Polycarbonate-polyorganosiloxane copolymers

Abstract

A polycarbonate-polyorganosiloxane copolymer containing a polycarbonate block (A-1) containing a repeating unit having a specific structure and a polyorganosiloxane block (A-2) containing a repeating unit having a specific structure, the difference delta haze between the haze value (haze A) after the polycarbonate-polyorganosiloxane copolymer or the resin composition thereof is retained at 300 DEG C or 340 DEG C for 3 minutes and the haze value (haze B) after the polycarbonate-polyorganosiloxane copolymer or the resin composition thereof is retained for 20 minutes is less than 0.4.

Description

[0001] This application is a divisional application of an application filed on December 25, 2020, with application number 202080090284.1 and invention name “Polycarbonate-polysiloxane copolymer”. Technical Field

[0002] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, and more particularly to a polycarbonate-polyorganosiloxane copolymer which has excellent thermal stability even in molding at high temperatures and can provide a molded product having excellent transparency. Background Art

[0003] Polycarbonate resins (hereinafter sometimes referred to as PC resins) manufactured using bisphenol A and the like are known as resins having very high impact resistance and excellent heat resistance among engineering plastics. On the other hand, attempts are being made to manufacture polycarbonate-polyorganosiloxane copolymers by using polyorganosiloxane as a comonomer together with dihydric phenols such as bisphenol A to further improve impact resistance and heat resistance.

[0004] Polycarbonate-polyorganosiloxane copolymers (hereinafter sometimes referred to as PC-POS copolymers) are known as polycarbonate resins having excellent flame retardancy and impact resistance (e.g., Patent Document 1). PC-POS copolymers are expected to be widely used in various fields such as the electrical and electronic equipment field and the automotive field due to their excellent properties such as high impact resistance, chemical resistance and flame retardancy.

[0005] Patent Document 2 discloses a polycarbonate-polyorganosiloxane copolymer having improved transparency, and evaluates the total light transmittance, haze value, and the like.

[0006] Patent Documents 3 to 5 disclose molded products having improved lubricity, wear resistance, and the like by using PC-POS copolymers.

[0007] Patent Document 6 describes a method for producing a PC-POS copolymer having specific steps.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent No. 2662310

[0011] Patent Document 2: Japanese Patent Application Publication No. 2011-046911

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 05-202181

[0013] Patent Document 4: Japanese Patent Application Laid-Open No. 05-202182

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 05-200761

[0015] Patent Document 6: Japanese Patent No. 5919294 Summary of the invention

[0016] Problem that the invention aims to solve

[0017] In recent years, materials with the characteristics of PC-POS copolymers have been desired in many applications, resulting in the need to form various molded product shapes. Therefore, it is necessary to ensure the fluidity of the resin, and there is a trend of increasing the temperature during molding. However, PC-POS copolymers have a problem that the transparency is easily reduced compared to ordinary polycarbonate during molding at high temperatures.

[0018] Although Patent Document 2 reports that the total light transmittance (88% or more) is improved by using a PC-POS copolymer having a specific average microdomain size and standardized variance, this total light transmittance has been achievable in the past. Although Patent Documents 3 to 5 show improvement in the mechanical strength of PC-POS copolymers, there is no research on improving thermal stability such as transparency during molding at high temperatures. Although Patent Document 6 discloses a method for producing a PC-POS copolymer with excellent impact resistance and transparency, thermal stability such as transparency during molding at high temperatures is still insufficient.

[0019] In view of the above circumstances, an object of the present invention is to provide a polycarbonate-polyorganosiloxane copolymer which is excellent in mechanical properties such as impact resistance and also excellent in transparency after being molded at a high temperature.

[0020] Means used to solve problems

[0021] The present inventors have conducted intensive studies and have found that a polycarbonate-polyorganosiloxane copolymer having a specific structure of a polyorganosiloxane block and specific haze conditions has high transparency. That is, the present invention relates to the following.

[0022] [1] A polycarbonate-polyorganosiloxane copolymer comprising: a polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) comprising a repeating unit represented by the following formula (II),

[0023] The difference Δhaze between the haze value (haze A) of the polycarbonate-polyorganosiloxane copolymer after being allowed to stand at 300° C. or 340° C. for 3 minutes and the haze value (haze B) after being allowed to stand at 300° C. or 340° C. for 20 minutes is less than 0.4.

[0024] [Chemical formula 1]

[0025]

[0026] [Where 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-, -SO2-, -O-, or -CO-. a and b each independently represent an integer of 0 to 4. 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. n represents the average chain length of the polyorganosiloxane, and n-1 is an integer greater than 1 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 by 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 by an oxygen atom, a nitrogen atom, or a sulfur atom. k represents an integer of 2 or 3.]

[0027] [2] The polycarbonate-polyorganosiloxane copolymer according to [1] above, wherein the platinum content is 0.05 mass ppb or more and less than 0.5 mass ppm.

[0028] [3] The polycarbonate-polyorganosiloxane copolymer according to [1] or [2] above, wherein Z in the formula (II) is represented by the following general formula (II-a).

[0029] [Chemical formula 2]

[0030]

[0031] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of the hydrogen atoms contained in the monovalent hydrocarbon group may be substituted by a halogen atom. At least one of the carbon atoms of the monovalent hydrocarbon group may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4, and the wavy line represents a bonding site.]

[0032] [4] The polycarbonate-polyorganosiloxane copolymer according to any one of [1] to [3] above, wherein the average chain length n of the polyorganosiloxane block (A-2) is 10 or more and 300 or less.

[0033] [5] A polycarbonate-polysiloxane copolymer according to any one of [1] to [4] above, comprising a polycarbonate-polysiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), wherein the ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of groups represented by formula (v-ii) and the hydroxyl groups in formula (f) and formula (g)] is less than 0.01.

[0034] [Chemical formula 3]

[0035]

[0036] [Wherein, Z is as described above. k is 2 or 3.]

[0037] [Chemical formula 4]

[0038]

[0039] [Where R 3 ~R 6 , n, and k are as described above. (PC) in the formula represents the bond to the polycarbonate block.]

[0040] [Chemical formula 5]

[0041]

[0042] [Where R 3 ~R 6 , n as described above.]

[0043] [6] A polycarbonate-polyorganosiloxane copolymer obtained as follows:

[0044] An organohydrogensiloxane represented by the following general formula (2), a compound represented by the following general formula (3) and a platinum catalyst are continuously supplied to a reactor, and a hydrosilylation reaction is carried out while passing through the reactor to obtain a hydrocarbyl alcohol-modified polyorganosiloxane, and the hydrocarbyl alcohol-modified polyorganosiloxane is copolymerized with a dihydric phenol and a carbonate precursor, or the hydrocarbyl alcohol-modified polyorganosiloxane is copolymerized with an oligomer having a repeating unit represented by the following general formula (I).

[0045] [Chemical formula 6]

[0046]

[0047] [Where 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 6They may be the same or different from each other. f is an integer of 0 to 500.]

[0048] [Chemical formula 7]

[0049]

[0050] [Where R 22 represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom.]

[0051] [Chemical formula 8]

[0052]

[0053] [Where 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-, -SO2-, -O-, or -CO-. a and b each independently represent an integer of 0 to 4.]

[0054] [7] The polycarbonate-polyorganosiloxane copolymer according to [6] above, wherein the amount of the platinum catalyst used is 0.005 ppm by mass or more and less than 1.0 ppm by mass, calculated as platinum metal, relative to the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3) and the platinum catalyst.

[0055] [8] The polycarbonate-polyorganosiloxane copolymer according to [6] or [7], wherein the amount of the platinum catalyst used is greater than or equal to 0.005 ppm by mass and less than or equal to 0.2 ppm by mass, calculated as platinum metal, relative to the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3) and the platinum catalyst.

[0056] [9] The polycarbonate-polyorganosiloxane copolymer according to any one of [6] to [8] above, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (33).

[0057] [Chemical formula 9]

[0058]

[0059] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of the hydrogen atoms contained in the monovalent hydrocarbon group may be substituted by a halogen atom. At least one of the carbon atoms of the monovalent hydrocarbon group may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.]

[0060]

[10] The polycarbonate-polyorganosiloxane copolymer according to any one of [6] to [9], wherein the hydrocarbon alcohol-modified polyorganosiloxane is represented by the following general formula (222): a A hydrocarbyl alcohol-modified polyorganosiloxane wherein 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 less than 0.01.

[0061] [Chemical formula 10]

[0062]

[0063] {In the formula, R 3 ~R 6 , f as described above. R a Each is independently a group represented by the following general formula (v) or (vi):

[0064] [Chemical formula 11]

[0065]

[0066] [Wherein, Z is as described above. k is 2 or 3.]

[0067] [Chemical formula 12]

[0068]

[0069] [wherein, Z is as described above. R 33 represents a vinyl group, an allyl group, or a -(CH2) group derived from the reaction of Si-H of the following general formula (2) with a vinyl group or an allyl group k -SiR 5 R 6 O-terminal group, k is 2 or 3.]

[0070] [Chemical formula 13]

[0071]

[0072] [Where R 3 ~R 6 ,fAs described above. ]}

[0073]

[11] The polycarbonate-polyorganosiloxane copolymer according to

[10] , which contains 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), wherein [{-OZR in formula (b) and formula (c) 33}] / [the number of groups represented by formula (vi) and {-OZR in formula (b) and formula (c) 33 The ratio of the total number of groups represented by ] is less than 0.01.

[0074] [Chemical formula 14]

[0075]

[0076] {In the formula, R 3 ~R 6 , f as described above. R a Each is independently a group represented by the following general formula (vi):

[0077] [Chemical formula 15]

[0078]

[0079] [In the formula, Z is as described above. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3.]}

[0080] [Chemical formula 16]

[0081]

[0082] [Where R 3 ~R 6 , Z, R 33 , f, and k are as described above. (PC) in the formula represents the bonding to the polycarbonate block.]

[0083] [Chemical formula 17]

[0084]

[0085] [Where R 3 ~R 6 , Z, R 33 , f as described above.]

