Polycarbonate resin composition and molded article

Abstract

The present invention is: [1] a polycarbonate resin composition containing an elastomer (B) and a polycarbonate resin (S) that includes a polycarbonate-polyorganosiloxane copolymer (A) having a polyorganosiloxane block (A-1) containing a specific structural unit and a polycarbonate block (A-2) containing a specific structural unit; and [2] a molded article containing the polycarbonate resin composition described in [1].

Description

[Technical Field]

[0001] This invention relates to polycarbonate-based resin compositions and molded articles. [Background technology]

[0002] Polycarbonate-polyorganosiloxane copolymers are attracting attention due to their excellent properties such as impact resistance, chemical resistance, and flame retardancy. Therefore, they are expected to have a wide range of applications in various fields, including electrical and electronic equipment and the automotive industry. Examples of technologies relating to such polycarbonate-polyorganosiloxane copolymers include those described in Patent Documents 1 and 2.

[0003] Patent Document 1 describes a method for producing a polysiloxane / polycarbonate block cocondensation product, which involves reacting (a) a hydroxyaryloxy-terminated dimethylsiloxane and (b) an oligocarbonate having a weight-average molecular weight of 3000 to 24000 and a molar ratio of OH-terminated groups to aryl-terminated groups of 10:90 to 70:30 in a molten state at a temperature of 250 to 320°C and a pressure of 0.01 to 100 millibars, with the weight ratio of (a) to (b) being between 1:99 and 40:60.

[0004] Patent Document 2 describes a method for producing a polysiloxane-polycarbonate block cocondensate, comprising reacting a polydialkylsiloxane having at least one hydroxyaryl terminus with at least one polycarbonate in a molten product, wherein the method is carried out in at least two steps, using a reactor combination consisting of at least one pre-reactor, a high-viscosity reactor, and a discharge device. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 10-251408 [Patent Document 2] Special Publication No. 2016-532733 [Overview of the project] [Problems that the invention aims to solve]

[0006] According to our investigations, it has become clear that polycarbonate-polyorganosiloxane copolymers obtained by compounding an elastomer with polycarbonate-polyorganosiloxane copolymers having aryl terminology, such as those described in Patent Documents 1 and 2, have room for improvement in terms of the balance between tensile properties and impact resistance.

[0007] The present invention has been made in view of the above circumstances, and provides a polycarbonate-based resin composition that can produce molded articles with an improved balance of tensile properties and impact resistance. Furthermore, the present invention provides a polycarbonate-based resin molded article with an improved balance of tensile properties and impact resistance. [Means for solving the problem]

[0008] The present inventors have found that a polycarbonate-polyorganosiloxane copolymer (A) having a specific structure and an elastomer (B) can provide a molded article with an improved balance of tensile properties and impact resistance.

[0009] In other words, the present invention provides the following polycarbonate-based resin composition and molded article.

[0010] [1] A polycarbonate-polyorganosiloxane copolymer (A) having a polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) and a polycarbonate block (A-2) containing a structural unit represented by general formula (2), and a polycarbonate resin (S) comprising these, A polycarbonate resin composition containing elastomer (B). [ka] [In the formula, R 1 ~R 4 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C12 aryl group, or a C7-C22 alkylaryl group. 6 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of -. Multiple R 8 These may be the same or different, and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of -. 111 represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. z and u represent 0 or 1. a represents an integer from 2 to 500, and b represents an integer from 2 to 200. R 10 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. These groups may be substituted with substituents and may contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms. y represents an integer between 10 and 500. [2] The polycarbonate resin composition according to [1], wherein the polycarbonate block (A-2) comprises at least one of a structural unit represented by general formula (111) and a structural unit represented by general formula (112). [ka] [wherein, R 55 and R 56 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O- or -CO-. R 100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, the divalent aliphatic hydrocarbon group may optionally contain at least one selected from the group consisting of a branched structure and a cyclic structure, and may optionally contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. y represents an integer of 10 to 500. s and t each independently represent an integer of 0 to 4.]] [3] The polycarbonate-based resin composition according to [1] or [2], wherein the polycarbonate block (A-2) comprises a structural unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecene, isosorbide, cyclohexane-1,4-dimethanol, tricyclodecanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol. [4] The polycarbonate-based resin composition according to any one of [1] to [3], wherein the polycarbonate block (A-2) comprises at least one selected from the group consisting of structural units represented by general formulas (a-i) to (a-v). [ka] [5] A polycarbonate resin composition according to any one of [1] to [4], wherein a is an integer between 2 and 300. [6] A polycarbonate resin composition according to any one of [1] to [5], wherein b is 10 or more. [7] The polycarbonate resin composition according to any one of [1] to [6], wherein the polyorganosiloxane block (A-1) comprises at least one selected from the group consisting of structural units represented by general formulas (1-1) to (1-3). [ka] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, and b have the same meaning as above. 5 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of -. 7 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of - 111 This represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 1 b represents 0 or 1. 1 β represents an integer between 2 and 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide. [8] The aforementioned R 1 ~R 4 A polycarbonate resin composition according to any one of the above [1] to [7], wherein all of the groups are methyl groups. [9] The aforementioned R 6 A polycarbonate resin composition according to any one of the above [1] to [8], wherein is a trimethylene group.

[10] The aforementioned R 8 A polycarbonate resin composition according to any one of [1] to [9], wherein is a dimethylene group, a methyl-substituted dimethylene group (-CH2CHMe-), or a trimethylene group, and z is 1.

[11] A polycarbonate-based resin composition according to any one of [1] to

[10] , wherein the polycarbonate-polyorganosiloxane copolymer (A) contains 0.1% by mass or more and 60% by mass or less of the polyorganosiloxane block (A-1).

[12] A polycarbonate-based resin composition according to any one of [1] to

[11] , wherein the viscosity-average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is 5,000 or more and 50,000 or less.

[13] A polycarbonate resin composition according to any one of [1] to

[12] above, wherein a molded piece obtained by molding the polycarbonate resin composition, which is a JIS K 7139:2009 dumbbell-type tensile test specimen type A22, has a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, has a tensile elongation at break of 10% or more, as measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm.

[14] A polycarbonate resin composition according to any one of [1] to

[13] above, obtained by molding the polycarbonate resin composition, measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm, wherein the molded piece, a JIS K 7139:2009 dumbbell-type tensile test specimen type A22, has a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, has a tensile modulus of 2250 MPa or more.

[15] In accordance with ISO-179-1:2010, the Charpy impact strength of a molded piece obtained by molding the polycarbonate resin composition, measuring 80 mm in length, 10 mm in width, and 4 mm in thickness, and to which a notch (r=0.25 mm ± 0.05 mm) was added by post-processing, measured at a measurement temperature of 23°C, was 38 kJ / m². 2 The polycarbonate resin composition described in any of the above [1] to

[14] .

[16] A polycarbonate-based resin composition according to any one of [1] to

[15] , wherein the elastomer (B) comprises a core / shell type graft copolymer.

[17] The polycarbonate resin composition according to any one of [1] to

[16] , wherein the elastomer (B) comprises at least one selected from the group consisting of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-acrylic rubber copolymer, methyl methacrylate-acrylic rubber-styrene copolymer, methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic / silicone IPN rubber) copolymer.

[18] The polycarbonate resin composition according to any one of [1] to

[17] , wherein the content of the elastomer (B) is 1.0 part by mass or more and 40 parts by mass or less per 100 parts by mass of the polycarbonate resin (S).

[19] The polycarbonate-polyorganosiloxane copolymer (A) is a copolymer obtained by melt polymerization, the polycarbonate-based resin composition according to any one of [1] to

[18] above.

[20] The polycarbonate-polyorganosiloxane copolymer (A) is a copolymer obtained using a diol monomer (a1), the polycarbonate-based resin composition according to any one of [1] to

[19] above. [twenty one] A molded article comprising the polycarbonate resin composition described in any of the above [1] to

[20] . [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a polycarbonate-based resin composition that can produce a molded article with an improved balance of tensile properties and impact resistance, and a polycarbonate-based resin molded article with an improved balance of tensile properties and impact resistance. [Modes for carrying out the invention]

[0012] The polycarbonate resin composition and molded articles thereof of the present invention will be described in detail below. In this specification, the provisions that are considered preferred can be adopted at will, and combinations of preferred provisions are considered more preferred. In this specification, the notation "XX~YY" means "XX or more and YY or less". If, with respect to a single technical matter, there are multiple lower limits such as "x or greater," or multiple upper limits such as "y or less," then these upper and lower limits may be arbitrarily selected and combined.

[0013] 1. Polycarbonate resin composition The polycarbonate resin composition of the present invention contains a polycarbonate resin (S) comprising a polycarbonate-polyorganosiloxane copolymer (A) having a polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) and a polycarbonate block (A-2) containing a structural unit represented by general formula (2), and an elastomer (B). According to the polycarbonate-based resin composition of the present invention, it is possible to obtain a molded article with an improved balance of tensile properties and impact resistance.

[0014] <Polycarbonate-polyorganosiloxane copolymer (A)> The polycarbonate-polyorganosiloxane copolymer (A) comprises a polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) and a polycarbonate block (A-2) containing a structural unit represented by general formula (2).

[0015] [ka] [In the formula, R 1 ~R 4 Each of these independently represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C12 aryl group, or a C7-C22 alkylaryl group. 6 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of -. Multiple R 8 These may be the same or different, and represent an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111- May include at least one group selected from the group consisting of -. 111 represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. z and u represent 0 or 1. a represents an integer from 2 to 500, and b represents an integer from 2 to 200. R 10 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. These groups may be substituted with substituents and may contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms. y represents an integer between 10 and 500.

