer flask, 3 g of the PC-POS copolymer described in the following Production Example was dissolved in 20 mL of dichloromethane to obtain a solution, to which 30 mL of a 1 wt% sodium hydroxide / methanol solution was added and stirred at room temperature for 2 hours. After stirring, the mixture in the Erlenmeyer flask was naturally filtered using a pleated filter paper (150 mm, No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.). The solid remaining on the filter paper and the Erlenmeyer flask were washed with 10 mL of dichloromethane, and the resulting washing solution was filtered using the pleated filter paper. This process was repeated twice. The entire amount of the liquid that had passed through the filter paper, 40 mL of dichloromethane, and 50 mL of pure water were added to the separatory funnel, and the mixture was vigorously shaken and then left to stand for 1 minute to separate the aqueous and organic phases, and the organic phase was isolated. Then, 20 mL of dichloromethane was added to the aqueous phase remaining in the separatory funnel, and the mixture was vigorously shaken and then left to stand for 1 minute to separate the aqueous and organic phases, and the organic phase was isolated. The entire organic phase that had been isolated and 35 mL of 1N aqueous sodium hydroxide solution were added to the separatory funnel, and the mixture was vigorously shaken and then left to stand for 1 minute to separate the aqueous and organic phases, and the process of isolating the organic phase was repeated twice, and then the 1N aqueous sodium hydroxide solution was replaced with 1N aqueous hydrochloric acid, and the same process was repeated twice. 5.0 g of sodium sulfate was added to the isolated organic phase and stirred, after which the sodium sulfate in the solution was removed by suction filtration. After suction filtration, the filtrate was concentrated to dryness using an evaporator (water bath temperature: 40°C), and the resulting oily product was 29 Si-NMR measurement was performed, and the ratio of [hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] was calculated. The ratio of [hydroxy groups in formulae (f) and (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formulae (f) and (g)] also corresponds to the ratio of [total number of hydroxy groups in formulae (d) and (e)] / [total number of groups represented by formula (vi) and hydroxy groups in formulae (d) and (e)]. < 29 Si-NMR measurement conditions> NMR device: JEOL RESONANCE ECA-500 Probe: FG probe, compatible with 10φ NMR sample tubes Observation kernel: 29 S Observation range: -65~35ppm Observation center: -15ppm Pulse repetition time: 18.3 seconds Pulse width: 90° Accumulation count: 5000 times NMR sample tube: 10φ Sample size: 750mg Relaxation agent: Tris(acetylacetonato)chromium(III) 20mM Solvent: deuterated chloroform Measurement temperature: room temperature A: Integrated value of allylphenol-bound Si observed at δ7.5-9.0 ppm B: Integral value of silanols observed at δ-9.6 to -9.9 ppm [hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)]=B / (A+B)

[0098] Preparation Example 1 <Production of Carbinol-Modified Polyorganosiloxane: PDMS-A> To a 150 L tubular reactor, 132 kg / h of an organohydrogenpolysiloxane represented by the average formula (2-1) below, all heated to 50°C, 14.5 kg / h of 2-allylphenol, and a platinum catalyst (a toluene solution of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex neutralized with chloroplatinic acid) were each supplied so that the platinum metal concentration relative to the total mixed liquid in the system was 0.08 ppm by mass, and the mixture was allowed to pass through the tubular reactor for 20 minutes at 80°C to react, and then continuously removed into a storage tank. Thereafter, excess 2-allylphenol was removed at 160°C using a thin-film evaporator to synthesize a carbinol-modified polyorganosiloxane represented by the following average formula (II-I). The terminal impurity ratio of the obtained carbinol-modified polyorganosiloxane was 0.0015. It should be noted that formula (2-1) and formula (II-I) are average formulas, and "36" refers to the average repeating number of dimethylsiloxane units. [ka] [ka]