[0086]

[12] The polycarbonate-polyorganosiloxane copolymer according to any one of [6] to [9], wherein the hydrocarbon alcohol-modified polyorganosiloxane is represented by the following general formula (223): bA hydrocarbyl alcohol-modified polyorganosiloxane wherein the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by the formula (v)] is less than 0.01.

[0087] [Chemical formula 18]

[0088]

[0089] {In the formula, R 3 ~R 6 , f as described above. R a Each is independently a hydroxyl group or a group represented by the following general formula (v):

[0090] [Chemical formula 19]

[0091]

[0092] [Wherein, Z is as described above. k is 2 or 3.]}

[0093]

[13] The polycarbonate-polyorganosiloxane copolymer according to the above

[12] , which contains 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), and the ratio of [the total number of hydroxyl groups in formula (d) and formula (e)] / [the total number of groups represented by formula (vi) and the hydroxyl groups in formula (d) and formula (e)] is less than 0.01.

[0094] [Chemical formula 20]

[0095]

[0096] {In the formula, R 3 ~R 6 , f as described above. R b-i Each is independently a group represented by the following general formula (vi):

[0097] [Chemical formula 21]

[0098]

[0099] [In the formula, Z is as described above. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3.]}

[0100] [Chemical formula 22]

[0101]

[0102] [Where R 3 ~R 6, f, and k are as described above. (PC) in the formula represents the bonding to the polycarbonate block.]

[0103] [Chemical formula 23]

[0104]

[0105] [Where R 3 ~R 6 , f as described above.]

[0106]

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

[13] above.

[0107]

[15] A molded article formed from the polycarbonate resin composition according to

[14] above.

[0108] The present invention also relates to the following aspects.

[0109]

[101] A method for producing a polycarbonate-polyorganosiloxane copolymer, comprising:

[0110] (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 subjecting them to a hydrosilylation reaction while passing through the reactor to obtain a hydrocarbyl alcohol-modified polyorganosiloxane; and

[0111] (X2) A step of copolymerizing the hydrocarbyl alcohol-modified polyorganosiloxane obtained in the above step (X1) with a dihydric phenol and a carbonate precursor, or copolymerizing it with an oligomer having a repeating unit represented by the following general formula (I).

[0112] [Chemical formula 24]

[0113]

[0114] [Where 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 They may be the same or different from each other. f is an integer of 0 to 500.]

[0115] [Chemical formula 25]

[0116]

[0117] [Where R 22represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom.]

[0118] [Chemical formula 26]

[0119]

[0120] [Where 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-, -SO2-, -O-, or -CO-. a and b each independently represent an integer of 0 to 4.]

[0121]

[102] A method for producing a polycarbonate-polyorganosiloxane copolymer according to the above

[101] , wherein in the above step (X1), the amount of the platinum catalyst used is greater than 0.005 mass ppm and less than 1.0 mass ppm, calculated as platinum metal, relative to the total amount of the organohydrogensiloxane represented by the above general formula (2), the compound represented by the above general formula (3) and the above platinum catalyst.

[0122]

[103] A method for producing a polycarbonate-polyorganosiloxane copolymer according to

[101] or

[102] , wherein in the step (X1), the amount of the platinum catalyst used is greater than 0.005 ppm by mass and less than 0.2 ppm by mass, calculated as platinum metal, relative to the total amount of the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3) and the platinum catalyst.

[0123]

[104] The method for producing a polycarbonate-polyorganosiloxane copolymer according to any one of

[101] to

[103] above, wherein the compound represented by the general formula (3) is a compound represented by the following general formula (33).

[0124] [Chemical formula 27]

[0125]

[0126] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of the hydrogen atoms contained in the monovalent hydrocarbon group may be substituted by a halogen atom. At least one of the carbon atoms of the monovalent hydrocarbon group may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.]

[0127] Effects of the Invention

[0128] According to the present invention, a polycarbonate-polyorganosiloxane copolymer can be produced which has excellent mechanical properties derived from a polyorganosiloxane block and which maintains excellent transparency even after molding at high temperatures, that is, has high thermal stability. DETAILED DESCRIPTION

[0129] The polycarbonate-polyorganosiloxane copolymer of the present invention is described in detail below. In this specification, any preferred limitation can be adopted, and a combination of preferred limitations can be said to be more preferred. In this specification, the description of "XX to YY" means "XX or more and YY or less".

[0130] The polycarbonate-polyorganosiloxane copolymer of the present invention is characterized in that it is a polycarbonate-polyorganosiloxane copolymer containing a polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) comprising a repeating unit represented by the following general formula (II), and the difference Δhaze between the haze value (haze A) after the polycarbonate-polyorganosiloxane copolymer or its resin composition is retained at 300° C. or 340° C. for 3 minutes and the haze value (haze B) after the same is retained for 20 minutes is less than 0.4.

[0131] [Chemical formula 28]

[0132]

[0133] [Where 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-, -SO2-, -O-, or -CO-. a and b each independently represent an integer of 0 to 4. 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. n represents the average chain length of the polyorganosiloxane, and n-1 is an integer greater than 1 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 by 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 by an oxygen atom, a nitrogen atom, or a sulfur atom. k represents an integer of 2 or 3.]

[0134] <Polycarbonate-polysiloxane copolymer>

[0135] The polycarbonate-polyorganosiloxane copolymer of the present invention comprises a polycarbonate block (A-1) comprising a repeating unit represented by the above general formula (I) and a polyorganosiloxane block (A-2) comprising a repeating unit represented by the above general formula (II).

[0136] The polycarbonate block (A-1) represented by the general formula (I) is described in detail. 1 and R 2 Examples of the halogen atom independently represented include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0137] As R 1 and R 2 The alkyl groups independently represented by each of them include methyl, ethyl, n-propyl, isopropyl, various butyl groups ("various" means including straight-chain and all branched groups, the same below), various pentyl groups, and various hexyl groups. 1 and R 2 The alkoxy groups independently represented include the case where the alkyl moiety is the above-mentioned alkyl group.

[0138] As the alkylene group represented by X, for example, methylene, ethylene, trimethylene, tetramethylene, hexamethylene, etc. can be mentioned, and alkylene groups having 1 to 5 carbon atoms are preferred. As the alkylidene group represented by X, ethylidene, isopropylidene, etc. can be mentioned. As the cycloalkylene group represented by X, cyclopentanediyl, cyclohexanediyl, cyclooctanediyl, etc. can be mentioned, and cycloalkylene groups having 5 to 10 carbon atoms are preferred. As the arylene group represented by X, phenylene, naphthylene, biphenylene, etc. can be mentioned. As the cycloalkylidene group represented by X, for example, cyclohexylidene, 3,5,5-trimethylcyclohexylidene, 2-adamantylidene, etc. can be mentioned, and cycloalkylene groups having 5 to 10 carbon atoms are preferred, and cycloalkylene groups having 5 to 8 carbon atoms are more preferred. As the aryl part of the arylalkylene group represented by X, aryl groups having 6 to 14 ring carbon atoms such as phenyl, naphthyl, biphenyl, anthracenyl, etc. can be mentioned. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl, naphthyl, biphenylyl and anthracenyl.

[0139] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1. Among them, a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 0 and X is an alkylidene group, particularly an isopropylidene group.

[0140] In the general formula (II), R 3 ~R 6 The halogen atom represented independently of each other includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 3 ~R 6 The alkyl group represented independently of each other includes methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 3 ~R 6 The alkoxy groups independently represented by each of them include the case where the alkyl moiety is the above-mentioned alkyl group. 3 ~R 6 Examples of the aryl group independently represented include phenyl and naphthyl.

[0141] As R 3 ~R 6 , preferably all are 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 are methyl groups.

[0142] Z represents a divalent hydrocarbon group. The carbon number of the divalent hydrocarbon group is not particularly limited, but is preferably 1 to 20, and more preferably 1 to 10.

[0143] The divalent hydrocarbon group may be any of linear, branched, and cyclic, and specifically, may include linear, branched, or cyclic alkylene groups such as methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, cyclohexylene, and octamethylene; arylene groups such as o-phenylene, m-phenylene, p-phenylene, methylphenylene, ethylphenylene, methoxyphenylene, and naphthylene; and groups in which a part or all of the hydrogen atoms of these groups are substituted with halogen atoms, monovalent hydrocarbon groups having 1 to 20 carbon atoms, and the like. A part 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 a monovalent hydrocarbon group having 1 to 10 carbon atoms, may be any of linear, branched, and cyclic groups. 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; cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl; aryl groups such as phenyl, tolyl, xylyl, and naphthyl; aralkyl groups such as benzyl, phenethyl, and phenylpropyl; and groups in which a part or all of the hydrogen atoms of these groups are substituted with halogen atoms, etc.

[0144] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0145] 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, -CH2- is substituted with -O-, -NH- or -S-.

[0146] k represents an integer of 2 or 3, and preferably 3.

[0147] Among them, Z is preferably a phenylene group which may be substituted with Q represented by the following general formula (II-a).

[0148] [Chemical formula 29]

[0149]

[0150] [Wherein, w is an integer from 0 to 4, and the wavy line represents the bonding site.]

[0151] Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and a part of the carbon atoms may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of the group in which a part of the carbon atoms of the monovalent hydrocarbon group are substituted by oxygen atoms include alkoxy groups having 1 to 5 carbon atoms such as methoxy, ethoxy, isopropoxy, n-butoxy and tert-butoxy.

[0152] Q is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably a methyl group or a methoxy group.

[0153] w is an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

[0154] More specifically, as Z in the above formula (II), a group represented by the following formula is preferred.

[0155] [Chemical formula 30]

[0156]

[0157] [In the formula, the wavy line represents a bonding site. d, e and g each independently represent an integer of 0 to 50, preferably 0 to 10.]

[0158] Among them, more preferred are the group represented by formula (Z-1), the group represented by formula (Z-2), the group represented by formula (Z-8) (wherein d=6), or the group represented by formula (Z-9) (wherein e=1, g=0).

[0159] The polycarbonate-polyorganosiloxane copolymer of the present invention will be described in more detail from another aspect.