[0016] By incorporating the structural unit represented by the general formula (1) above, the affinity between the polycarbonate block (A-2) and the polyorganosiloxane structural portion of the polyorganosiloxane block (A-1) can be increased. As a result, separation between components can be reduced, and it is estimated that a molded article with an improved balance of tensile properties and impact resistance can be obtained. Furthermore, during the production of the polycarbonate-polyorganosiloxane copolymer (A), the monomer derived from the polyorganosiloxane block (A-1) possesses a structural unit represented by general formula (1), thereby improving its compatibility with other raw material components. As a result, it is estimated that the reaction rate of the monomer is increased, and the polyorganosiloxane structure can be incorporated into the polycarbonate-polyorganosiloxane copolymer (A) with high randomness. By possessing the structural unit represented by the above general formula (1), it is possible to reduce the amount of unreacted polyorganosiloxane that could not be copolymerized and copolymers in which polyorganosiloxane is excessively incorporated. As a result, separation between components caused by these components can be reduced, and it is estimated that a molded article with an improved balance of tensile properties and impact resistance can be obtained.

[0017] Polyorganosiloxane block (A-1), which is one of the constituent units of the polycarbonate-polyorganosiloxane copolymer (A), contains a structural unit represented by general formula (1). A polyorganosiloxane block (A-1) is a structural unit located between the two closest polycarbonate bonds on the main chain of a polycarbonate-polyorganosiloxane copolymer (A), and contains at least one repeating unit represented by the following general formula (X).

[0018] [ka]

[0019] [In the formula, R 1 and R 2 This expresses the same meaning as above.

[0020] A polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) preferably contains at least one selected from the group consisting of structural units represented by general formulas (1-1) to (1-3), and more preferably contains a structural unit represented by general formula (1-1).

[0021] [ka] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, and b have the same meaning as above. 5 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of -. 7 This represents an arylene group having 6 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, and these groups have -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of - 111This represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 1 b represents 0 or 1. 1 β represents an integer between 2 and 200. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.

[0022] In the formula, R 1 ~R 4 Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms. 1 ~R 4 Examples of C1-C10 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups (in this specification, "various" means including linear and branched groups, and the same applies hereinafter). 1 ~R 4 Examples of alkoxy groups having 1 to 10 carbon atoms as shown include alkoxy groups in which the alkyl group portion is the same as the alkyl group. 1 ~R 4 Examples of aryl groups having 6 to 12 carbon atoms as shown are the phenyl group and the naphthyl group. 1 ~R 4 Examples of alkylaryl groups having 7 to 22 carbon atoms as shown include alkylaryl groups in which the alkyl group portion is the same as the alkyl group and the aryl group portion is the same as the aryl group. R 1 ~R 4 Preferably, each of these is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an arylalkyl group having 7 to 22 carbon atoms; more preferably, each is an alkyl group having 1 to 6 carbon atoms; and even more preferably, each is a methyl group.

[0023] R 5 , R 6 , R 7 , or R 8Examples of arylene groups having 6 to 20 carbon atoms, as shown, include phenylene groups and naphthylene groups. 5 , R 6 , R 7 , or R 8 Examples of alkylene groups having 1 to 10 carbon atoms as shown include methylene groups, dimethylene groups, trimethylene groups, methyl-substituted dimethylene groups, and various butylene groups. The various butylene groups are preferably tetramethylene groups. 5 , R 6 , R 7 , or R 8 Examples of alkylarylene groups represented by include alkylarylene groups in which the alkyl group portion is the same as that of the alkylene group and the arylene group portion is the same as that of the arylene group. However, these groups include -O-, -COO- (the group may be either -C(=O)O- or -OC(=O)-), -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. 111 - May include at least one group selected from the group consisting of - 111 R represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. 111 Examples of C1-C10 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 111 Examples of aryl groups having 6 to 10 carbon atoms as shown include the phenyl group and the naphthyl group. R 5 , R 6 , R 7 , and R 8 These are preferably alkylene groups having 1 to 10 carbon atoms, more preferably alkylene groups having 1 to 5 carbon atoms, and even more preferably dimethylene groups, methyl-substituted dimethylene groups (-CH2CHMe- or -CHMeCH2-), or trimethylene groups. 5 and R 6 R is more preferably a trimethylene group. 7 and R 8 It is more preferably a dimethylene group. In the present specification, "-Me" represents a methyl group (-CH3 group).

[0024] z and z 1 are each preferably 1, and z and z 1 are more preferably both 1. R 1 to R 8 , z, z 1 , a, b, and b 1 when a plurality of these groups / parameters exist, they may each be the same or different from each other.

[0025] In general formula (1), R 1 to R 4 are all methyl groups, R 6 is a trimethylene group, R 8 is a dimethylene group, and z is 1; it is further more preferable that R 1 ~R 4 are all methyl groups, R 6 is a trimethylene group, R 8 is a dimethylene group, z is 1, and u is 1. In general formulas (1-1) to (1-3), R 1 to R 4 are all methyl groups, R 5 and R 6 are all trimethylene groups, R 7 and R 8 are all dimethylene groups, and z and z 1 are all 1; this is further more preferable.

[0026] Examples of the divalent group derived from a diisocyanate compound represented by β, or the divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid include divalent groups represented by the following general formulas (iii) to (vii).

[0027]

Chemical

[0028] a represents the number of repeating units of the polyorganosiloxane, preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, even more preferably 35 or more, and preferably an integer of 500 or less, more preferably 300 or less, even more preferably 100 or less, even more preferably 70 or less, even more preferably 65 or less, and even more preferably 50 or less. The average number of repeating units of the polyorganosiloxane, which is the average value of a, is preferably 2 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, even more preferably 35 or more, and preferably 500 or less, more preferably 300 or less, even more preferably 100 or less, even more preferably 70 or less, even more preferably 65 or less, and even more preferably 50 or less. It is preferable that the average number of repeating units of the polyorganosiloxane is within the above range because the polycarbonate-polyorganosiloxane copolymer has a higher total light transmittance and becomes a highly transparent copolymer.

[0029] b and b 1 represents the number of repeating units of the terminally modified group of the polyorganosiloxane, and each is independently preferably 2 or more, more preferably 5 or more, even more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, and preferably an integer of 200 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 45 or less, even more preferably 40 or less, and even more preferably 38 or less. b and b 1The average number of repeating units of the terminal modifying groups of the polyorganosiloxane, which is the average value, is preferably 2 or more, more preferably 5 or more, even more preferably 8 or more, even more preferably 10 or more, even more preferably 12 or more, and preferably 200 or less, more preferably 100 or less, even more preferably 50 or less, even more preferably 45 or less, even more preferably 40 or less, and even more preferably 38 or less. The above range is preferable due to the ease of obtaining the raw materials. A value of 10 or more average repeating units of the terminal modifying groups of the polyorganosiloxane is more preferable because it can further improve the balance between the tensile properties and impact resistance of the resulting molded article. A value of 100 or less average repeating units of the terminal modifying groups of the polyorganosiloxane is more preferable because it can suppress the decrease in handlingability due to the increase in viscosity and melting point of the polyorganosiloxane. A value of 50 or less average repeating units of the terminal modifying groups of the polyorganosiloxane is more preferable because it can maintain the polyorganosiloxane block content in the resin at an amount that can maintain the physical property improvement effect. In the above general formula (1), or general formulas (1-1) to (1-3), z and z 1 Each of these independently represents either 0 or 1, preferably 1. In the above general formula (1), u represents 0 or 1, and is preferably 1.

[0030] In the above general formula (2), R 10 Examples of divalent aliphatic hydrocarbon groups having 2 to 40 carbon atoms include ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethylhexylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, and n-octadecylene. However, these groups may be substituted with substituents, and may also contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms. In the above general formula (2), R10 Examples of divalent alicyclic hydrocarbon groups having 3 to 40 carbon atoms include cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclotetradecylene, adamantylene, bicycloheptylene, bicyclodecylene, and tricyclodecylene groups. However, these groups may be substituted with substituents, and may also contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms.

[0031] In the above general formula (2), R 10 Examples of divalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include 2,2-bis(4-hydroxyphenyl)propane (also known as bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (also known as bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (also known as bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane (also known as bisphenol 3MZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (also known as bisphenol HTG), 1,1-bis(4-hydroxyphenyl)cyclododecene, hydroquinone, resorcinol (also known as resorcinol), and divalent aromatic hydrocarbon groups derived from catechol. Such divalent aromatic hydrocarbon groups can be derived, for example, by using the above compounds during manufacturing. However, these groups may be substituted with substituents, and may also contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms.

[0032] The polycarbonate block (A-2) containing the structural unit represented by the general formula (2) above preferably contains at least one of the structural unit represented by the general formula (111) and the structural unit represented by the general formula (112), and more preferably contains the structural unit represented by the general formula (111). In a preferred embodiment of the present invention, the polycarbonate block (A-2) contains structural units represented by general formula (111) in an amount of preferably 90 mol% or more, more preferably 95 mol% or more, even more preferably 98 mol% or more, even more preferably 99 mol% or more, and even more preferably 100 mol% or more, of the structural units represented by general formula (2) in 100 mol%.