[0099] Preparation Example 2 <Production of Carbinol-Modified Polyorganosiloxane: PDMS-B> To a 150 L tubular reactor, 380 kg / h of an organohydrogenpolysiloxane represented by the following average formula (2-11) heated to 50°C, 19 kg / h of 2-allylphenol, and a platinum catalyst (a toluene solution of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex neutralized with chloroplatinic acid) were each supplied so that the platinum metal concentration relative to the entire mixed liquid in the system was 0.10 ppm by mass, and the mixture was allowed to pass through the tubular reactor for 20 minutes at 80°C to react, and then continuously removed into a storage tank. Thereafter, excess 2-allylphenol was removed at 160°C using a thin-film evaporator to synthesize a carbinol-modified polyorganosiloxane represented by the following average formula (II-I'). The terminal impurity ratio of the obtained carbinol-modified polyorganosiloxane was 0.0025. Incidentally, formula (2-11) and formula (II-I') are average formulas, and "89" refers to the average number of repeating dimethylsiloxane units. [ka] [ka]

[0100] Preparation Example 3 <Production of carbinol-modified polyorganosiloxane: PDMS-C> The same operation as in the production of PDMS-B was carried out, except that the concentration of the platinum catalyst was 0.02 mass ppm in terms of platinum metal. The terminal impurity ratio of the obtained carbinol-modified polyorganosiloxane was 0.0010.

[0101] <kf-2201> KF-2201 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., lot. 801015) was produced by carrying out the carbinol modification of the organosiloxane in Preparation Example 1 through a batch reaction.

[0102] <kf-1922> KF-1922 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., lot. 704020) was produced by carrying out the carbinol modification of the organosiloxane in Preparation Example 2 through a batch reaction.

[0103] <Production of polycarbonate oligomer> Sodium dithionite was added to a 5.6% by mass aqueous solution of sodium hydroxide so that the concentration was 2000 ppm relative to the amount of bisphenol A (BPA) to be dissolved later. BPA was then dissolved in the solution so that the BPA concentration was 13.5% by mass, and an aqueous solution of sodium hydroxide for BPA was prepared. The aqueous sodium hydroxide solution of BPA was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 L / hr, methylene chloride at 15 L / hr, and phosgene at 4.0 kg / hr. The tubular reactor had a jacket, and cooling water was passed through the jacket to keep the temperature of the reaction liquid below 40°C. The reaction liquid leaving the tubular reactor was continuously introduced into a baffled tank reactor with an internal volume of 40 L and equipped with a swept-back blade, to which an aqueous sodium hydroxide solution of BPA was further added at a flow rate of 2.8 L / hr, a 25% by mass aqueous sodium hydroxide solution at 0.07 L / hr, water at 17 L / hr, and a 1% by mass aqueous triethylamine solution at 0.64 L / hr to carry out the reaction. The reaction liquid overflowing from the tank reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer thus obtained had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.

[0104] <Production Examples 1 to 8 of Polycarbonate-Polyorganosiloxane Copolymer> The values ​​(i) to (xiv) described below indicate the amounts of each component used, as shown in Table 1. A 50 L tank-type reactor equipped with a baffle plate, a paddle-type stirring blade, and a cooling jacket was charged with (i) kg of the polycarbonate oligomer solution (PCO) produced as described above, (ii) kg of methylene chloride (MC), (iv) g of allylphenol-terminated polydimethylsiloxane having an average chain length of polydimethylsiloxane n = (iii) (hereinafter, polydimethylsiloxane may be referred to as PDMS) dissolved in (v) L of methylene chloride (MC), and (vi) mL of triethylamine (TEA), and (vii) g of an 8.0 mass % aqueous sodium hydroxide solution (NaOHaq) was added thereto with stirring, and the polycarbonate oligomer and the allylphenol-terminated PDMS were reacted for 20 minutes (prepolymerization step). This polymerization solution was mixed with a methylene chloride solution of p-tert-butylphenol (PTBP) (PTBP(viii) g dissolved in methylene chloride (MC)(ix) L), a sodium hydroxide solution of BPA (NaOH(x) g and sodium dithionite (Na 2 S 2 O 4 (xi) g was dissolved in (xii) L of water to obtain an aqueous solution in which BPA (xiii) g was dissolved), and the polymerization reaction was carried out for 60 minutes (main polymerization step). For dilution, methylene chloride (MC) (xiv) kg was added and stirred for 10 minutes, after which the mixture was separated into an organic phase containing the PC-POS copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated. The methylene chloride solution of the PC-POS copolymer thus obtained was successively washed with a 15 volume % 0.03 mol / L aqueous NaOH solution and 0.2 mol / L hydrochloric acid, and then repeatedly washed with pure water until the electrical conductivity of the aqueous phase after washing was 0.01 μS / m or less. The methylene chloride solution of the polycarbonate obtained by washing was concentrated, and then 3 L of acetone (Wako Pure Chemical Industries, special grade) was added. The solid matter obtained after further concentration was pulverized, and the obtained powder was dried under reduced pressure at 100° C. The PDMS concentration, viscosity average molecular weight, and ratio of [hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] of the obtained flakes were measured, and the results are shown in Tables 1 and 2.