[0160] 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, subjecting them to a hydrosilylation reaction while passing through the reactor to obtain a hydrocarbyl alcohol-modified polyorganosiloxane, copolymerizing the hydrocarbyl alcohol-modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or copolymerizing the hydrocarbyl alcohol-modified polyorganosiloxane with an oligomer having a repeating unit represented by the following general formula (I), thereby obtaining the polycarbonate-polyorganosiloxane. It should be noted that the polycarbonate-polyorganosiloxane copolymer of the present invention can also be obtained by refining the above-mentioned alkyl alcohol modified polyorganosiloxane using a known method as needed, copolymerizing the refined alkyl alcohol modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or copolymerizing the refined alkyl alcohol modified polyorganosiloxane with an oligomer having a repeating unit shown in the following general formula (I). Refining is described below.

[0161] [Chemical formula 31]

[0162]

[0163] [Where 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 They may be the same or different from each other. f is an integer of 0 to 500.]

[0164] [Chemical formula 32]

[0165]

[0166] [Where R 22 represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom.]

[0167] [Chemical formula 33]

[0168]

[0169] [Where R 1 and R 2Each 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-, -SO2-, -O-, or -CO-. a and b each independently represent an integer of 0 to 4.]

[0170] R 3 ~R 6 Preferred examples of are as described above, and combinations of preferred groups are also preferred. f is an integer of 0 to 500, more preferably 0 to 300, and further preferably 30 to 200.

[0171] Another preferred embodiment of f is an integer of 8 to 298, more preferably 28 or more, further preferably 33 or more, further preferably 38 or more, further preferably 198 or less, further preferably 148 or less, further preferably 98 or less, and particularly preferably 93 or less. When f is 500 or less, the molecular weight of the obtained hydrocarbyl alcohol-modified polyorganosiloxane is within a preferred range from the viewpoints of transparency and mechanical properties of the copolymer.

[0172] R in formula (3) 22 represents a vinyl group or an allyl group, and more preferably an allyl group.

[0173] Examples of Z are as described above, and preferred examples and preferred combinations are the same.

[0174] As the compound represented by the formula (3), a compound represented by the following general formula (33) is more preferable.

[0175] [Chemical formula 34]

[0176]

[0177] [In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and at least one of the hydrogen atoms contained in the monovalent hydrocarbon group may be substituted by a halogen atom. At least one of the carbon atoms of the monovalent hydrocarbon group may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. w is an integer of 0 to 4.]

[0178] The platinum catalyst is a catalyst for promoting hydrosilylation. As specific examples thereof, known catalysts such as platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, and diacetyl platinum acetate can be used. The amount of the above-mentioned platinum catalyst used is 0.005 mass ppm or more and less than 1.0 mass ppm in terms of platinum metal relative to 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 above-mentioned platinum catalyst. If the amount of the platinum catalyst is 0.005 mass ppm or more, the hydrosilylation reaction is fully carried out. If the amount of the platinum catalyst is less than 1.0 mass ppm, side reactions can be suppressed at the reaction site at the end of the organosiloxane.

[0179] The amount of platinum catalyst is more preferably 0.005 mass ppm or more and 0.5 mass ppm or less, further preferably 0.005 mass ppm or more and 0.2 mass ppm or less, and still further preferably 0.01 mass ppm or more and 0.10 mass ppm or less.

[0180] The above-mentioned alkyl alcohol-modified polyorganosiloxane can be prepared by the following steps:

[0181] (i) a step of continuously supplying the organohydrogensiloxane represented by the general formula (2), the compound represented by the general formula (3) and a platinum catalyst to a reactor,

[0182] (ii): a step of allowing the above (2), (3) and a platinum catalyst to pass through the above reactor while performing a hydrosilylation reaction, and

[0183] (iii): A step of taking out the reaction product.

[0184] Process (i)

[0185] In the above step (i), the above (2), (3) and the platinum catalyst can be independently and continuously supplied to the reactor through a supply pipe, or part or all of the above (2), (3) and the platinum catalyst can be mixed in a tank equipped with a stirrer in advance and then continuously supplied to the reactor.

[0186] The reactor is preferably a tubular reactor. The tubular reactor is not particularly limited and can be appropriately selected from known flow reactors that can react while allowing (2), (3) and a platinum catalyst to pass through the reactor.

[0187] In the above step (i), there is no particular restriction on the temperature of the supplied (2), (3) and platinum catalyst. In order to smoothly advance the reaction in step (ii), it is preferably above 0°C and below 150°C, more preferably above 10°C and below 100°C, and further preferably above 20°C and below 80°C.

[0188] In step (i), a solvent may be added in addition to (2), (3) and the platinum catalyst.

[0189] 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, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; alcohols such as ethanol, 1-propanol, and 2-propanol, etc.

[0190] Step (ii)

[0191] Step (ii) is a step of causing the components (2) and (3) to undergo a hydrosilylation reaction while passing the components (2), (3) and a platinum catalyst through a reactor.

[0192] The temperature in the reactor in this step is not particularly limited, but is preferably 20°C to 180°C, more preferably 40°C to 150°C, and even more preferably 50°C to 120°C, from the perspective of improving reaction efficiency and suppressing side reactions.

[0193] It should be noted that the total time of step (i) and step (ii) is not particularly limited, but is preferably from 1 minute to 60 minutes, more preferably from 3 minutes to 45 minutes, and more preferably from 5 minutes to 30 minutes, from the perspective of production efficiency.

[0194] Process (iii)

[0195] Step (iii) is a step of taking out the reaction product obtained in the above step (ii).

[0196] The take-out amount depends on the supply amount in step (i) and is not particularly limited, but is preferably 100 kg / hour or more, more preferably 200 kg / hour or more, and further preferably 300 kg / hour or more from the viewpoint of efficient production.

[0197] The reaction product can be used directly or purified by known methods as needed. For example, the process comprises removing the compound represented by the general formula (3). As a specific example of the process (iv), the excess compound represented by the general formula (3) is removed by heating, for example, at 160° C., using a thin film evaporator.

[0198] By using the above-mentioned hydrocarbyl alcohol-modified polyorganosiloxane, the platinum content finally contained in the PC-POS copolymer can be adjusted to the above-mentioned value.

[0199] As a preferred embodiment of the above-mentioned hydrocarbon alcohol-modified polyorganosiloxane, there can be mentioned: represented by the following general formula (222) wherein R a A hydrocarbyl alcohol-modified polyorganosiloxane wherein 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 less than 0.01.

[0200] [Chemical formula 35]

[0201]

[0202] {In the formula, R 3 ~R 6 , f as described above. R a Each is independently a group represented by the following general formula (v) or (vi):

[0203] [Chemical formula 36]

[0204]

[0205] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. k is 2 or 3.]

[0206] [Chemical formula 37]

[0207]

[0208] [In the formula, Z has the same meaning as in the above formula (v). 33 represents a vinyl group, an allyl group, or a -(CH2)-containing group derived from the reaction of Si-H of the following general formula (2) with a vinyl group or an allyl group k -SiR 5 R 6 O-terminal group, k is 2 or 3.]

[0209] [Chemical formula 38]

[0210]

[0211] [Where R 3 ~R 6 ,fAs described above. ]}

[0212] If 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 less than 0.01, the formation of side reaction products can be suppressed, and the decrease in transparency and color tone of the copolymer obtained by using the polyorganosiloxane modified with the hydrocarbon alcohol due to molding at high temperature can be suppressed, and the appearance of the molded product using the copolymer can be appropriately maintained.

[0213] 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, further preferably 0.006 or less, and still more preferably 0.005 or less.

[0214] The hydrocarbon alcohol-modified polyorganosiloxane satisfying the above 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)] can be obtained, for example, by continuously supplying the organohydrogensiloxane represented by the above general formula (2), the compound represented by the above general formula (3) and a platinum catalyst to a reactor and causing them to undergo a hydrosilylation reaction while passing through the reactor.

[0215] The above ratios in this specification are 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure Si and the integral value of -O-Si(R 5 )(R 6 )-OZ-structured Si.

[0216] Another preferred embodiment of the hydrocarbon alcohol-modified polyorganosiloxane is as follows: b A polycarbonate-polyorganosiloxane copolymer obtained by modifying a polyorganosiloxane with a hydrocarbon alcohol wherein the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by the formula (v)] is less than 0.01.

[0217] [Chemical formula 39]

[0218]

[0219] {In the formula, R 3 ~R 6 , f as described above. R b Each is independently a hydroxyl group or a group represented by the following general formula (v):

[0220] [Chemical formula 40]

[0221]

[0222] [Wherein, Z is as described above. k is 2 or 3.]}

[0223] If the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by formula (v)] is less than 0.01, the formation of side reaction products can be suppressed, and the decrease in transparency and color tone of the copolymer obtained by using the hydrocarbon alcohol-modified polyorganosiloxane due to molding at high temperature can be suppressed, and the appearance of the molded product using the copolymer can be appropriately maintained.

[0224] The ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by formula (v)] is more preferably 0.008 or less, further preferably 0.006 or less, and still more preferably 0.005 or less.

[0225] The hydrocarbon alcohol-modified polyorganosiloxane satisfying 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 the organohydrogensiloxane represented by the above general formula (2), the compound represented by the above general formula (3) and a platinum catalyst to a reactor and causing them to undergo a hydrosilylation reaction while passing through the reactor.

[0226] The above ratios in this specification are 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure and the integral value of Si from -O-Si(R 5 )(R 6 )-OH structure Si integral value calculated.

[0227] The above-mentioned polycarbonate-polyorganosiloxane copolymer can be manufactured by adding polyorganosiloxane to the reaction system in which dihydric phenol and carbonate precursor are polymerized by interfacial polymerization (phosgene method), transesterification (melting method), etc. In the case of interfacial polymerization, phosgene, triphosgene, etc. can be used as carbonate precursors, and in the case of transesterification, diphenyl carbonate can be used as carbonate precursors. Alternatively, as described later, after preparing a bisphenol monomer or bisphenol polycarbonate oligomer with a chloroformate structure at both ends by reacting dihydric phenol with phosgene in advance, the method in which the bisphenol monomer or bisphenol polycarbonate oligomer is reacted with polyorganosiloxane is also suitable. In particular, when interfacial polymerization is adopted, it is easy to separate the organic phase containing PC-POS copolymer from the aqueous phase containing unreacted products, catalyst residues, etc., and it is easy to separate the organic phase containing PC-POS copolymer from the aqueous phase in each cleaning process such as alkali cleaning, acid cleaning, pure water cleaning, etc. Therefore, PC-POS copolymer can be obtained efficiently. As a method for producing a PC-POS copolymer, for example, the method described in Japanese Patent Application Laid-Open No. 2014-80462 can be referred to.