[0033] [ka] [In the formula, R 55 and R 56 Each of these independently represents a halogen atom, a C1-C6 alkyl group, or a C1-C6 alkoxy group. X represents a single bond, a C1-C8 alkylene group, a C2-C8 alkylidene group, a C5-C15 cycloalkylene group, a C6-C20 arylene group, a C5-C15 cycloalkylidene group, a fluoranthyl group, a C7-C15 arylalkylene group, a C7-C15 arylalkylidene group, -S-, -SO-, -SO2-, -O-, or -CO-. 100 represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and the divalent aliphatic hydrocarbon group may include at least one selected from the group consisting of branched and cyclic structures, and may also include at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms. y represents an integer from 10 to 500. s and t each independently represent an integer from 0 to 4.

[0034] R 55 or R 56 Examples of halogen atoms represented by include fluorine, chlorine, bromine, and iodine atoms. R 55 or R 56 Examples of C1-C6 alkyl groups represented by include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 55 or R 56Examples of alkoxy groups represented by include alkoxy groups in which the alkyl group portion is the same as the alkyl group.

[0035] Examples of alkylene groups having 1 to 8 carbon atoms represented by X include methylene, ethylene, trimethylene, tetramethylene, and hexamethylene groups, with alkylene groups having 1 to 5 carbon atoms being preferred. Examples of alkylidene groups having 2 to 8 carbon atoms represented by X include ethylidene and isopropylidene groups. Examples of cycloalkylene groups having 5 to 15 carbon atoms represented by X include cyclopentanediyl, cyclohexanediyl, and cyclooctanediyl groups, with cycloalkylene groups having 5 to 10 carbon atoms being preferred. Examples of arylene groups having 6 to 20 carbon atoms represented by X include phenylene, naphthylene, and biphenylene groups. Examples of cycloalkylidene groups having 5 to 15 carbon atoms represented by X include cyclohexylidene, 3,5,5-trimethylcyclohexylidene, and 2-adamantylidene, with cycloalkylidene groups having 5 to 10 carbon atoms being preferred, and cycloalkylidene groups having 5 to 8 carbon atoms being more preferred. Examples of arylalkylene groups having 7 to 15 carbon atoms represented by X include arylalkylene groups in which the aryl moiety is a ring-forming aryl group having 6 to 14 carbon atoms, such as a phenyl group, naphthyl group, biphenyl group, or anthryl group, and the alkylene moiety is the same as the alkylene. Examples of arylalkylidene groups having 7 to 15 carbon atoms represented by X include arylalkylidene groups in which the aryl moiety is a ring-forming aryl group having 6 to 14 carbon atoms, such as a phenyl group, naphthyl group, biphenyl group, or anthryl group, and the alkylidene moiety is the same as the alkylidene.

[0036] s and t each independently represent integers from 0 to 4, preferably from 0 to 2, more preferably 0 or 1. In particular, it is preferable that s and t are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, and it is also preferable that s and t are 0 and X is an alkylidene group, and especially preferable that s and t are 0 and X is an isopropylidene group.

[0037] R100 Examples of divalent aliphatic hydrocarbon groups having 2 to 40 carbon atoms, as shown, include alkylene groups having 2 to 40 carbon atoms, cycloalkylene groups having 4 to 40 carbon atoms, and divalent saturated heterocyclic groups containing oxygen or nitrogen having 4 to 40 carbon atoms. The number of carbon atoms in the alkylene group is preferably 2 to 18, more preferably 2 to 10, and even more preferably 3 to 6. The number of carbon atoms in the cycloalkylene group is preferably 4 to 20, more preferably 5 to 20. The number of carbon atoms in the divalent saturated heterocyclic group containing oxygen or nitrogen is preferably 4 to 20, and more preferably 5 to 20. However, these groups may include at least one selected from the group consisting of branched structures and cyclic structures, and may also include at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms.

[0038] Examples of alkylene groups having 2 to 40 carbon atoms include ethylene, n-propylene, isopropylene, n-butylene, isobutylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, 2-ethylhexylene, n-nonylene, n-decylene, n-undecylene, n-dodecylene, n-tridecylene, n-tetradecylene, n-pentadecylene, n-hexadecylene, n-heptadecylene, and n-octadecylene. Examples of the cycloalkylene group having 4 to 40 carbon atoms include cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclotetradecylene, adamantylene, bicycloheptylene, bicyclodecylene, and tricyclodecylene. Examples of the divalent heterocyclic group having 4 to 40 carbon atoms and containing oxygen or nitrogen include those containing oxygen or nitrogen atoms in the cycloalkylene group skeleton.

[0039] The polycarbonate block (A-2) consisting of repeating units represented by the above general formula (2) preferably includes at least one selected from the group consisting of structural units represented by the following general formulas (ai) to (a-xiii), more preferably includes at least one selected from the group consisting of structural units represented by the following general formulas (ai) to (av), more preferably includes at least one selected from the group consisting of structural units represented by (ai), (a-ii), and (av), and even more preferably includes the structural unit represented by (av). Including such preferred structural units results in higher transparency.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] The polycarbonate block (A-2) represented by general formula (2) preferably contains structural units derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecene, isosorbide, cyclohexane-1,4-dimethanol, tricyclodecanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol. Such structural units are derived, for example, by using the compound during manufacturing.

[0044] y is more preferably 20 or more, even more preferably 40 or more, and more preferably 200 or less, and even more preferably 100 or less. Setting y to 20 or more is preferable because it suppresses the increase of low molecular weight components in the copolymer. Setting y to 40 or more is preferable because it increases the toughness of the copolymer. Setting y to 200 or less is preferable because it provides adequate fluidity during molding, and setting it to 100 or less is preferable because the reaction mixture during production has adequate fluidity, thus improving productivity.

[0045] The polyorganosiloxane block (A-1) preferably contains structural units represented by general formula (1) as its main component. In this specification, "main component" means that its content relative to all structures is 50% by mass or more. The polyorganosiloxane block (A-1) preferably contains 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 98% by mass or more, relative to all structures of the polyorganosiloxane block (A-1). The polycarbonate block (A-2) preferably contains structural units represented by general formula (2) as its main component. The polycarbonate block (A-2) preferably contains structural units represented by general formula (2) in an amount of 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 98% by mass or more, relative to all the structures of the polyorganosiloxane block (A-1).

[0046] The content of polyorganosiloxane block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 20% by mass or less, and even more preferably 10% by mass or less. If the polyorganosiloxane block content in the polycarbonate-polyorganosiloxane copolymer (A) is within the above range, superior impact resistance and transparency can be obtained. The polycarbonate block (A-2) content in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 40% by mass or more, more preferably 60% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and preferably 99.9% by mass or less, more preferably 99.5% by mass or less, even more preferably 99.0% by mass or less, and even more preferably 97.0% by mass or less.

[0047] In this specification, "content of polyorganosiloxane block (A-1) in polycarbonate-polyorganosiloxane copolymer (A)" is the percentage of the total mass of the structural unit represented by general formula (X) to the total mass of the end structures derived from the polycarbonate block (A-2), the structural unit represented by general formula (X), the structural unit represented by general formula (Y) below, and optionally the end-terminating agent contained in the polycarbonate-polyorganosiloxane copolymer (A) as described below. The same applies to "content of polyorganosiloxane block (A-1) in polycarbonate resin (S)" and "content of polyorganosiloxane block (A-1) in polycarbonate resin composition" as described below.

[0048] [ka]

[0049] [In the formula, R Y is R 7 or R 8 That is. R Y R 8 If that is the case, then z 0 is z, and R Y R 7 If that is the case, then z 0 is z 1 That is. R 7 , R 8 , z, and z 1 This expresses the same meaning as above.

[0050] In this specification, the terms "content" and "content percentage" may be used interchangeably.

[0051] The viscosity-average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 5,000 or more, more preferably 12,000 or more, even more preferably 14,000 or more, even more preferably 16,000 or more, and preferably 50,000 or less, more preferably 30,000 or less, even more preferably 23,000 or less, and even more preferably 21,000 or less. In this specification, the viscosity-average molecular weight (Mv) is the value calculated from the Schnell formula below, after measuring the intrinsic viscosity [η] of a methylene chloride solution (concentration: g / L) at 20°C. [η] = 1.23 × 10 -5 Mv 0.83

[0052] A polycarbonate-polyorganosiloxane copolymer (A) can be produced, for example, by using a diol monomer (a1) and a polyorganosiloxane (a2) as raw material monomers.

[0053] <<Diol monomer (a1)>> The above-mentioned diol monomer (a1) is not particularly limited as long as it has the structure shown by the following general formula (a1). As the diol monomer (a1), an aromatic dihydroxy compound or an aliphatic dihydroxy compound can be used.

[0054] [ka]

[0055] In the above general formula (a1), R 10 The above applies to the preferable ones as well.

[0056] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably has the structure represented by the following general formula (a2-0).

[0057] [ka] [In the formula, R 1 ~R 4 , R 6 , R 8 , z, a, b, and u have the same meaning as above. However, there are multiple R 1 , R 2 , R 6 , and R 8These can be the same or different. 40’’ [This represents a hydrocarbon group having 1 to 40 carbon atoms, which may have a structure containing one or more heteroatoms in at least one of its main chain and side chains. e and h represent 0 or 1.]