[0105] [Table 1]

[0106] [Table 2]

[0107] <Other ingredients> Antioxidant: IRGAFOS 168 [tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Japan Ltd.]

[0108] Examples 1 to 6, Comparative Examples 1 to 2, Reference Examples 1 to 8 The PC-POS copolymers A1 to A5 obtained in the above Production Examples were subjected to the residence heat stability evaluation (1) described below. The results are shown in Table 3. 0.10 parts by mass of Irgafos168 was blended with 100 parts by mass of each of the PC-POS copolymers A6 to A8 obtained in the above manufacturing examples, and fed to a vented twin-screw extruder (Toshiba Machine Co., Ltd., TEM35B), melt-kneaded at a screw speed of 150 rpm, a discharge rate of 20 kg / hr, and a resin temperature of 295 to 310 ° C., to prepare pellet samples, and the retention heat stability evaluation (2) described below was performed. The results are shown in Table 4. The PC-POS copolymer and other components were mixed in the blending ratios shown in Table 5, fed to a vented twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at a screw rotation speed of 150 rpm, a discharge rate of 20 kg / hr, and a resin temperature of 295 to 310° C., to prepare pellet samples for evaluation, and subjected to physical property tests described later. The results are shown in Table 5.

[0109] [Table 3]

[0110] [Table 4]

[0111]

Table 5

[0112] [Evaluation Test] <Melt Volume Rate (MVR)> Using the above pellets, in accordance with JIS K 7210-1:2014, the amount of molten resin (ml / 10 min) flowing out from a die with a diameter of 2.095 ± 0.005 mm and a length of 8.000 ± 0.025 mm was measured under a load of 1.2 kg at 300°C. <Q value (flow value) [unit: 10 -2 mL / sec]> Using the above pellets, in accordance with JIS K 7210-1:2014:Appendix JA, using an elevated flow tester, the amount of molten resin (10 -2 mL / sec) flowing out from a nozzle with a diameter of 1.00 mm and a length of 10.00 mm was measured under a pressure of 160 kgf at 280°C. The Q value represents the amount of flow per unit time, and the higher the numerical value, the better the fluidity.

[0113] <Impact Resistance> After drying the above-obtained pellets at 100°C for 8 hours, using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., NEX110, screw diameter 36 mmφ), injection molding was performed at a cylinder temperature of 280°C and a mold temperature of 80°C to prepare Izod test specimens (length 63.5 mm, width 12.7 mm, thickness 3.2 mm). Using the specimens with a notch (r = 0.25 mm ± 0.05 mm) applied by post-processing to this test specimen, in accordance with ASTM standard D-256, the notched Izod impact strength at -30°C, -20°C, -10°C, 0°C, and 23°C was measured.

[0114] <Heat Deflection Temperature under Load: HDT (unit: °C)> The pellets obtained above were dried at 100°C for 8 hours, and then injection molded using an injection molding machine (NEX110, screw diameter 36mmφ, manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 280°C and a mold temperature of 80°C to obtain a test piece (length 127mm, width 12.7mm, thickness 3.2mm). Using this test piece, a temperature increase rate of 120°C / h, a support distance of 100mm, and a load of 1.83MPa were applied in accordance with ASTM standard D-648, and the temperature at which the edgewise deflection of the test piece reached 0.26mm was recorded.