[0228] Specifically, the previously manufactured polycarbonate oligomer and the alkyl alcohol modified polyorganosiloxane described later can be dissolved in a water-insoluble organic solvent (such as dichloromethane), an alkaline compound aqueous solution (such as sodium hydroxide aqueous solution) of a dihydric phenol compound (such as bisphenol A) is added, and a tertiary amine (such as triethylamine) and a quaternary ammonium salt (such as trimethylbenzyl ammonium chloride) are used as a polymerization catalyst. The interfacial polycondensation reaction is carried out in the presence of a capping agent (monohydric phenol such as p-tert-butylphenol). In addition, the PC-POS copolymer can also be manufactured by copolymerizing the alkyl alcohol modified polyorganosiloxane, the dihydric phenol and phosgene, carbonate or chloroformate.

[0229] Polycarbonate oligomers can be produced by reacting dihydric phenol with carbonate precursors such as phosgene and triphosgene in an organic solvent such as dichloromethane, chlorobenzene, chloroform, etc. It should be noted that when polycarbonate oligomers are produced by transesterification, they can also be produced by reacting dihydric phenol with carbonate precursors such as diphenyl carbonate.

[0230] As the dihydric phenol, a dihydric phenol represented by the following general formula (viii) is preferably used.

[0231] [Chemical formula 41]

[0232]

[0233] In the formula, R 1 , R 2 , a, b and X are as described above.

[0234] 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'-dihydroxybiphenyl, bis(4-hydroxyphenyl)cycloalkanes, bis(4-hydroxyphenyl)ethers, bis(4-hydroxyphenyl)sulfides, bis(4-hydroxyphenyl)sulfones, bis(4-hydroxyphenyl)sulfoxides, and bis(4-hydroxyphenyl)ketones. These dihydric phenols may be used alone or in combination of two or more.

[0235] Among them, bis(hydroxyphenyl)alkane-based diphenols are preferred, and bisphenol A is more preferred. When bisphenol A is used as the diphenol, a PC-POS copolymer is obtained in which X is an isopropylidene group and a=b=0 in the general formula (i).

[0236] Examples of dihydric phenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxybiphenyls, dihydroxydiarylfluorenes, and dihydroxydiaryladamantanes. These dihydric phenols may be used alone or in combination of two or more.

[0237] Examples of the 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.

[0238] 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.

[0239] 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 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.

[0240] Examples of dihydroxybiphenyls include 4,4'-dihydroxybiphenyl. Examples of dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. 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.

[0241] Examples of dihydric phenols other than those described 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-dioxolane.

[0242] In order to adjust the molecular weight of the obtained PC-POS copolymer, an end-capping agent (molecular weight regulator) can be used. As the end-capping agent, for example, monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol can be cited. These monohydric phenols can be used alone or in combination of two or more.

[0243] The polycarbonate-polyorganosiloxane copolymer in one embodiment of the present invention can be obtained by reacting a hydrocarbon alcohol-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 a polyorganosiloxane unit represented by the following general formula (222-i).

[0244] [Chemical formula 42]

[0245]

[0246] {In the formula, R 3 ~R 6 , f as described above. R a-i Each is independently a group represented by the following general formula (vi).

[0247] [Chemical formula 43]

[0248]

[0249] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3. ]}

[0250] It should be noted that in the polyorganosiloxane unit represented by the general formula (222-i), R represented by the general formula (vi) a-i Group (CH2) k Directly bonds to silicon atoms (Si).

[0251] However, as described above, in the hydrocarbon alcohol-modified polyorganosiloxane represented by the general formula (222), R a The group represented by formula (vi) may be included, and the ratio of [the total number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and the groups represented by formula (vi)] is preferably less than 0.01. That is, in the polycarbonate-polyorganosiloxane copolymer in one embodiment of the present invention, in addition to the polycarbonate-polyorganosiloxane copolymer having the polyorganosiloxane unit represented by the above-mentioned general formula (222-i), it may also include a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (b) in which the compound represented by formula (vi) is introduced into the end, and a compound represented by the following general formula (c) that remains without reacting with a carbonate precursor and a dihydric phenol, or a polycarbonate oligomer, etc.

[0252] [Chemical formula 44]

[0253]

[0254] [Where R 3 ~R 6 , Z, R 33 , f, and k are as described above. (PC) in the formula represents the bonding to the polycarbonate block.]

[0255] [Chemical formula 45]

[0256]

[0257] [Where R 3 ~R 6 , Z, R 33 , f as described above.]

[0258] 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 preferably [{-OZR in formula (b) and formula (c)] 33} total number of groups represented by formula (vi) and {-OZR in formula (b) and formula (c) 33 If it is less than 0.01, the decrease in transparency and color tone of the PC-POS copolymer caused by molding at high temperature is suppressed, the Δ haze value of the PC-POS copolymer can be set to the above value, and the appearance of the molded product using the copolymer can be appropriately maintained.

[0259] In the above formula (b) and formula (c), {-OZR 33} total number of groups represented by formula (vi) and {-OZR in formula (b) and formula (c) 33 The ratio of {the total number of groups represented by} is more preferably 0.008 or less, further preferably 0.006 or less, and further preferably 0.005 or less.

[0260] Satisfying the above-mentioned {-OZR in formula (b) and formula (c) 33} total number of groups represented by formula (vi) and {-OZR in formula (b) and formula (c) 33 A PC-POS copolymer having a ratio of [the total number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and the groups represented by formula (vi)] can be obtained, for example, by using a hydrocarbon alcohol-modified polyorganosiloxane having a ratio of [the total number of groups represented by formula (vi)] / [the total number of groups represented by formula (v) and the groups represented by formula (vi)] of less than 0.01.

[0261] The above ratios in this specification are 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure Si and the integral value of -O-Si (R 5 )(R 6 )-OZ-structured Si.

[0262] The polycarbonate-polyorganosiloxane copolymer in another embodiment of the present invention can be obtained by reacting a hydrocarbon alcohol-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 a polyorganosiloxane unit represented by the following general formula (223-i).

[0263] [Chemical formula 46]

[0264]

[0265] {In the formula, R 3 ~R 6 , f as described above. R b-i Each is independently a group represented by the following general formula (vi):

[0266] [Chemical formula 47]

[0267]

[0268] [In the formula, Z represents a divalent hydrocarbon group, and at least one of the hydrogen atoms contained in the divalent hydrocarbon group may be substituted by 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 and monovalent hydrocarbon groups may be substituted by an oxygen atom, a nitrogen atom or a sulfur atom. The oxygen atom of formula (vi) is bonded to the polycarbonate unit. k is 2 or 3. ]}

[0269] It should be noted that in the polyorganosiloxane unit represented by the general formula (223-i), R represented by the general formula (vi) b-i Group (CH2) k Directly bonds to silicon atoms (Si).

[0270] As described above, in the hydrocarbon alcohol-modified polyorganosiloxane represented by the general formula (223), R b That is, the polycarbonate-polyorganosiloxane copolymer in one embodiment of the present invention, 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), also includes a polycarbonate-polyorganosiloxane copolymer represented by the following general formula (d) in which a hydroxyl group is introduced into the terminal, and a compound represented by the following general formula (e) that remains without reacting with a carbonate precursor and a dihydric phenol, or a polycarbonate oligomer, etc.

[0271] [Chemical formula 48]

[0272]

[0273] [Where R 3 ~R 6 , f, and k are as described above. (PC) in the formula represents the bonding to the polycarbonate block.]

[0274] [Chemical formula 49]

[0275]

[0276] [Where R 3 ~R 6 , f as described above.]

[0277] The polycarbonate-polyorganosiloxane copolymer represented by the above formula (d) and the compound represented by the above formula (e) are also included as the "impurities" in the polycarbonate-polyorganosiloxane copolymer in this embodiment. Their ratio is preferably [the total number of hydroxyl groups in formula (d) and formula (e)] / [the total number of hydroxyl groups in formula (vi) and formula (d) and formula (e)] The ratio is less than 0.01. If it is less than 0.01, the decrease in transparency and color tone of the PC-POS copolymer caused by molding at high temperature is suppressed, the Δ haze value of the PC-POS copolymer can be set to the above value, and the appearance of the molded product using the copolymer can be appropriately maintained.

[0278] The ratio of [the total number of hydroxyl groups in formula (d) and formula (e)] / [the total number of groups represented by formula (vi) and hydroxyl groups in formula (d) and formula (e)] is more preferably 0.008 or less, further preferably 0.006 or less, and more preferably 0.005 or less.

[0279] The PC-POS copolymer satisfying the above ratio of [the total number of hydroxyl groups in formula (d) and formula (e)] / [the total number of hydroxyl groups in formula (d) and formula (e)] can be prepared by using, for example, a PC-POS copolymer represented by the above general formula (223) wherein R b The polysiloxane is obtained by modifying the polysiloxane with a hydrocarbon alcohol in which the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by the formula (v)] is less than 0.01.

[0280] The above ratios in this specification are 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure Si and the integral value of -O-Si (R 5 )(R 6 Therefore, the ratio of [the total number of hydroxyl groups in formula (d) and formula (e)] / [the total number of hydroxyl groups in formula (d) and formula (e)] can be expressed in another way as [the total number of hydroxyl groups in formula (d) and formula (e)] / [-O-Si(R 5 )(R 6 )-CH2- to the total number of hydroxyl groups in formula (d) and formula (e).

[0281] The polycarbonate-polyorganosiloxane copolymer in another embodiment of the present invention is a polycarbonate-polyorganosiloxane copolymer comprising a polycarbonate block (A-1) containing 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).

[0282] The difference Δhaze between the haze value (haze A) of the polycarbonate-polyorganosiloxane copolymer after being retained at 300° C. or 340° C. for 3 minutes and the haze value (haze B) after being retained at 300° C. or 340° C. for 20 minutes is less than 0.4.