[0058] R 40’’ The hydrocarbon group represented by preferably includes a repeating chain structure in which at least two divalent structures are linked together, each containing at least one hydrocarbon group selected from the group consisting of a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and at least one heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. The divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms includes methylene and R 10 The same divalent aliphatic hydrocarbon groups with 2 to 40 carbon atoms as indicated by can be cited. As for the divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, R 10 The same divalent alicyclic hydrocarbon groups with 3 to 40 carbon atoms as shown can be cited. As for the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, R 10 The same divalent aromatic hydrocarbon groups with 6 to 20 carbon atoms as shown can be cited. Examples of divalent structures containing at least one heteroatom selected from the group consisting of oxygen, nitrogen, and sulfur atoms include -O-, -(C=O)-, -O(C=O)- (the divalent structure may be either -O(C=O)- or -(C=O)O-), -O(C=O)O-, -NR-, -NR-(C=O)- (the divalent structure may be either -NR-(C=O)- or -(C=O)-NR-), -N=CR- (the divalent structure may be either -N=CR- or -CR=N-), -SH, -S-, -SS-, and -(S=O)-. R represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and these may be substituted with substituents. The repeating chain structure preferably includes at least one structure selected from the group consisting of polyethers, polyacetals, polylactones, polyacrylates, polyesters, polycarbonates, polyketones, polysulfides, polysulfones, polyamides, and polyimides. In particular, it is preferable to include at least one structure selected from the group consisting of polyethers, polyacrylates, and polycarbonates, and most preferably to include a polyether. As the polyether, polyalkylene ethers are preferred, with polyethylene glycol, polypropylene glycol, polytrimethylene glycol, and polytetramethylene glycol being particularly preferred. The above structure is preferred from the viewpoint of increasing affinity with the diol monomer (a1) and achieving more uniform polymerization. Furthermore, the repeating chain structure may have at least one substituent selected from the group consisting of -OH, -NH2, and -NRH. R has the same meaning as described above.

[0059] The polyorganosiloxane (a2) is preferably a monomer having one of the structures represented by the following general formulas (a2-1) to (a2-3).

[0060] [ka]

[0061] In the above formula, R 1 ~R 4 , R 5 , R 6 , R 7 , R 8 , z, z 1 , β, a, b, and b 1 The same meaning applies as above. The same applies to desirable items, and combinations of desirable items are equally desirable. The method for producing polyorganosiloxane (a2) is not particularly limited. For example, according to the method described in Japanese Patent Publication No. 11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α,ω-dihydrogenorganopentasiloxane, and then, in the presence of a hydrosilylation catalyst, an oligomer or polymer (e.g., polyalkylene ether, polyester, polycarbonate, etc.) modified with an allyl group at one end is added to the α,ω-dihydrogenorganopentasiloxane to obtain polyorganosiloxane. Furthermore, according to the method described in Japanese Patent Publication No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of an acidic catalyst such as sulfuric acid, and the resulting α,ω-dihydrogenorganopolysiloxane is subjected to an addition reaction with an oligomer or polymer modified with an allyl group at one end, in the presence of a hydrosilylation catalyst, in the same manner as described above, to obtain a polyorganosiloxane. Note that the α,ω-dihydrogenorganopolysiloxane can be used after appropriately adjusting its average repeat number a depending on the polymerization conditions, or commercially available α,ω-dihydrogenorganopolysiloxane may be used. Similarly, the oligomer modified with an allyl group at one end can be used after appropriately adjusting its average repeat number b depending on the polymerization conditions, or commercially available oligomers modified with an allyl group at one end may be used. Among the oligomers with one end allyl group, polyethylene glycol with one end allyl group can be manufactured by referring to Japanese Patent No. 5652691, etc. Commercially available allyl group-modified polyethylene glycols include Uniox PKA-5001, Uniox PKA-5002, Uniox PKA-5003, Uniox PKA-5004, and Uniox PKA-5005, manufactured by NOF Corporation.

[0062] Polycarbonate-polyorganosiloxane copolymer (A) can be produced by polymerizing the raw material monomers by interfacial polymerization or melt polymerization (transesterification). When producing by interfacial polymerization, for example, the method described in Japanese Patent Application Publication No. 2014-80462 can be used. Preferably, polycarbonate-polyorganosiloxane copolymer (A) can be produced by reacting a raw material monomer, polyorganosiloxane (a2), a diol monomer (a1), and a carbonate ester compound by melt polymerization in the presence of a basic catalyst. At this time, an end-terminating agent may be added to carry out the polymerization reaction. Melt polymerization is environmentally and economically advantageous because it does not require solvents such as methylene chloride, which are necessary in interfacial polymerization. In addition, it is advantageous in terms of manufacturing because it does not use phosgene, which is highly toxic and used as a carbonate source in interfacial polymerization.

[0063] (Carbonate ester compounds) Examples of carbonate ester compounds include diaryl carbonates, dialkyl carbonates, and alkylaryl carbonates. Examples of diaryl carbonate compounds include compounds represented by the following general formula (11) and compounds represented by the following general formula (12).

[0064] [ka] [In formula (11), Ar 1 and Ar 2 Each of these represents an aryl group, and they may be the same or different from each other. In formula (12), Ar 3 and Ar 4 Each of these represents an aryl group, and they may be the same or different from each other. 1 [This indicates a residue obtained by removing two hydroxyl groups from the aforementioned aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0065] Examples of dialkyl carbonate compounds include compounds represented by the following general formula (13) and compounds represented by the following general formula (14).

[0066] [ka] [In formula (13), R 21 and R 22 Each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and they may be the same or different from each other. In formula (14), R 23 and R 24 Each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, and they may be the same or different from each other. 2 [This indicates a residue obtained by removing two hydroxyl groups from the aforementioned aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0067] Examples of alkylaryl carbonate compounds include compounds represented by the following general formula (15) and compounds represented by the following general formula (16).

[0068] [ka] [In formula (15), Ar 5 R is an aryl group. 25 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. In formula (16), Ar 6 R is an aryl group. 26 is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D 1 [This indicates a residue obtained by removing two hydroxyl groups from the aforementioned aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0069] Examples of diaryl carbonate compounds include diphenyl carbonate, dityl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, and bisphenol A bisphenyl carbonate. Examples of dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of alkylaryl carbonate compounds include methylphenyl carbonate, ethylphenyl carbonate, butylphenyl carbonate, cyclohexylphenyl carbonate, and bisphenol A methylphenyl carbonate. A preferred carbonate ester compound is diphenyl carbonate. One or more carbonate ester compounds can be used in the production of the polycarbonate-polyorganosiloxane copolymer (A).

[0070] (Terminal deactivators) In the production of the polycarbonate-polyorganosiloxane copolymer (A), end-terminating agents may be used as needed. Known end-terminating agents used in the production of polycarbonate resins may be used as end-terminating agents. Specific examples of such compounds include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monovalent phenols may be used individually or in combination of two or more.

[0071] (Branching agent) In the production of polycarbonate-polyorganosiloxane copolymer (A), branching agents can also be used. Examples of branching agents include phloroglucin, trimellitic acid, 1,1,1-tris(4-hydroxyphenyl)ethane, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4”-hydroxyphenyl)ethyl]benzene, α,α',α”-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, and isatinbis(o-cresol).

[0072] Specifically, for example, a polycarbonate-polyorganosiloxane copolymer (A) can be produced by melt polymerization using the following procedure. A diol monomer (a1), a polyorganosiloxane (a2), and a carbonate ester compound are subjected to a transesterification reaction. The amount of carbonate ester compound relative to the diol monomer is preferably 0.9 to 1.2 times the molar amount, and more preferably 0.98 to 1.02 times the molar amount. In the above transesterification reaction, it is preferable that the amount of end-terminating agent present is in the range of 0.05 to 10 mol% relative to the total amount of diol monomer (a1) and polyorganosiloxane (a2), as this sufficiently seals the hydroxyl group ends of the resulting polycarbonate-polyorganosiloxane copolymer, thereby yielding a polycarbonate resin with excellent heat resistance and water resistance. More preferably, the amount of end-terminating agent relative to the total amount of diol monomer (a1) and polyorganosiloxane (a2) is 1 to 6 mol%. The end-terminating agent may be added to the reaction system in its entirety beforehand, or a portion may be added to the reaction system beforehand, with the remainder added as the reaction progresses. It is preferable to add the diol monomer (a1), polyorganosiloxane (a2), and carbonate ester compound together with the antioxidant to the reactor at the same time, and carry out the transesterification reaction in the presence of the antioxidant.

[0073] There are no particular restrictions on the reaction temperature when carrying out a transesterification reaction; for example, it can be in the range of 100 to 330°C, preferably in the range of 180 to 300°C, and more preferably in the range of 200 to 240°C. Furthermore, it is preferable to gradually increase the temperature from 180 to 300°C as the reaction progresses. If the temperature of the transesterification reaction is 100°C or higher, the reaction rate will be sufficiently fast, while if it is 330°C or lower, many side reactions will not occur, and problems such as discoloration of the resulting polycarbonate-polyorganosiloxane copolymer will not occur.

[0074] The reaction pressure is set according to the vapor pressure of the monomer used and / or the reaction temperature. It is not particularly limited as long as it is set so that the reaction proceeds efficiently. For example, in the initial stages of the reaction, the pressure is set to atmospheric pressure (normal pressure) or pressurized state of 1 to 50 atm (760 to 38,000 torr), and in the later stages of the reaction, the pressure is reduced, and finally it is set to 1.33 to 1.33 × 10⁻⁶. 4 It is preferable to set Pa (0.01 to 100 torr). The reaction time should be sufficient to reach the target molecular weight, for example, 0.2 to 10 hours.