[0115] <Retention heat stability evaluation (1)> The powder thus obtained was subjected to a residence heat stability test by injection molding as described below, and the haze value of each of the obtained molded products was measured, and the difference between the haze value at a residence time of 3 minutes (haze A) and the haze value at a residence time of 20 minutes (haze B) was calculated as Δhaze. The haze value was measured three times based on ISO 14782:1999, and the average was calculated for each. The results are shown in Table 3. Furthermore, when the powder of Example 1 was used for injection molding, the haze value was 0.4. <Injection molding> Injection molding machine: MD50 (product name) manufactured by Niigata Machine Techno Co., Ltd. Molded product shape: 90mm x 50mm 3-tier plate (3mm thick section 45mm, 2mm thick section 22.5mm, 1mm thick section 22.5mm) Molding machine cylinder temperature: 300℃ Residence time in cylinder: 3 minutes or 20 minutes Mold temperature: 80℃

[0116] <Retention heat stability evaluation (2)> The pellets thus obtained were subjected to a residence heat stability test by injection molding as described below, and the haze values ​​of the obtained molded products were measured. The difference between the haze value at a residence time of 3 minutes (haze A) and the haze value at a residence time of 20 minutes (haze B) was calculated as Δhaze. The haze value was measured three times according to ISO 14782:1999, and the average was calculated for each. The results are shown in Table 4. <Injection molding> Injection molding machine: Toshiba Machine Industry Co., Ltd. EC40 (product name) Molded product shape: 80mm x 40mm x 3.2mm Molding machine cylinder temperature: 340℃ Residence time in cylinder: 3 minutes or 20 minutes Mold temperature: 80℃

Claims

1. A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A-1) having a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) having a repeating unit represented by the following general formula (II): the difference Δhaze between the haze value (haze A) after the polycarbonate-polyorganosiloxane copolymer is allowed to reside for 3 minutes at 300° C. or 340° C. and the haze value (haze B) after the polycarbonate-polyorganosiloxane copolymer is allowed to reside for 20 minutes is less than 0.4; A polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), in which the ratio of [total number of hydroxy groups in formula (f) and formula (g)] / [total number of groups represented by formula (v-ii) and hydroxy groups in formula (f) and formula (g)] is less than 0.

01. 【Chemistry 1】 [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O-, or -CO-; a and b each independently represent an integer of 0 to 4. 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n represents the average chain length of the polyorganosiloxane, and n-1 is an integer of 1 or more representing the number of repetitions of the polyorganosiloxane unit. Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In these divalent hydrocarbon groups or monovalent hydrocarbon groups, at least one of the carbon atoms may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. k represents an integer of 2 or 3.] 【Chemistry 2】 [In the formula, Z is as defined above. k is 2 or 3.] 【Chemistry 3】 [In the formula, R 3 to R 6 , n, and k are as defined above. (PC) in the formula indicates a bond to a polycarbonate block.] 【Chemistry 4】 [In the formula, R 3 to R 6 and n are as defined above.]

2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, having a platinum content of 0.05 mass ppb or more and less than 0.5 mass ppm.

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein Z in the formula (II) is represented by the following general formula (II-a): 【Chemistry 5】 [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. w represents an integer of 0 to 4, and the wavy line represents a bonding site.]

4. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3, wherein the average chain length n of the polyorganosiloxane block (A-2) is 10 or more and 300 or less.

5. A polycarbonate-polyorganosiloxane copolymer obtained by continuously supplying an organohydrogensiloxane represented by the following general formula (2), a compound represented by the following general formula (3), and a platinum catalyst to a reactor and carrying out a hydrosilylation reaction while passing through the reactor to obtain a carbinol-modified polyorganosiloxane, and copolymerizing the carbinol-modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or with an oligomer having a repeating unit represented by the following general formula (I). 【Chemistry 6】 [In the formula, R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms; 3 ~R 6 may be the same or different, and f is an integer of 0 to 500. 【Chemistry 7】 [In the formula, R 22 represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, at least one of the hydrogen atoms contained in this divalent hydrocarbon group may be substituted with a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. At least one of the carbon atoms in these divalent hydrocarbon groups and monovalent hydrocarbon groups may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom.] 【Chemistry 8】 [In the formula, R 1 and R 2 each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO 2 represents -, -O-, or -CO-; a and b each independently represent an integer of 0 to 4.