[0283] Contains a polycarbonate-polysiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), wherein the ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of groups represented by formula (v-ii) and the hydroxyl groups in formula (f) and formula (g)] is less than 0.01.

[0284] [Chemical formula 50]

[0285]

[0286] [Where R 1 ~R 6 , X, Z, a, b, n, k are as described above.]

[0287] [Chemical formula 51]

[0288]

[0289] [Wherein, Z is as described above. k is 2 or 3.]

[0290] [Chemical formula 52]

[0291]

[0292] [Where R 3 ~R 6 , n, and k are as described above. (PC) in the formula represents the bond to the polycarbonate block.]

[0293] [Chemical formula 53]

[0294]

[0295] [Where R 3 ~R 6 , n as described above.]

[0296] The polycarbonate-polyorganosiloxane copolymer represented by the above formula (f) and the compound represented by the above formula (g) are contained as the "impurities" in the polycarbonate-polyorganosiloxane copolymer in this embodiment. The ratio of them is preferably [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of hydroxyl groups in formula (v-ii) and formula (f) and formula (g)] is less than 0.01. If it is less than 0.01, the decrease in transparency and color tone of the PC-POS copolymer caused by molding at high temperature is suppressed, the Δ haze value of the PC-POS copolymer can be set to the above value, and the appearance of the molded product using the copolymer can be appropriately maintained.

[0297] 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) contain a group represented by the formula (v-ii).

[0298] The ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of hydroxyl groups in formula (v-ii) and formula (f) and formula (g)] is more preferably 0.008 or less, and further preferably 0.006 or less. Also, it is more preferably 0.005 or less.

[0299] The PC-POS copolymer satisfying the ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of groups represented by formula (v-ii) and hydroxyl groups in formula (f) and formula (g)] can be prepared, for example, by using the above-mentioned general formula (223) wherein R b The polysiloxane is obtained by modifying the polysiloxane with a hydrocarbon alcohol in which the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by the formula (v)] is less than 0.01.

[0300] The above ratios in this specification are 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure Si and the integral value of -O-Si (R 5 )(R 6 Therefore, the ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of hydroxyl groups in formula (f) and formula (g) represented by the group shown in formula (v-ii)] can be expressed in other words as [the total number of hydroxyl groups in formula (f) and formula (g)] / [-O-Si(R 5 )(R 6 )-CH2- to the total number of hydroxyl groups in formula (f) and formula (g).

[0301] After the above-mentioned interfacial polycondensation reaction, the phase can be separated into an aqueous phase and an organic solvent phase by appropriate standing [separation process], the organic solvent phase is washed (preferably with an alkaline aqueous solution, an acidic aqueous solution, and water in that order) [washing process], the obtained organic phase is concentrated [concentration process], and dried [drying process], thereby obtaining a PC-POS copolymer.

[0302] The PC-POS copolymer of the present invention has a characteristic that the difference Δhaze between the haze value (haze A) after the copolymer or its composition is retained at 300°C or 340°C for 3 minutes and the haze value (haze B) after being 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. Usually, when the average chain length of the polyorganosiloxane is relatively long, the haze difference is sometimes not obvious at 300°C, so in this case, the haze difference is measured at a retention temperature of 340°C, but it is not limited to this record. This feature indicates that the PC-POS copolymer of the present invention has excellent transparency and thermal stability.

[0303] Without being bound by theory, as described above, if subjected to a retention test, the siloxane portion is generally decomposed and has poor compatibility with the polycarbonate block portion, so there is a tendency for white turbidity to occur and the haze value to increase. Surprisingly, the present inventors have found that the PC-POS copolymer containing a polycarbonate block having a specific structure and a polyorganosiloxane block having a specific structure has excellent transparency and thermal stability as described above.

[0304] The Δ haze value is preferably 0.3 or less, and more preferably 0.2 or less.

[0305] Specifically, the platinum content of the polycarbonate-polyorganosiloxane copolymer of the present invention is 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 due to platinum can be suppressed, which is preferred.

[0306] The upper limit of the platinum content of the PC-POS copolymer of the present invention is more preferably 0.4 mass ppm or less, further preferably 0.3 mass ppm or less, further preferably 0.1 mass ppm or less, further preferably 50 mass ppb or less, further preferably 10 mass ppb or less, particularly preferably 1.0 mass ppb or less.

[0307] The platinum content in the polyorganosiloxane in the PC-POS copolymer of the present invention is measured using an ICP emission spectrometer.

[0308] Specifically, the organic matter in the PC-POS copolymer can be treated with sulfuric acid ashing, and the residual components can be dissolved with hydrofluoric acid and aqua regia. The platinum content in the copolymer can be measured using an ICP emission analyzer (for example, manufactured by Hitachi High-Tech Sciences, Ltd., trade name: "SPS5100") under the measurement conditions of the standard curve method.

[0309] 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.

[0310] 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 impact resistance of the polycarbonate resin composition finally obtained is more excellent. Although the reason is not clear, it is found that the polycarbonate resin composition of the present invention has extremely excellent impact resistance.

[0311] The average chain length n of the polyorganosiloxane block (A-2) is more preferably 30 or more, further preferably 35 or more, further preferably 40 or more, more preferably 200 or less, further preferably 150 or less, further preferably 100 or less, particularly preferably 95 or less.

[0312] 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 the polyorganosiloxane in the PC-POS copolymer is within the above range, more excellent impact resistance can be obtained. In addition, the decline in handling properties caused by the high content of the polyorganosiloxane can be avoided. If the content of the polyorganosiloxane is below the above upper limit, the obtained copolymer can be fully crushed, and powder agglomeration can be avoided, so it is preferred.

[0313] The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer is more preferably 2% by mass or more, further preferably 3% by mass or more, particularly preferably 4% by mass or more, preferably 45% by mass or less, more preferably 30% by mass or less, further preferably 15% by mass or less, particularly preferably 7% by mass or less.

[0314] The viscosity average molecular weight (Mv) of the PC-POS copolymer can be appropriately adjusted to reach the target molecular weight by using a molecular weight regulator (end capping agent) etc., depending on the application and product used. The viscosity average molecular weight of the PC-POS copolymer is preferably above 9000 and below 50000. If the viscosity average molecular weight is above 9000, a molded product with higher strength can be obtained. If the viscosity average molecular weight is below 50000, injection molding and extrusion molding can be more easily performed at a temperature that does not cause thermal degradation.

[0315] The viscosity average molecular weight of the PC-POS copolymer is more preferably 12,000 or more, further preferably 14,000 or more, particularly preferably 16,000 or more, more preferably 30,000 or less, further preferably 23,000 or less, particularly preferably 22,000 or less, and most preferably 20,000 or less.

[0316] 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 following Schnell equation.

[0317] [Mathematical formula 1]

[0318]

[0319] <Polycarbonate resin composition>

[0320] According to one embodiment of the present invention, a polycarbonate-based resin composition containing the PC-POS copolymer can be provided.

[0321] The polycarbonate resin composition may contain other PC-POS copolymers and other additives within a range that does not impair the effects of the present invention.

[0322] As other PC-POS copolymers, for example, PC-POS copolymers having the following structure can be mentioned.

[0323] [Chemical formula 54]

[0324]

[0325] The PC-POS copolymer may have a structure other than the PC-POS copolymer, and is not particularly limited. 111 , R 112 , X', a1 and b1 are respectively the same as R described in detail in formula (I) 1 , R 2 , X, a and b are the same, and the preferred items and combinations of preferred items are also the same. R in formula (i-II) 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.

[0326] In the above general formula (i-II), R 333 or R 444 The halogen atom represented independently of each other includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 333 or R 444The alkyl group represented independently of each other includes methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 333 or R 444 The alkoxy groups independently represented by each of them include the case where the alkyl moiety is the above-mentioned alkyl group. 333 or R 444 Examples of the aryl group independently represented include phenyl and naphthyl.

[0327] As R 333 and R 444 , preferably all are 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 are methyl groups.

[0328] The polyorganosiloxane block (A-2) containing a repeating unit represented by the general formula (i-II) preferably has units represented by the following general formulae (II-i) to (II-iii).

[0329] [Chemical formula 55]

[0330]

[0331] [Where 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 They may be the same or different from each other. 7 O-、-R 7 COO-、-R 7 NH-, -R 7 NR 8 -、-COO-、-S-、-R 7 COO-R 9 -O- or -R 7 OR 10 -O-, multiple Ys may be the same or different from each other. 7 R represents a single bond, a linear alkylene group, a branched alkylene group or a cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. 9 R represents a diarylene group. 10represents a linear alkylene group, a branched alkylene group or a 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 halide of a dicarboxylic acid. m represents the average chain length of the polyorganosiloxane, m-1, and p and q are each an integer greater than 1 representing the number of repetitions of the polyorganosiloxane unit, and the sum of p and q is m-2.]

[0332] As R 333 ~R 666 The halogen atom represented independently of each other includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 333 ~R 666 The alkyl group represented independently of each other includes methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 333 ~R 666 The alkoxy groups independently represented by each of them include the case where the alkyl moiety is the above-mentioned alkyl group. 333 ~R 666 Examples of the aryl group independently represented include phenyl and naphthyl.

[0333] As R 333 ~R 666 , preferably, they are 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.

[0334] Preferably, R in the general formula (II-i), (II-ii) and / or (II-iii) is 3 ~R 6 All are methyl.

[0335] -R as Y 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 Examples of the linear or branched alkylene group represented by include alkylene groups having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and examples of the cyclic alkylene group include cycloalkylene groups having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

[0336] As 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 may be, for example, the structure of the following general formula (i) or (ii). In the case of an aryl-substituted alkylene group, the alkylene group is bonded to Si.

[0337] [Chemical formula 56]

[0338]

[0339] (In the formula, c represents a positive integer, usually an integer from 1 to 6.)

[0340] R 7 , R 9 and R 10 The diarylene group represented by the formula is a group in which two arylene groups are connected directly or via a divalent organic group. Specifically, the diarylene group has -Ar 1 -W-Ar 2 - represents a group of the structure. 1 and Ar 2 W represents an arylene group, and W represents a single bond or a divalent organic group. Examples of the divalent organic group represented by W include an isopropylidene group, a methylene group, a dimethylene group, and a trimethylene group.