[0075] The above transesterification reaction is carried out, for example, in the absence of an inert solvent, but may be carried out in the presence of 1 to 150 parts by mass of an inert solvent per 100 parts by mass of the resulting polycarbonate resin, if necessary. Examples of inert solvents include aromatic compounds such as diphenyl ethers, halogenated diphenyl ethers, benzophenone, polyphenyl ethers, dichlorobenzene, and methylnaphthalene; and tricyclo[5.2.1.0 2,6 Examples include decane, cyclooctane, and cycloalkanes such as cyclodecane. If necessary, the process may be carried out under an inert gas atmosphere. Examples of inert gases include argon, carbon dioxide, nitrous oxide, nitrogen, etc.; alkanes such as chlorofluorohydrocarbons, ethane, and propane; and alkenes such as ethylene and propylene.

[0076] In melt polymerization, it is preferable to use a basic catalyst. Examples of basic catalysts include at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing aryl groups, and metal compounds. These compounds can be used individually or in combination. Preferred basic catalysts include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing aryl groups. The basic catalyst can be used individually or in combination of two or more.

[0077] Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, disodium salt, dicesium salt, and dilithium salt of bisphenol A, as well as sodium salt, potassium salt, cesium salt, and lithium salt of phenol. Examples of alkaline earth metal compounds include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate.

[0078] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl or aryl groups, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Furthermore, examples include ammonia, bases or basic salts such as tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0079] Examples of metallic compounds include zinc-aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0080] Specific examples of quaternary phosphonium salts containing an aryl group include, for example, tetra(aryl or alkyl)phosphonium hydroxides such as tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide; tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(pt-butylphenyl)phosphonium diphenyl phosphate, triphenylbutylphosphonium phenolate, and triphenylbutylphosphonium tetraphenylborate. Quaternary phosphonium salts containing an aryl group are preferably combined with nitrogen-containing organic basic compounds, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0081] The amount of basic catalyst used is preferably 1 × 10⁻¹⁶ per mole of diol monomer (a1). -9 ~1 × 10 -2 Moles, comfort level 1 × 10 -8 ~1 × 10 -2 Moles, more preferably 1 × 10 -7 ~1 × 10 -3 You can choose within the range of moles.

[0082] A catalyst deactivator can also be added in the later stages of the reaction. Known catalyst deactivators are effectively used. Examples of catalyst deactivators include ammonium salts of sulfonic acids and phosphonium salts of sulfonic acids.

[0083] When using at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds, the amount of catalyst deactivator used is preferably 0.5 to 50 moles, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles per mole of catalyst. It is preferable to add a catalyst deactivator and then mix in an antioxidant after the polymerization reaction has been completed.

[0084] The reaction in the melt polymerization method may be carried out in either a continuous or batch manner. The reactor used for melt polymerization may be a vertical reactor equipped with anchor-type impellers, Maxblende impellers, or helical ribbon-type impellers, or a horizontal reactor equipped with paddle impellers, grid impellers, or spectacle-type impellers. Furthermore, an extruder type equipped with a screw may also be used. In the case of a continuous reaction, it is preferable to use a combination of such reactors as appropriate.

[0085] <Polycarbonate resin (S)> The polycarbonate resin (S) may also contain polycarbonate resins (P) other than the polycarbonate-polyorganosiloxane copolymer (A) (hereinafter sometimes referred to as polycarbonate resin (P)). The content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate resin (S) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, from the viewpoint of improving the balance of impact resistance, tensile properties and chemical resistance. There is no particular upper limit to the content of the polycarbonate-polyorganosiloxane copolymer (A) in the polycarbonate resin (S), but from the viewpoint of obtaining a resin composition with desired properties, it is, for example, 100% by mass or less.

[0086] The content of polyorganosiloxane block (A-1) in the polycarbonate resin (S) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 7.0% by mass or less.

[0087] The content of polyorganosiloxane block (A-1) in the polycarbonate resin composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, preferably 40% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, and even more preferably 7.0% by mass or less.

[0088] The viscosity-average molecular weight of the polycarbonate resin (S) is preferably 5,000 or more, more preferably 12,000 or more, even more preferably 14,000 or more, even more preferably 16,000 or more, and preferably 50,000 or less, more preferably 30,000 or less, even more preferably 23,000 or less, and even more preferably 21,000 or less.

[0089] <Polycarbonate resin (P)> There are no particular restrictions on the polycarbonate resin (P), and various known polycarbonate resins can be used. The polycarbonate resin (P) is preferably a polycarbonate resin that does not contain polyorganosiloxane blocks (A-1) containing structural units represented by the general formula (1), but contains polycarbonate blocks (A-2) containing structural units represented by the general formula (2). The structural units represented by general formula (2) contained in the polycarbonate resin (P) are the same as the structural units represented by general formula (2) contained in the polycarbonate-polyorganosiloxane copolymer (A). The preferred form is also the same. The polycarbonate resin (P) preferably contains structural units represented by general formula (2) as its main component. The content of structural units represented by general formula (2) in the polycarbonate resin (P) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 98% by mass or more, relative to the total structure of the polycarbonate resin (P). The viscosity-average molecular weight of the polycarbonate resin (P) is preferably 5,000 or more, more preferably 12,000 or more, even more preferably 14,000 or more, even more preferably 16,000 or more, and preferably 50,000 or less, more preferably 30,000 or less, even more preferably 23,000 or less, and even more preferably 21,000 or less.

[0090] <Elastomer (B)> The polycarbonate resin composition according to the present invention contains a polycarbonate resin (S) and an elastomer (B). Preferably, the polycarbonate resin composition contains 1.0 part by mass or more and 40 parts by mass of elastomer (B) per 100 parts by mass of polycarbonate resin (S). When the elastomer (B) content is 1.0 part by mass or more, the balance between tensile properties and impact resistance can be further improved. When the elastomer (B) content is 40 parts by mass or less, for example, impact resistance, mechanical strength, heat resistance, chemical resistance, transparency, etc. can be further improved. The elastomer (B) content in the polycarbonate resin composition according to the present invention is more preferably 2.0 parts by mass or more, even more preferably 3.0 parts by mass or more, and even more preferably 4.0 parts by mass or more, per 100 parts by mass of polycarbonate resin (S), from the viewpoint of further improving the balance between tensile properties and impact resistance. From the viewpoint of further improving impact resistance, mechanical strength, heat resistance, chemical resistance, transparency, etc., it is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 8.0 parts by mass or less. The polycarbonate resin composition according to the present invention may contain one or more elastomers as elastomer (B).

[0091] As for the elastomer (B), a graft copolymer is preferred, which is obtained by graft copolymerizing a rubber component with a monomer component that can copolymerize with the rubber component, from the viewpoint of further improving the balance between tensile properties and impact resistance. The method for producing the graft copolymer may be any of the following: bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be single-stage grafting or multi-stage grafting. The glass transition temperature of the rubber component is preferably 0°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower. Examples of rubber components include polybutadiene rubber; polyisoprene rubber; polyalkyl acrylate rubber such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymer; silicone-based rubber such as polyorganosiloxane rubber; butadiene-acrylic composite rubber; IPN (Interpenetrating Polymer Network) type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber; styrene-butadiene rubber; ethylene-propylene rubber; ethylene-α-olefin-based rubber such as ethylene-butene rubber and ethylene-octene rubber; ethylene-acrylic rubber; and fluororubber. These rubber components may be used individually or in mixtures of two or more. Among these, from the viewpoint of mechanical properties and appearance, at least one selected from the group consisting of polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN-type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber is preferred, at least one selected from the group consisting of polybutadiene rubber and styrene-butadiene rubber is more preferred, and polybutadiene rubber is even more preferred.

[0092] Examples of monomer components that can be graft copolymerized with rubber components include aromatic vinyl compounds; vinyl cyanide compounds; (meth)acrylic acid ester compounds; (meth)acrylic acid compounds; epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomeric components may be used individually or in combination of two or more. Among these, at least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, and (meth)acrylic acid compounds is preferred in terms of mechanical properties and surface appearance, with (meth)acrylic acid ester compounds being more preferred. Examples of (meth)acrylic acid ester compounds include at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate, with at least one selected from the group consisting of methyl (meth)acrylate and ethyl (meth)acrylate being preferred, and methyl (meth)acrylate being more preferred.

[0093] Elastomer (B) is a graft copolymer obtained by copolymerizing rubber components, and from the viewpoint of impact resistance and appearance, a core / shell type graft copolymer is preferred, and more preferably a core / shell type graft copolymer is obtained in which at least one rubber component selected from the group consisting of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, and IPN-type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as the core layer, and a shell layer formed by copolymerizing (meth)acrylic acid ester around it is preferred. In the above core / shell type graft copolymer, it is preferred that the rubber component is contained in 40% by mass or more, and more preferably 60% by mass or more. In addition, it is preferred that the (meth)acrylic acid is contained in 10% by mass or more. Note that the term core / shell type here does not necessarily mean that the core layer and shell layer are clearly distinguishable, and broadly includes compounds obtained by graft polymerization of rubber components around the core portion.

[0094] From the viewpoint of further improving the balance between tensile properties and impact resistance, elastomer (B) is preferably at least one selected from the group consisting of methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic / silicone IPN rubber) copolymer. More preferably, at least one selected from the group consisting of methyl methacrylate-butadiene-styrene copolymer (MBS) and methyl methacrylate-butadiene copolymer (MB) is preferred, and methyl methacrylate-butadiene copolymer (MB) is even more preferred. Such elastomer (B) may be used alone or in combination of two or more types. These elastomers (B) are preferably the aforementioned core / shell type graft copolymers.