6. The platinum catalyst is used in an amount of 0.005 ppm by mass or more and less than 1.0 ppm by mass in terms of platinum metal relative to the total of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst. The polycarbonate-polyorganosiloxane copolymer according to claim 5.

7. The platinum catalyst is used in an amount of 0.005 ppm by mass or more and 0.2 ppm by mass or less in terms of platinum metal relative to the total of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3), and the platinum catalyst. The polycarbonate-polyorganosiloxane copolymer according to claim 5 or 6.

8. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 5 to 7, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (33): 【Chemistry 9】 [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom. At least one carbon atom of the monovalent hydrocarbon group may be substituted with an oxygen atom, a nitrogen atom, or a sulfur atom. w is an integer of 0 to 4.]

9. The carbinol-modified polyorganosiloxane is represented by the following general formula (222), in which R a The polycarbonate-polyorganosiloxane copolymer according to any one of claims 5 to 8, wherein the ratio of [the number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and the group represented by formula (vi)] is less than 0.

01. 【Chemistry 10】 {In the formula, R 3 ~R 6 , f is as described above. a are each independently a group represented by the following general formula (v) or (vi): 【Chemistry 11】 [In the formula, Z is as defined above. k is 2 or 3.] 【Chemistry 12】 [In the formula, Z is as defined above. 33 is a vinyl group, an allyl group, or a -(CH 2 ) k -SiR 5 R 6 represents an end group having O-, and k is 2 or 3. 【Chemistry 13】 [In the formula, R 3 ~R 6 , f is as defined above.]}

10. A polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane unit represented by the following general formula (222-i), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (b), and a compound represented by the following general formula (c), 33 The total number of groups represented by the formula (vi) and the group represented by the formula (b) and the group represented by the formula (c) 33 The polycarbonate-polyorganosiloxane copolymer according to claim 9, wherein the ratio of the number of groups represented by the formula (I) to the number of groups represented by the formula (II) is less than 0.

01. 【Chemistry 14】 {In the formula, R 3 ~R 6 , f is as described above. a-i are each independently a group represented by the following general formula (vi): 【Chemistry 15】 [wherein Z is as defined above. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3.]} 【Chemistry 16】 [In the formula, R 3 ~R 6 , Z, R 33 , f, and k are as defined above. In the formula, (PC) indicates a bond to the polycarbonate block. 【Chemistry 17】 [In the formula, R 3 ~R 6 , Z, R 33 , f is as defined above.]

11. The carbinol-modified polyorganosiloxane is represented by the following general formula (223), in which R b The polycarbonate-polyorganosiloxane copolymer according to any one of claims 5 to 8, wherein the ratio of [number of hydroxy groups] / [total number of hydroxy groups and groups represented by formula (v)] is less than 0.

01. 【Chemistry 18】 {In the formula, R 3 ~R 6 and f are as defined above. Each R is independently a hydroxy group or a group represented by the following general formula (v): 【Chemistry 19】 [wherein Z is as defined above; and k is 2 or 3.]

12. A polycarbonate-polyorganosiloxane copolymer having a polyorganosiloxane unit represented by the following general formula (223-i), a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (d), and a compound represented by the following general formula (e), wherein the ratio of [the total number of hydroxy groups in formula (d) and formula (e)] / [the total number of groups represented by formula (vi) and the hydroxy groups in formula (d) and formula (e)] is less than 0.

01. The polycarbonate-polyorganosiloxane copolymer according to claim 11. 【Chemistry 20】 {In the formula, R 3 ~R 6 , f is as described above. b-i are each independently a group represented by the following general formula (vi): 【Chemistry 21】 [wherein Z is as defined above. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3.]} 【Chemical 22】 [In the formula, R 3 ~R 6 , f, and k are as defined above. In the formula, (PC) indicates a bond to the polycarbonate block. 【Chemistry 23】 [In the formula, R 3 ~R 6 , f is as defined above.]

13. A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 12.

14. A molded article comprising the polycarbonate resin composition according to claim 13.

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