[0341] As R 7 ,Ar 1 and Ar 2 The arylene group represented by includes arylene groups having 6 to 14 ring carbon atoms such as phenylene, naphthylene, biphenylene, and anthracene. These arylene groups may have an optional substituent such as an alkoxy group or an alkyl group.

[0342] As R 8 The alkyl group represented by is a linear or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched alkenyl group having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0343] R 10 The straight chain alkylene group, branched chain alkylene group or cyclic alkylene group represented by R 7 same.

[0344] As Y, -R 7 O-, R 7 It 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.

[0345] As for p and q in formula (II-ii), p=q is preferred.

[0346] β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid, and examples thereof include divalent groups represented by the following general formulae (iii) to (vii).

[0347] [Chemical formula 57]

[0348]

[0349] The number of repetitions of the polyorganosiloxane block (A′-2) in the other PC-POS copolymer is preferably 10 or more and 500 or less, more preferably 20 or more and 300 or less, and even more preferably 30 to 150 or less.

[0350] The repetition number is calculated by nuclear magnetic resonance (NMR) measurement. When the repetition number of the polyorganosiloxane block (A-2) is within the above range, both excellent transparency and flexibility can be achieved, and peeling after the production of the molded article can be suppressed.

[0351] The content of the polyorganosiloxane block (A'-2) in other PC-POS copolymers is preferably 1% by mass or more and 50% by mass or less, more preferably 2% by mass or more and 45% by mass or less, further preferably 3% by mass or more and 30% by mass or less, and still further preferably 3% by mass or more and less than 20% by mass.

[0352] The viscosity average molecular weight (Mv) of other PC-POS copolymers can be appropriately adjusted to reach the target molecular weight by using a molecular weight regulator (end capping agent) etc. according to the application and product used. The viscosity average molecular weight of other PC-POS copolymers is preferably 9000 or more and 50000 or less. If the viscosity average molecular weight is 9000 or more, a molded product with higher strength can be obtained. If the viscosity average molecular weight is 50000 or less, injection molding and extrusion molding can be more easily performed at a temperature that does not cause thermal degradation.

[0353] The viscosity average molecular weight of other PC-POS copolymers is more preferably 12,000 or more, further preferably 14,000 or more, particularly preferably 16,000 or more, more preferably 30,000 or less, further preferably 23,000 or less, particularly preferably 22,000 or less, and most preferably 20,000 or less.

[0354] 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 following Schnell equation.

[0355] [Mathematical formula 2]

[0356]

[0357] The above-mentioned other polycarbonate-polyorganosiloxane copolymers can be manufactured by known manufacturing methods such as interfacial polymerization (phosgene method), pyridine method and transesterification method. In particular, when the interfacial polymerization method is adopted, it is easy to separate the organic phase containing the PC-POS copolymer from the aqueous phase containing unreacted substances, catalyst residues, etc., and it is easy to separate the organic phase containing the PC-POS copolymer from the aqueous phase in each cleaning process such as alkali cleaning, acid cleaning, and pure water cleaning. Therefore, the PC-POS copolymer can be obtained efficiently. As a method for manufacturing the PC-POS copolymer, for example, the method described in Japanese Patent Gazette No. 2014-80462 can be referred to.

[0358] Examples of other additives include antioxidants, alicyclic epoxy compounds, ultraviolet absorbers, mold release agents, reinforcing materials, fillers, elastomers for improving impact resistance, dyes, pigments, antistatic agents, and resins other than polycarbonate.

[0359] The blending and kneading can be carried out by the following methods: pre-mixing is carried out using commonly used equipment, such as a ribbon mixer, a drum mixer, etc., and using a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi-screw extruder, and a co-kneader, etc. The heating temperature during kneading is usually appropriately selected within the range of more than 240° C. and less than 320° C. As the melt kneading, an extruder, especially a vented extruder, is preferably used.

[0360] [Molding products]

[0361] The polycarbonate resin composition of the present invention which has been melt-kneaded as described above, or the obtained pellets can be used as raw materials to produce various molded bodies by injection molding, injection compression molding, extrusion molding, blow molding, stamping molding, vacuum molding, foam molding, 3D printers, etc. In particular, the pellets obtained by melt-kneading can be suitably used for the production of injection molded bodies by injection molding and injection compression molding.

[0362] The molded articles formed from the PC-POS copolymer of the present invention and the polycarbonate resin composition containing the copolymer can be suitably used as, for example, exterior and interior parts of parts for electrical and electronic equipment such as televisions, radios, cameras, camcorders, audio players, DVD players, air conditioners, mobile phones, smart phones, walkie-talkies, displays, computers, tablet terminals, portable game devices, fixed game devices, wearable electronic devices, cash registers, calculators, copiers, printers, fax machines, communication base stations, batteries, robots, etc.; exterior and interior parts of automobiles, railways, ships, aircraft, space industry equipment, and medical equipment; and parts of building materials, etc.

[0363] Example

[0364] The present invention will be further described in detail by way of examples, but the present invention is not limited to these examples. The characteristic values ​​and evaluation results in each example were obtained according to the following procedures.

[0365] (1) Polydimethylsiloxane chain length and content

[0366] The integrated value ratio of the methyl group of polydimethylsiloxane is calculated by NMR measurement. In addition, in this specification, polydimethylsiloxane may be abbreviated as PDMS.

[0367] <Quantitative method for chain length of polydimethylsiloxane>

[0368] 1 H-NMR measurement conditions

[0369] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0370] Probe: 50TH5AT / FG2

[0371] Observation range: -5~15ppm

[0372] Observation center: 5ppm

[0373] Pulse repetition time: 9 seconds

[0374] Pulse width: 45°

[0375] NMR sample tube: 5φ

[0376] Sample amount: 30-40 mg

[0377] Solvent: deuterated chloroform

[0378] Measuring temperature: room temperature

[0379] Total times: 256 times

[0380] Allylphenol-terminated polydimethylsiloxane

[0381] A: Integrated value of the methyl group of the dimethylsiloxane part observed at δ -0.02 to 0.5

[0382] B: Integrated value of the methylene group of allylphenol observed around δ2.50-2.75

[0383] Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0384] Eugenol-terminated polydimethylsiloxane

[0385] A: Integrated value of the methyl group of the dimethylsiloxane part observed at δ -0.02 to 0.5

[0386] B: Integrated value of the methylene group of eugenol observed around δ2.40-2.70

[0387] Chain length of polydimethylsiloxane = (A / 6) / (B / 4)

[0388] <Quantitative method for determining the content of polydimethylsiloxane>

[0389] Method for quantifying the amount of polydimethylsiloxane copolymerized in PTBP-terminated polycarbonate copolymerized with allylphenol-terminated polydimethylsiloxane

[0390] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0391] Probe: 50TH5AT / FG2

[0392] Observation range: -5~15ppm

[0393] Observation center: 5ppm

[0394] Pulse repetition time: 9 seconds

[0395] Pulse width: 45°

[0396] Total times: 256 times

[0397] NMR sample tube: 5φ

[0398] Sample amount: 30-40 mg

[0399] Solvent: deuterated chloroform

[0400] Measuring temperature: room temperature

[0401] A: Integrated value of the methyl group in the BPA moiety observed near δ1.5 to 1.9

[0402] B: Integrated value of the methyl group of the dimethylsiloxane part observed at δ -0.02 to 0.3

[0403] C: Integrated value of butyl groups in the p-tert-butylphenyl moiety observed at δ 1.2 to 1.4

[0404] a=A / 6

[0405] b=B / 6

[0406] c=C / 9

[0407] T=a+b+c

[0408] f=a / T×100

[0409] g=b / T×100

[0410] h=c / T×100

[0411] TW=f×254+g×74.1+h×149

[0412] PDMS (wt%) = g × 74.1 / TW × 100

[0413] (2) Viscosity average molecular weight

[0414] The viscosity average molecular weight (Mv) was determined by measuring the viscosity of a dichloromethane solution at 20° C. using an Ubbelohde viscometer to determine the intrinsic viscosity [η], which was calculated using the following formula (Schnell formula).

[0415] [Mathematical formula 3]

[0416]

[0417] (3) 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)]

[0418] is 29 In the Si-NMR spectrum, the -O-Si(R 5 )(R 6 )-CH2- structure Si and the integral value derived from -O-Si(R 5 )(R 6 )-OZ-structured Si. Hereinafter, it is also referred to as "terminal impurity ratio".

[0419] (4) Ratio of [the number of hydroxyl groups in formula (f) and formula (g)] / [the total number of the group represented by formula (v-ii) and the number of hydroxyl groups in formula (f) and formula (g)]

[0420] In a 100 mL conical flask, 3 g of the PC-POS copolymer described in the following manufacturing example was dissolved in 20 mL of dichloromethane, and 30 mL of a 1 wt% sodium hydroxide / methanol solution was added to the resulting solution, and stirred at room temperature for 2 hours. After stirring, the mixture in the conical flask was naturally filtered using a chrysanthemum filter paper (150 mm, No. 5C, manufactured by Toyo Filter Paper Co., Ltd.). 10 mL of dichloromethane was added to the solid remaining on the filter paper and the above-mentioned conical flask for washing, and the washing liquid was filtered using the above-mentioned chrysanthemum filter paper, and the above-mentioned process was repeated twice.

[0421] In a separating funnel, add the total amount of the liquid through filter paper, methylene chloride 40mL and pure water 50mL, after vigorous vibration, stand for 1 minute to separate water and organic phase, isolate organic phase.Afterwards, in the water remaining in the separating funnel, add methylene chloride 20mL, after vigorous vibration, stand for 1 minute to separate water and organic phase, isolate organic phase.In a separating funnel, add isolated whole organic phases and 1N sodium hydroxide aqueous solution 35ml and vigorous vibration, stand for 1 minute to separate water and organic phase, isolate organic phase, after the above-mentioned procedure is repeated 2 times, 1N sodium hydroxide aqueous solution is changed to 1N hydrochloric acid aqueous solution, and the same procedure is repeated 2 times.