[0095] Examples of commercially available elastomers (B) include, for example, "Paraloid (registered trademark, same hereinafter) EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid KCZ201" from Rohm & Haas Japan Co., Ltd., and Mitsubishi Electric. Examples include "Metablen (registered trademark, same hereinafter) C-223A", "Metablen E-901", "Metablen S-2001", and "Metablen SRK-200" manufactured by I-Yon Co., Ltd., "KaneAce (registered trademark, same hereinafter) M-511", "KaneAce M-600", "KaneAce M-400", "KaneAce M-580", "KaneAce M-711", and "KaneAce MR-01" manufactured by Kaneka Corporation, and "UBESTA XPA" manufactured by Ube Industries, Ltd.

[0096] The total content of the polycarbonate resin (S) and elastomer (B) in the polycarbonate resin composition according to the present invention is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99% by mass or more, when the total polycarbonate resin composition is considered to be 100% by mass. There is no particular upper limit to the total content of the polycarbonate resin (S) and elastomer (B), but from the viewpoint of obtaining a resin composition with desired properties, it is, for example, 100% by mass or less.

[0097] <Antioxidant (C)> The polycarbonate resin composition according to the present invention may appropriately contain an antioxidant (C) to the extent that it does not impair the objective of the present invention. Antioxidant (C) can suppress the decomposition of the resin during the manufacturing and molding of the polycarbonate resin composition. Known antioxidants can be used as antioxidant (C), and preferably at least one selected from phosphorus-based antioxidants and phenol-based antioxidants can be used. From the viewpoint of suppressing oxidative degradation of molded articles containing polycarbonate resin compositions during high-temperature molding, the phosphorus-based antioxidant is more preferably a phosphorus-based antioxidant having an aryl group, and more preferably a compound represented by the following general formula (C1).

[0098] [ka] In formula (C1), R C21 ~R C25 R is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 14 carbon atoms, and may be the same or different. However, from the viewpoint of its effect as an antioxidant, C21 ~R C25 Not all of them become hydrogen atoms, R C21 ~R C25 At least two of these are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms. Preferably, R C21 ~R C25 A compound in which any two of the members are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms, with the remainder being hydrogen atoms, more preferably R C21 ~R C25 Among the compounds in which any two of them are alkyl groups having 1 to 12 carbon atoms or aryl groups having 6 to 14 carbon atoms and the rest are hydrogen atoms, R C21 or R C25 The compound is one in which at least one of the elements is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 14 carbon atoms. Examples of alkyl groups having 1 to 12 carbon atoms include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, and various dodecyl groups. In particular, from the viewpoint of providing long-term resistance to humidity and heat, one or more selected from the group consisting of methyl groups, ethyl groups, n-propyl groups, isopropyl groups, various butyl groups, various pentyl groups, various hexyl groups, and various octyl groups are preferred, one or more selected from the group consisting of methyl groups, ethyl groups, isopropyl groups, and tert-butyl groups are more preferred, and tert-butyl groups are even more preferred. Examples of aryl groups with 6 to 14 carbon atoms include phenyl, tolyl, and xylyl groups. Among these, R is particularly suitable because it is less prone to thermal decomposition and has excellent effects in improving long-term resistance to humid heat and long-term heat resistance. C21 ~R C25 It is more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group, and even more preferably a hydrogen atom or a tert-butyl group. Particularly preferred, R C21 and R C23 is a tert-butyl group, R C22 , R C24 and R C25 It is tris(2,4-di-tert-butylphenyl) phosphite, where the atom is a hydrogen atom.

[0099] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl(2-ethylhexyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, diphenyl isooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono(tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-ethylhexyl) phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, 4,4' -Isopropylidene diphenol dodecyl phosphite, 4,4'-Isopropylidene diphenol tridecyl phosphite, 4,4'-Isopropylidene diphenol tetradecyl phosphite, 4,4'-Isopropylidene diphenol pentadecyl phosphite, 4,4'-Butylidene bis(3-methyl-6-tert-butylphenyl) ditridecyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-Tris(2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl)butane, 3,4,5,6-dibenzo-1,Examples include 2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, etc.

[0100] Specifically, commercially available phosphorus-based antioxidants include "Irgafos168" (manufactured by BASF Japan Ltd., trademark), "Irgafos12" (manufactured by BASF Japan Ltd., trademark), "Irgafos38" (manufactured by BASF Japan Ltd., trademark), "ADKSTAB 329K" (manufactured by ADEKA Corporation, trademark), "ADKSTAB PEP-36" (manufactured by ADEKA Corporation, trademark), "ADKSTAB PEP-8" (manufactured by ADEKA Corporation, trademark), "Sandstab P-EPQ" (manufactured by Clariant, trademark), "Weston 618" (manufactured by GE Inc., trademark), "Weston 619G" (manufactured by GE Inc., trademark), and "Weston 624" (manufactured by GE Inc., trademark), and "Doverphos S-9228PC" (manufactured by Dover Chemical Corporation).

[0101] Phenolic antioxidants are preferably hindered phenols. Specific examples of phenolic antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di Examples include (-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0102] Specifically, commercially available phenolic antioxidants include "Irganox 1010" (manufactured by BASF Japan Ltd., trademark), "Irganox 1076" (manufactured by BASF Japan Ltd., trademark), "Irganox 1330" (manufactured by BASF Japan Ltd., trademark), "Irganox 3114" (manufactured by BASF Japan Ltd., trademark), "Irganox 3125" (manufactured by BASF Japan Ltd., trademark), "BHT" (manufactured by Takeda Pharmaceutical Company Limited, trademark), "Cyanox 1790" (manufactured by Cyanamide Inc., trademark), and "Sumilizer GA-80" (manufactured by Sumitomo Chemical Co., Ltd., trademark).

[0103] The antioxidant (C) may be used alone or in combination of two or more types. The content of the antioxidant (C) in the polycarbonate resin composition according to the present invention is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, even more preferably 0.04 parts by mass or more, even more preferably 0.08 parts by mass or more, preferably 1.0 part by mass or less, more preferably 0.50 parts by mass or less, even more preferably 0.25 parts by mass or less, and even more preferably 0.15 parts by mass or less, per 100 parts by mass of the polycarbonate resin (S). When multiple types of antioxidant (C) are used, the total amount will be within the above range.

[0104] <Additives> The polycarbonate resin composition according to the present invention may appropriately contain additives other than the elastomer (B) and antioxidant (C) as long as the objectives of the present invention are not impaired. Examples of additives include various fillers, heat stabilizers, plasticizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, mold release agents, and ultraviolet absorbers.

[0105] The method for producing the polycarbonate resin composition according to the present invention is not particularly limited as long as it includes a step of mixing a polycarbonate resin (S), an elastomer (B), and an optional additive. For example, it can be produced by mixing the polycarbonate resin (S), the elastomer (B), and an optional additive using a mixer or the like, and then performing melt kneading. Melt kneading can be carried out by commonly used methods, such as using a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, cone-type extruder, multi-screw extruder, etc. The heating temperature during melt kneading is appropriately selected in the range of, for example, 150°C to 300°C, preferably 220°C to 300°C.

[0106] From the viewpoint of further improving the tensile properties of the resulting molded article, the tensile elongation at break of a JIS K 7139:2009 dumbbell-shaped tensile test piece type A22, obtained by molding the polycarbonate resin composition according to the present invention, with a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, is preferably 10% or more, more preferably 13% or more, even more preferably 20% or more, even more preferably 30% or more, and even more preferably 40% or more. From the viewpoint of further improving the tensile properties of the resulting molded article, the higher the tensile elongation at break, the better, so there is no particular upper limit, but from the viewpoint of improving mechanical strength, it is preferably 200% or less, more preferably 150% or less, even more preferably 120% or less, even more preferably 100% or less, even more preferably 80% or less, and even more preferably 60% or less. The tensile elongation at break can be measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm. Specifically, it can be measured by the method described in the embodiments below. The molding conditions for the above-mentioned molded piece are a cylinder temperature of 280°C, a mold temperature of 100°C, and a cycle time of 60 seconds. Specifically, the molded piece is obtained by the method described in the examples below.

[0107] The tensile modulus of a molded piece of JIS K 7139:2009 dumbbell-shaped tensile test specimen type A22, obtained by molding the polycarbonate resin composition according to the present invention, with a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, is preferably 2250 MPa or higher, more preferably 2300 MPa or higher, even more preferably 2350 MPa or higher, and even more preferably 2400 MPa or higher, from the viewpoint of further improving the tensile properties of the resulting molded article. From the viewpoint of further improving the mechanical strength of the resulting molded article, a higher tensile modulus is preferable, so there is no particular upper limit, but from the viewpoint of improving impact resistance, it is preferably 10000 MPa or lower, more preferably 5000 MPa or lower, and even more preferably 3000 MPa or lower. The aforementioned tensile modulus can be measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm. Specifically, it can be measured by the method described in the examples below. The molding conditions for the above-mentioned molded piece are a cylinder temperature of 280°C, a mold temperature of 100°C, and a cycle time of 60 seconds. Specifically, the molded piece is obtained by the method described in the examples below.

[0108] The Charpy impact strength of a molded piece obtained by molding a polycarbonate resin composition according to the present invention, which is 80 mm long, 10 mm wide, and 4 mm thick, and to which a notch (r=0.25 mm ± 0.05 mm) is added by post-processing, is preferably 38 kJ / m², from the viewpoint of further improving the impact resistance of the resulting molded body. 2 More preferably 40 kJ / m 2 More preferably 41 kJ / m 2 That concludes the explanation. From the viewpoint of further improving the impact resistance of the resulting molded article, a higher Charpy impact strength is preferable, so there is no particular upper limit, but from the viewpoint of improving tensile properties, 100 kJ / m is preferred. 2 More preferably 80 kJ / m 2 More preferably 60 kJ / m 2 The following applies: The Charpy impact strength can be measured in accordance with ISO-179-1:2010 at a measurement temperature of 23°C, and specifically, it can be measured by the method described in the examples below. The molding conditions for the above-mentioned molded piece are a cylinder temperature of 280°C, a mold temperature of 100°C, and a cycle time of 60 seconds. Specifically, the molded piece is obtained by the method described in the examples below.