[0422] 5.0 g of sodium sulfate was added to the separated organic phase and stirred, and then the sodium sulfate in the solution was removed by suction filtration. After suction filtration, the filtrate was concentrated to dryness by an evaporator (water bath temperature: 40°C), and the obtained oily substance was subjected to 29 The Si-NMR measurement was performed to calculate the ratio of [the hydroxyl groups in the formula (f) and (g)] / [the total number of the group represented by the formula (v-ii) and the hydroxyl groups in the formula (f) and (g)].

[0423] It should be noted that the ratio of [the hydroxyl groups in formula (f) and (g)] / [the total number of the groups represented by formula (v-ii) and the hydroxyl groups in formula (f) and (g)] is also equivalent to the ratio of [the total number of the hydroxyl groups in formula (d) and (e)] / [the total number of the groups represented by formula (vi) and the hydroxyl groups in formula (d) and (e)].

[0424] < 29 Si-NMR measurement conditions>

[0425] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0426] Probe: FG probe corresponding to 10φNMR sample tube

[0427] Observation core: 29 Si

[0428] Observation range: -65~35ppm

[0429] Observation center: -15ppm

[0430] Pulse repetition time: 18.3 seconds

[0431] Pulse width: 90°

[0432] Cumulative times: 5000 times

[0433] NMR sample tube: 10φ

[0434] Sample size: 750 mg

[0435] Relaxation reagent: tris(acetylacetonate)chromium(III) 20mM

[0436] Solvent: deuterated chloroform

[0437] Measuring temperature: room temperature

[0438] A: Integrated value of Si bonded to allylphenol observed at δ7.5-9.0 ppm

[0439] B: Integrated value of silanol observed at δ-9.6 to -9.9 ppm

[0440] [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)]=B / (A+B)

[0441] Preparation Example 1

[0442] <Production of alkyl alcohol-modified polyorganosiloxane: PDMS-A>

[0443] Into a 150 L tubular reactor, 132 kg / hour of an organohydrogenpolysiloxane represented by the following average formula (2-1) heated to 50° C., 14.5 kg / hour of 2-allylphenol, and 0.08 ppm by mass of a platinum catalyst (a toluene solution of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a neutralized product of chloroplatinic acid) were supplied, respectively, and reacted at 80° C. for 20 minutes in the tubular reactor, and then continuously taken out to a storage tank.

[0444] Thereafter, excess 2-allylphenol was removed at 160° C. using a thin film evaporator to synthesize a hydrocarbyl alcohol-modified polyorganosiloxane represented by the following average formula (II-I). The terminal impurity ratio of the obtained hydrocarbyl alcohol-modified polyorganosiloxane was 0.0015.

[0445] It should be noted that formula (2-1) and formula (II-I) are average formulas, and "36" refers to the average number of repetitions of dimethylsiloxane units.

[0446] [Chemical formula 58]

[0447]

[0448] [Chemical formula 59]

[0449]

[0450] Preparation Example 2

[0451] <Production of alkyl alcohol-modified polyorganosiloxane: PDMS-B>

[0452] Into a 150 L tubular reactor, 380 kg / hour of an organohydrogenpolysiloxane represented by the following average formula (2-11) heated to 50° C., 19 kg / hour of 2-allylphenol, and 0.10 ppm by mass of a platinum catalyst (a toluene solution of a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of a neutralized product of chloroplatinic acid) were supplied, respectively, and after being allowed to react at 80° C. for 20 minutes, the mixture was continuously taken out to a storage tank.

[0453] Thereafter, excess 2-allylphenol was removed at 160° C. using a thin film evaporator to synthesize a hydrocarbyl alcohol-modified polyorganosiloxane represented by the following average formula (II-I′). The terminal impurity ratio of the obtained hydrocarbyl alcohol-modified polyorganosiloxane was 0.0025.

[0454] It should be noted that formula (2-11) and formula (II-I') are average formulas, and "89" refers to the average repeating number of dimethylsiloxane units.

[0455] [Chemical formula 60]

[0456]

[0457] [Chemical formula 61]

[0458]

[0459] Preparation Example 3

[0460] <Production of alkyl alcohol-modified polyorganosiloxane: PDMS-C>

[0461] The same operation as in the preparation of PDMS-B was performed 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 hydrocarbyl alcohol-modified polyorganosiloxane was 0.0010.

[0462] <KF-2201>

[0463] KF-2201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., lot. 801015) was produced by methanol-modifying the organosiloxane in Preparation Example 1 by a batch reaction.

[0464] <KF-1922>

[0465] KF-1922 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., lot. 704020) was produced by methanol-modifying the organosiloxane in Preparation Example 2 by performing a batch reaction.

[0466] <Manufacturing of polycarbonate oligomer>

[0467] 2000 ppm of sodium dithionite was added to a 5.6 mass % sodium hydroxide aqueous solution relative to bisphenol A (BPA) to be dissolved later, and BPA was dissolved therein so that the BPA concentration was 13.5 mass %, thereby preparing a sodium hydroxide aqueous solution of BPA.

[0468] The sodium hydroxide aqueous solution of BPA was continuously introduced into a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 L / hour, dichloromethane at 15 L / hour, and phosgene at 4.0 kg / hour. The tubular reactor had a jacket portion, and cooling water was introduced into the jacket to maintain the temperature of the reaction liquid at 40°C or less. The reaction liquid discharged from the tubular reactor was continuously introduced into a tank reactor with baffles having an internal volume of 40 L and equipped with swept blades, and further sodium hydroxide aqueous solution of BPA was added at a flow rate of 2.8 L / hour, 25 mass % sodium hydroxide aqueous solution at 0.07 L / hour, water at 17 L / hour, and 1 mass % triethylamine aqueous solution at 0.64 L / hour to carry out the reaction. The reaction liquid overflowing from the tank reactor was continuously discharged, the aqueous phase was removed by static separation, and the dichloromethane phase was collected.

[0469] The polycarbonate oligomer thus obtained had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.

[0470] <Production Examples 1 to 8 of Polycarbonate-Polyorganosiloxane Copolymers>

[0471] The values ​​(i) to (xiv) described below represent the usage amounts of the respective components, as shown in Table 1.

[0472] In a 50 L tank reactor equipped with baffles, a paddle stirring blade and a cooling jacket, (i) kg of the polycarbonate oligomer solution (PCO) produced as described above, (ii) kg of dichloromethane (MC), (iv) g of a solution prepared by dissolving allylphenol-terminated polydimethylsiloxane having an average chain length n=(iii) of polydimethylsiloxane (hereinafter sometimes referred to as PDMS) in dichloromethane (MC), (v) L of triethylamine (TEA), and (vi) mL of triethylamine (TEA), 8.0 mass % of an aqueous sodium hydroxide solution (NaOHaq) (vii) g was added thereto with stirring, and a reaction between the polycarbonate oligomer and the allylphenol-terminated PDMS was carried out for 20 minutes (preliminary polymerization step).

[0473] To the polymerization liquid, a dichloromethane solution of p-tert-butylphenol (PTBP) (formed by dissolving (viii) g of PTBP in (ix) L of dichloromethane) and an aqueous sodium hydroxide solution of BPA (formed by dissolving (xiii) g of BPA in an aqueous solution formed by dissolving (x) g of NaOH and (xi) g of sodium dithionite (Na2S2O4) in (xii) L of water) were added, and a polymerization reaction was carried out for 60 minutes (main polymerization step).

[0474] Methylene chloride (MC) (xiv) kg was added for dilution, and after stirring for 10 minutes, 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 separated.

[0475] The thus obtained dichloromethane solution of PC-POS copolymer was washed with 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid in sequence at 15 vol% relative to the solution, and then repeatedly washed with pure water until the conductivity of the aqueous phase after washing reached 0.01 μS / m or less.

[0476] The dichloromethane solution of the polycarbonate obtained by washing was concentrated, and 3 L of acetone (Wako Pure Chemical Industries, Ltd., special grade) was added, and the solid obtained was pulverized after further concentration, and the obtained powder was dried at 100° C. under reduced pressure. The PDMS concentration, viscosity average molecular weight, and ratio of [hydroxyl groups in formula (f) and formula (g)] / [the total number of groups represented by formula (v-ii) and hydroxyl groups in formula (f) and formula (g)] of the obtained sheet were measured, and the results are shown in Tables 1 and 2.

[0477] [Table 1]

[0478]

[0479] [Table 2]

[0480]

[0481] <Other ingredients>

[0482] Antioxidant: IRGAFOS168 [Tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Japan Ltd.]

[0483] Examples 1 to 6, Comparative Examples 1 to 2, Reference Examples 1 to 8

[0484] The PC-POS copolymers A1 to A5 obtained in the above-mentioned Production Examples were used to carry out the later-described retention thermal stability evaluation (1).

[0485] 100 parts by mass of each of the PC-POS copolymers A6 to A8 obtained in the above manufacturing example was mixed with 0.10 parts by mass of Irgafos 168, and supplied to a vented twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd.), and melt-kneaded at a screw speed of 150 rpm, a discharge rate of 20 kg / hour, and a resin temperature of 295 to 310° C. to prepare pellet samples, and the retention heat stability evaluation (2) described later was performed. The results are shown in Table 4.

[0486] The PC-POS copolymer and other components were mixed in the proportions shown in Table 5, supplied to a vented twin-screw extruder (TEM35B manufactured by Toshiba Machine Co., Ltd.), melt-kneaded at a screw speed of 150 rpm, a discharge rate of 20 kg / hour, and a resin temperature of 295 to 310°C, to prepare pellet samples for evaluation, and subjected to the physical property tests described below. The results are shown in Table 5.

[0487] [Table 3]

[0488]

[0489] [Table 4]

[0490]

[0491] [Table 5]

[0492]

[0493] [Evaluation test]

[0494] <Liquidity Rating>(MVR)

[0495] Using the pellets, the amount of molten resin (ml / 10 minutes) flowing out from a die having a diameter of 2.095±0.005 mm and a length of 8.000±0.025 mm was measured at 300° C. and a load of 1.2 kg in accordance with JIS K 7210-1:2014.

[0496] <Q value (flow value)〔unit; 10 -2 mL / sec〕>

[0497] The pellets were used to measure the amount of molten resin (10 μm) flowing out of a nozzle having a diameter of 1.00 mm and a length of 10.00 mm at 280° C. and a pressure of 160 kgf using an elevated flow tester in accordance with JIS K 7210-1:2014: Annex JA. - 2 mL / sec). The Q value indicates the outflow per unit time. The higher the value, the better the fluidity.

[0498] <Impact resistance>

[0499] After drying the pellets obtained above at 100°C for 8 hours, an injection molding machine (NEX110 manufactured by Nissei Plastic Industry Co., Ltd., screw diameter 36 mmφ) was used to perform injection molding at a barrel temperature of 280°C and a mold temperature of 80°C to prepare an IZOD test piece (length 63.5 mm, width 12.7 mm, thickness 3.2 mm). Using a test piece to which a notch (r = 0.25 mm ± 0.05 mm) was given by subsequent processing, the notched Izod impact strength at -30°C, -20°C, -10°C, 0°C and 23°C was measured in accordance with ASTM standard D-256.

[0500] <Load deflection temperature: HDT (unit: °C)>

[0501] After drying the pellets obtained above at 100° C. for 8 hours, an injection molding machine (NEX110 manufactured by Nissei Plastic Industry Co., Ltd., screw diameter 36 mmφ) was used to perform injection molding at a barrel temperature of 280° C. and a mold temperature of 80° C. to obtain a test piece (length 127 mm, width 12.7 mm, thickness 3.2 mm). Using this test piece, according to ASTM standard D-648, the temperature increase rate was 120° C. / hour, the distance between the fulcrums was 100 mm, and a load of 1.83 MPa was applied, and the temperature when the deflection of the test piece based on the side-standing (Edgewise) reached 0.26 mm was recorded.

[0502] <Evaluation of thermal stability of retention (1)>

[0503] The obtained powder was subjected to a retention heat stability test by injection molding as shown below, and the haze values ​​of the obtained molded products were measured. The difference between the haze value (haze A) at a retention time of 3 minutes and the haze value (haze B) at a retention time of 20 minutes was obtained as Δhaze. The haze value was measured 3 times based on ISO 14782:1999, and the average was obtained. The results are shown in Table 3.

[0504] In addition, the haze value when injection molding was performed using the powder of Example 1 was 0.4.

[0505] 〈Injection molding〉

[0506] Injection molding machine: MD50 (trade name) manufactured by NIIGATA MACHINE TECHNO Co., Ltd.

[0507] Shape of molded product: 90mm×50mm 3-stage plate (3mm thickness part 45mm, 2mm thickness part 22.5mm, 1mm thickness part 22.5mm)

[0508] Molding machine barrel temperature: 300℃

[0509] Retention time in barrel: 3 minutes or 20 minutes

[0510] Mold temperature: 80℃

[0511] <Evaluation of thermal stability of retention (2)>

[0512] The obtained pellets were subjected to a retention heat stability test by injection molding as shown below, and the haze values ​​of the obtained molded products were measured. The difference between the haze value (haze A) when the retention time was 3 minutes and the haze value (haze B) when the retention time was 20 minutes was obtained as Δhaze. The haze value was measured 3 times based on ISO 14782:1999, and the average was obtained. The results are shown in Table 4.

[0513] 〈Injection molding〉

[0514] Injection molding machine: EC40 (trade name) manufactured by Toshiba Machine Co., Ltd.

[0515] Shape of molded product: 80mm×40mm×3.2mm

[0516] Molding machine barrel temperature: 340℃

[0517] Retention time in barrel: 3 minutes or 20 minutes

[0518] Mould temperature: 80℃.

Claims

1. A polycarbonate-polyorganosiloxane copolymer, comprising: A polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I), and A polyorganosiloxane block (A-2) comprising a repeating unit represented by the following general formula (II), The difference Δhaze between the haze value of the polycarbonate-polyorganosiloxane copolymer after retention at 300° C. or 340° C. for 3 minutes, i.e., haze A, and the haze value of the polycarbonate-polyorganosiloxane copolymer after retention at 300° C. or 340° C. for 20 minutes, i.e., haze B, is less than 0.

4. 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-, -SO2-, -O-, or -CO-; a and b each independently represent an integer from 0 to 4; 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; n represents the average chain length of the polyorganosiloxane, and n-1 is an integer greater than 1 representing the number of repetitions of the polyorganosiloxane unit; Z represents a divalent hydrocarbon group, at least one of the hydrogen atoms contained in the divalent hydrocarbon group is optionally substituted by 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 is optionally substituted by an oxygen atom, a nitrogen atom, or a sulfur atom; and k represents an integer of 2 or 3.

2. The polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein The platinum content is 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): In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, at least one of the hydrogen atoms contained in the monovalent hydrocarbon group is optionally substituted by a halogen atom, and at least one of the carbon atoms of the monovalent hydrocarbon group is optionally substituted by an oxygen atom, a nitrogen atom or a sulfur atom, w is an integer of 0 to 4, and the wavy line represents the 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. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 4, wherein Containing a polycarbonate-polysiloxane copolymer represented by the following general formula (f) and a compound represented by the following general formula (g), wherein the ratio of [the total number of hydroxyl groups in formula (f) and formula (g)] / [the total number of the group represented by formula (v-ii) and the hydroxyl groups in formula (f) and formula (g)] is less than 0.01, Wherein, Z is as described above; k is 2 or 3; In the formula, R 3 ~R 6 , n, k are as described above; (PC) in the formula represents bonding to the polycarbonate block; In the formula, R 3 ~R 6 , n as described above.

6. A polycarbonate-polyorganosiloxane copolymer obtained as follows: The organohydrogensiloxane represented by the following general formula (2), the compound represented by the following general formula (3), and a platinum catalyst are continuously supplied to a reactor, and are subjected to a hydrosilylation reaction while passing through the reactor to obtain a hydrocarbyl alcohol-modified polyorganosiloxane. The polycarbonate-polyorganosiloxane copolymer is obtained by copolymerizing the alkyl alcohol-modified polyorganosiloxane with a dihydric phenol and a carbonate precursor, or copolymerizing the alkyl alcohol-modified polyorganosiloxane with an oligomer having a repeating unit represented by the following general formula (I). 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 are optionally the same or different from each other, and f is an integer from 0 to 500; In the formula, R 22 represents a vinyl group or an allyl group, and Z represents a divalent hydrocarbon group, wherein at least one of the hydrogen atoms contained in the divalent hydrocarbon group is optionally substituted by a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and at least one of the carbon atoms of these divalent hydrocarbon groups and monovalent hydrocarbon groups is optionally substituted by an oxygen atom, a nitrogen atom or a sulfur atom; 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 fluorene diyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-; a and b each independently represent an integer of 0 to 4.

7. The polycarbonate-polyorganosiloxane copolymer according to claim 6, wherein The amount of the platinum catalyst used is 0.005 ppm by mass or more and less than 1.0 ppm by mass in terms of platinum metal relative to 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 claim 6 or 7, wherein The amount of the platinum catalyst used is 0.005 mass ppm or more and 0.2 mass ppm or less in terms of platinum metal relative to 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 claims 6 to 8, wherein The compound represented by the general formula (3) is a compound represented by the following general formula (33), In the formula, Q represents a halogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, at least one of the hydrogen atoms contained in the monovalent hydrocarbon group is optionally substituted by a halogen atom, at least one of the carbon atoms of the monovalent hydrocarbon group is optionally substituted by an oxygen atom, a nitrogen atom or a sulfur atom, and w is an integer of 0 to 4.

10. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 6 to 9, wherein As the hydrocarbon alcohol-modified polyorganosiloxane, a polyorganosiloxane represented by the following general formula (222) is used, wherein R a a hydrocarbon alcohol-modified polyorganosiloxane wherein 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 less than 0.01, In the formula, R 3 ~R 6 , f as described above; R a Each is independently a group represented by the following general formula (v) or (vi): Wherein, Z is as described above; k is 2 or 3; Wherein, Z is as described above; R 33 represents a vinyl group, an allyl group, or a -(CH2) group derived from the reaction of Si-H of the following general formula (2) with a vinyl group or an allyl group k -SiR 5 R 6 O-terminal group, k is 2 or 3; In the formula, R 3 ~R 6 , f as described above.

11. The polycarbonate-polyorganosiloxane copolymer according to claim 10, wherein 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), [{-OZR in formula (b) and formula (c) 33 } total number of groups represented by formula (vi) and {-OZR in formula (b) and formula (c) 33 The total number of groups represented by In the formula, R 3 ~R 6 , f as described above; R a-i Each is independently a group represented by the following general formula (vi): wherein Z is as described above; the oxygen atom of formula (vi) is bonded to the polycarbonate unit; k is 2 or 3; In the formula, R 3 ~R 6 , Z, R 33 , f, k are as described above; (PC) in the formula represents bonding to the polycarbonate block; In the formula, R 3 ~R 6 , Z, R 33 , f as described above.

12. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 6 to 9, wherein As the hydrocarbon alcohol-modified polyorganosiloxane, a polyorganosiloxane represented by the following general formula (223) is used, wherein R b a hydrocarbon alcohol-modified polyorganosiloxane wherein the ratio of [the number of hydroxyl groups] / [the total number of hydroxyl groups and the groups represented by formula (v)] is less than 0.01, In the formula, R 3 ~R 6 , f as described above; R a Each is independently a hydroxyl group or a group represented by the following general formula (v): In the formula, Z is as described above; k is 2 or 3.

13. The polycarbonate-polyorganosiloxane copolymer according to claim 12, wherein A polycarbonate-polyorganosiloxane copolymer containing 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 hydroxyl groups in formula (d) and formula (e)] / [the total number of groups represented by formula (vi) and the hydroxyl groups in formula (d) and formula (e)] is less than 0.01, In the formula, R 3 ~R 6 , f as described above; R b-i Each is independently a group represented by the following general formula (vi): wherein Z is as described above; the oxygen atom of formula (vi) is bonded to the polycarbonate unit; k is 2 or 3, In the formula, R 3 ~R 6 , f, k are as described above; (PC) in the formula represents the bonding with the polycarbonate block, In the formula, R 3 ~R 6 , f as described above. 14 . A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to claim 1 . 15 . A molded article formed from the polycarbonate resin composition according to claim 14 .

Images