[0109] 2. Molded body The form of the present invention comprises the polycarbonate resin composition of the present invention. The molded article can be manufactured using a molten kneaded product of the polycarbonate resin composition, or pellets obtained through molten kneading, as a raw material by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and foam molding, etc. In particular, it is preferable to manufacture the molded article using the obtained pellets by injection molding or injection compression molding.

[0110] The thickness of the molded body can be set arbitrarily depending on the application. In particular, when transparency of the molded body is required, a thickness of 0.2 to 4.0 mm is preferred, 0.3 to 3.0 mm is more preferred, and 0.3 to 2.0 mm is even more preferred. If the thickness of the molded body is 0.2 mm or more, warping will not occur and good mechanical strength can be obtained. If the thickness of the molded body is 4.0 mm or less, high transparency can be obtained.

[0111] The molded article may be coated with a hard coat film, an anti-fogging film, an antistatic film, or an anti-reflective film as needed, or it may be a composite film of two or more types. In particular, it is preferable that a hard coat film is formed on the molded body because it has good weather resistance and can prevent wear of the molded body surface over time. The material of the hard coat film is not particularly limited, and known materials such as acrylate-based hard coat agents, silicone-based hard coat agents, and inorganic hard coat agents can be used.

[0112] The molded articles according to the present invention can be suitably used, for example, for: 1) automotive parts such as sunroofs, door visors, rear windows, and side windows; 2) building parts such as architectural glass, soundproof walls, carports, sunrooms, and gratings; 3) windows for railway vehicles and ships; 4) electrical equipment parts such as various parts for televisions, radio cassette players, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, cash registers, photocopiers, printers, and facsimile machines, as well as various parts for exterior panels or housings; 5) precision equipment parts such as cases or covers for precision machinery such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as greenhouses and greenhouses; and 7) furniture parts such as lighting covers, blinds, and interior fixtures. [Examples]

[0113] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In this specification, polydimethylsiloxane may be abbreviated as PDMS.

[0114] 1. Production of terminally modified polyorganosiloxanes Manufacturing Example 1: Manufacturing of PDMS-1 Under a nitrogen atmosphere, the following equation: [ka] For a polyorganosiloxane (100g) with an average repeating unit count of 45, as shown by the formula below: [ka] Polyethylene glycol with an average oxyethylene chain length of 8, as shown in the formula, was added in a molar amount equal to 2 times the amount of polyorganosiloxane. 338 g of toluene was then added as a solvent, and the mixture was kept warm at 80°C and stirred thoroughly. Next, a toluene solution of a platinum vinylsiloxane complex was added in an amount such that the mass of platinum atoms was 5 ppm by mass relative to the siloxane (-(SiMe2O)n-), and the mixture was stirred at a reaction temperature of 110°C for 10 hours. Toluene and the platinum catalyst were removed from the resulting mixture to obtain polyether-modified polyorganosiloxane PDMS-1.

[0115] Manufacturing Example 2: Manufacturing of PDMS-2 Except for setting the average oxyethylene chain length of polyethylene glycol to 38, the polyether-modified polyorganosiloxane PDMS-2 was obtained by the same procedure as in Production Example 1.

[0116] Manufacturing Example 3: Manufacturing of PDMS-3 Under a nitrogen atmosphere, the following equation: [ka] A polyorganosiloxane with an average repeating unit count of 39, as shown by [formula], was to be mixed with 2-allylphenol in an amount equal to 2 molars relative to the polyorganosiloxane, and then thoroughly stirred while being kept warm at 100°C. Next, a toluene solution of a platinum vinylsiloxane complex was added in an amount such that the mass of platinum atoms was 5 ppm by mass relative to the siloxane (-(SiMe2O)n-), and the mixture was stirred at a reaction temperature of 100°C for 10 hours. The platinum catalyst was removed from the resulting mixture to obtain allylphenol-modified polyorganosiloxane PDMS-3.

[0117] Table 1 shows the structural formulas of PDMS-1 to PDMS-3 obtained in manufacturing examples 1 to 3.

[0118] [Table 1]

[0119] <Method for measuring the average number of repeating units of polyorganosiloxanes and the average number of repeating units of terminally modified groups of polyorganosiloxanes> The average number of repeating units in polyorganosiloxanes was calculated by NMR measurement using the integral ratio of methyl groups of polydimethylsiloxanes. The average number of repeating units in terminally modified groups of polyorganosiloxanes was calculated by NMR measurement using the integral ratio of dimethylene groups of polyethylene glycols. 1 H-NMR measurement conditions NMR spectrometer: ECA-500, manufactured by JEOL RESONANCE Co., Ltd. Probe: 50TH5AT / FG2 Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5φ Sample amount: 30-40 mg Solvent: Deuterated chloroform Measurement temperature: 23℃ Total number of times: 256

[0120] 2. Production of polycarbonate-polyorganosiloxane (PC-POS) copolymer Manufacturing Example 4: Manufacturing of PC-POS Copolymer 1 A polycarbonate-polyorganosiloxane copolymer was produced using the following raw materials and conditions. In a 10L stainless steel reactor equipped with a stirrer, a trap to capture distilled phenol, and a vacuum device, 2,489.9g of BisP-A as a diol monomer and 2,500g of DPC as a diester carbonate compound (molar ratio of each raw material: BisP-A / DPC = 100 / 107), and 179.7g of polyether-modified polyorganosiloxane PDMS-1 were added. The reactor was heated to 150°C until these raw material monomers were completely melted, and the inside of the reactor was purged with nitrogen. 1.64mL of 0.01mol / L sodium hydroxide was used as a catalyst (1.5 × 10⁶ times the total number of moles of diol monomer). -6The mixture (twice the amount) was added to start polymerization, and the temperature inside the reactor was raised to 180°C and the pressure inside the reactor to 200 mmHg (26.6 kPa) over approximately 60 minutes, while the reaction conditions were maintained until 0.2 L of phenol was distilled out. Then, the temperature inside the reactor was raised to 200°C and the pressure inside the reactor to 10 mmHg (1.3 kPa) over approximately 60 minutes, while the conditions were maintained until 1.0 L of phenol was distilled out.

[0121] Next, the internal temperature of the reactor was raised to 240°C over approximately 120 minutes, and these conditions were maintained until 1.5 L of phenol was distilled out. Subsequently, the internal temperature of the reactor was adjusted to 280°C and the internal pressure to 1 mmHg (0.1 kPa) or less over approximately 120 minutes, allowing more than 2 L of phenol to be distilled out, and the reaction was continued until the predetermined stirring torque was achieved. After that, nitrogen was introduced to restore the pressure to atmospheric pressure, and 0.037 g of p-toluenesulfonate butyl (10 times the amount of moles of NaOH) was added as a deactivator. Antioxidant 1 and Antioxidant 2 were each added in an amount of 0.05 parts by mass relative to the resulting polymer, and the mixture was thoroughly stirred. After that, the resin strands were extracted from the bottom of the reactor by nitrogen pressure and cut with a pelletizer to obtain a polycarbonate-polyorganosiloxane copolymer. Table 2 shows the analytical values ​​of the obtained PC-POS copolymer 1. The raw materials used in the manufacturing process are as follows: • BisP-A: Bisphenol A [Manufactured by Idemitsu Kosan Co., Ltd.] • DPC: Diphenyl Carbonate [Manufactured by Mitsui Chemicals Fine Co., Ltd.] • 0.01 mol / L sodium hydroxide aqueous solution [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] • Antioxidant (C) Antioxidant 1: Tris(2,4-di-tert-butylphenyl) phosphite [BASF Japan Ltd., Irgafos168] Antioxidant 2: Pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][Manufactured by BASF Japan Ltd., Irganox1010]

[0122] Manufacturing Example 5: Manufacturing of PC-POS Copolymer 2 PC-POS copolymer 2 was obtained by polymerization under the same conditions as in Production Example 4, except that 179.7 g of PDMS-2 was used instead of PDMS-1 as the polyorganosiloxane. Table 2 shows the analytical values ​​of the obtained PC-POS copolymer 2.

[0123] Manufacturing Example 6: Manufacturing of PC-POS Copolymer 3 PC-POS copolymer 3 was obtained by polymerization under the same conditions as in Production Example 4, except that 179.7 g of PDMS-3 was used instead of PDMS-1 as the polyorganosiloxane. The analytical values ​​of the obtained PC-POS copolymer 3 are shown in Table 2.

[0124] 2. Measurement of physical properties of polycarbonate-polyorganosiloxane copolymers (1) Method for determining the polydimethylsiloxane content in the obtained polycarbonate-polyorganosiloxane copolymer NMR spectrometer: ECA-500, manufactured by JEOL RESONANCE Co., Ltd. Probe: TH5 Compatible with 5φ NMR sample tubes Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Total number of times: 256 NMR sample tube: 5φ Sample amount: 30-40 mg Solvent: Deuterated chloroform Measurement temperature: 23℃ A: Integral value of the meta position of the phenyl moiety observed around δ7.3~7.5 B: Integral value of the methylene group in the PEG portion observed around δ3.3~4.5 The integral value of the methyl group in the bisphenol A moiety observed around C:δ1.50~2.00 D:Integral value of the methyl group in the dimethylsiloxane moiety observed around δ-0.02~0.4 E: Integral value of the methylene group at the dimethylsiloxane terminal end observed near δ 0.52 a=A / 2 b=B / 4 c=(C-e×2) / 6 d=D / 6 e=E / 2 T=a+b+c+d f=a / T×100 g=b / T×100 h=c / T×100 i=d / T×100 TW=f×93+g×44+h×254+i×74.1 PDMS(wt%)=(i×74.1) / TW×100

[0125] (2) Method for measuring the viscosity-average molecular weight of polycarbonate-polyorganosiloxane copolymers Using an Ubbelohde viscometer, the viscosity of a methylene chloride solution (concentration: g / L) at 20°C was measured, the intrinsic viscosity [η] was obtained therefrom, and the viscosity-average molecular weight (Mv) was calculated by the following formula (Schnell's formula). [η]=1.23×10 -5 Mv 0.83

[0126]

Table 2

[0127] 3. Raw materials used (resins and additives) The following raw materials were used in the Examples and Comparative Examples. (1) Polycarbonate-polyorganosiloxane copolymer (A) (however, containing antioxidant (C)) • PC-POS copolymer 1: Manufacturing example 4 above • PC-POS copolymer 2: Production example 5 (2) Polycarbonate-polyorganosiloxane copolymers other than polycarbonate-polyorganosiloxane copolymer (A) (provided that they contain antioxidant (C)) • PC-POS copolymer 3: Production example 6

[0128] (3) Elastomer (B) • Elastomer 1: Methyl methacrylate-butadiene binary copolymer (a core / shell type graft copolymer consisting of a butadiene core and a methyl methacrylate shell, manufactured by Kaneka Corporation, Kaneace M-711)

[0129] 4. Examples 1-2 and Comparative Example 1 (1) Preparation of polycarbonate resin composition Each component was mixed in the proportions shown in Table 3 and supplied to a twin-screw extruder [DSM Xplore: Micro 15cc Twin Screw Compounder]. The mixture was melt-kneaded at a barrel temperature of 280°C and a screw rotation speed of 50 rpm to obtain polycarbonate-based resin compositions. Here, the unit of the blending amount of each component shown in Table 3 is parts by mass. (2) Preparation of molded pieces for evaluation Using an injection molding machine [DSM Xplore: 10cc Injection Moulding Machine], the polycarbonate resin composition obtained in (1) above was injection molded under the conditions of a cylinder temperature of 280°C, a mold temperature of 100°C, and a cycle time of 60 seconds to form molded pieces (molded bodies) for evaluating tensile properties and impact resistance.

[0130] (3) Evaluation The evaluations described below were performed using the evaluation molded pieces obtained in (2) above. The results are shown in Table 3. • Tensile properties (tensile elongation at fracture, tensile modulus) Using a tensile testing machine [INSTRON 5567], the tensile elongation at break and tensile modulus were measured for a JIS K 7139:2009 dumbbell-type tensile test specimen (Type A22) with a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm. The values ​​indicate better tensile properties. • Impact resistance The impact resistance of the polycarbonate resin composition was evaluated using the following Charpy impact strength. Using molded strips measuring 80 mm in length, 10 mm in width, and 4 mm in thickness, to which notches (r=0.25 mm ± 0.05 mm) were added by post-processing, the Charpy impact strength at 23°C was measured using a Charpy impact tester (Toyo Seiki Seisakusho Co., Ltd., Charpy Impact Tester, Model 611) in accordance with ISO-179-1:2010.

[0131] [Table 3]

Claims

1. A polycarbonate resin (S) comprising a polycarbonate-polyorganosiloxane copolymer (A) having a polyorganosiloxane block (A-1) containing a structural unit represented by general formula (1) and a polycarbonate block (A-2) containing a structural unit represented by general formula (2), A polycarbonate resin composition containing elastomer (B). 【Chemistry 1】 [In the formula, R １ ~R ４ Each of these independently represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C6-C12 aryl group, or a C7-C22 alkylaryl group. ６ This represents an alkylene group having 1 to 10 carbon atoms, and these groups are present in at least one of the main chain and side chains as -O-, -COO-, -CO-, -S-, -NH-, and -NR １１１ - May include at least one group selected from the group consisting of R. ８ These may be the same or different, and each represents an alkylene group having 1 to 10 carbon atoms, and these groups include -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and side chain. １１１ - May include at least one group selected from the group consisting of R. １１１ R represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. z and u represent 1. a represents an integer from 2 to 500, and b represents an integer from 5 to 100. １０ represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms. These groups may be substituted with substituents, and may also contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms. y represents an integer from 10 to 500.

2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block (A-2) comprises at least one of a structural unit represented by general formula (111) and a structural unit represented by general formula (112). 【Chemistry 2】 [wherein R ５５ and R ５６ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 20 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ２ -, -O- or -CO-. R １００ represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, the divalent aliphatic hydrocarbon group may optionally contain at least one selected from the group consisting of a branched structure and a cyclic structure, and may optionally contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom. y represents an integer of 10 to 500. s and t each independently represent an integer of 0 to 4.]]

3. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block (A-2) comprises a structural unit derived from at least one compound selected from the group consisting of 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclododecene, isosorbide, cyclohexane-1,4-dimethanol, tricyclodecanedimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol.

4. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block (A-2) comprises at least one selected from the group consisting of structural units represented by general formulas (a-i) to (a-v). 【Transformation 3】

5. The polycarbonate resin composition according to claim 1, wherein a is an integer between 2 and 300.

6. The polycarbonate resin composition according to claim 1, wherein b is 10 or more.

7. The polycarbonate resin composition according to claim 1, wherein the polyorganosiloxane block (A-1) comprises at least one selected from the group consisting of structural units represented by general formulas (1-1) to (1-3). 【Chemistry 4】 [In the formula, R １ ~R ４ , R ６ , R ８ , z, a, and b have the same meaning as above. R ５ This represents an alkylene group having 1 to 10 carbon atoms, and these groups are present in at least one of the main chain and side chains as -O-, -COO-, -CO-, -S-, -NH-, and -NR １１１ - May include at least one group selected from the group consisting of R. ７ This represents an alkylene group having 1 to 10 carbon atoms, and these groups are present in at least one of the main chain and side chains as -O-, -COO-, -CO-, -S-, -NH-, and -NR １１１ - May include at least one group selected from the group consisting of R. １１１ This represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. １ b indicates 1. １ β represents an integer between 5 and 100. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.

8. The aforementioned R １ ~R ４ The polycarbonate resin composition according to claim 1, wherein all of the groups are methyl groups.

9. The aforementioned R ６ The polycarbonate resin composition according to claim 1, wherein is a trimethylene group.

10. The aforementioned R ８ is a dimethylene group, a methyl-substituted dimethylene group (-CH ２ The polycarbonate resin composition according to claim 1, wherein the group is CHMe- or a trimethylene group, and z is 1.

11. The polycarbonate-based resin composition according to claim 1, wherein the polyorganosiloxane block (A-1) content in the polycarbonate-polyorganosiloxane copolymer (A) is 0.1% by mass or more and 60% by mass or less.

12. The polycarbonate-based resin composition according to claim 1, wherein the viscosity-average molecular weight (Mv) of the polycarbonate-polyorganosiloxane copolymer (A) is 5,000 or more and 50,000 or less.

13. The polycarbonate resin composition according to claim 1, wherein the tensile elongation at break of a molded piece obtained by molding the polycarbonate resin composition, which is a JIS K 7139:2009 dumbbell-type tensile test specimen type A22, has a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, is 10% or more, as measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm.

14. The polycarbonate resin composition according to claim 1, wherein the tensile modulus of a molded piece obtained by molding the polycarbonate resin composition, which is a JIS K 7139:2009 dumbbell-type tensile test specimen type A22 with a total length of 75 mm, a parallel section length of 30 mm, an end width of 10 mm, a central parallel section width of 5 mm, and a thickness of 2 mm, is 2250 MPa or more, as measured under the conditions of a tensile speed of 25 mm / min, a measurement temperature of 23°C, and a chuck distance of 57 mm.

15. The Charpy impact strength of a molded piece obtained by molding the polycarbonate resin composition, measuring 80 mm in length, 10 mm in width, and 4 mm in thickness, and then post-processing to add a notch (r = 0.25 mm ± 0.05 mm), was 38 kJ / m², measured under conditions of ISO 179-1:2010 and a measurement temperature of 23°C. ２ The polycarbonate resin composition according to claim 1 is as described above.

16. The polycarbonate-based resin composition according to claim 1, wherein the elastomer (B) comprises a core / shell type graft copolymer.

17. The polycarbonate resin composition according to claim 1, wherein the elastomer (B) comprises at least one selected from the group consisting of methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene copolymer, methyl methacrylate-acrylic rubber copolymer, methyl methacrylate-acrylic rubber-styrene copolymer, methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and methyl methacrylate-(acrylic / silicone IPN rubber) copolymer.

18. The polycarbonate resin composition according to claim 1, wherein the content of the elastomer (B) is 1.0 part by mass or more and 40 parts by mass or less per 100 parts by mass of the polycarbonate resin (S).

19. The polycarbonate-polyorganosiloxane copolymer (A) is a copolymer obtained by melt polymerization, as described in claim 1.

20. The polycarbonate-polyorganosiloxane copolymer (A) is a copolymer obtained using a diol monomer (a1), as described in claim 1.

21. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 20.

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