Polycarbonate-polyorganosiloxane copolymer

Abstract

The present invention relates to a polycarbonate-polyorganosiloxane copolymer (A) comprising a polyorganosiloxane containing block (A-1) that includes a constitutional unit expressed by general formula (1), and a polycarbonate block (A-2) that is formed from a repetition of a constitutional unit expressed by general formula (2), wherein: the content of the polyorganosiloxane containing block (A-1) accounts for 2-30 mass%; and the ratio of the average value of nb to the average value of na [(average value of nb) / (average value of na)] is 0.2-0.4.

Description

Polycarbonate-polyorganosiloxane copolymer

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate resin composition, and a molded article.

[0002] Polycarbonate resin is an engineering plastic that has excellent transparency and mechanical properties, as well as very high impact resistance. Polycarbonate-polyorganosiloxane copolymers, in which polycarbonate is copolymerized with polyorganosiloxane, are known to have excellent low-temperature impact resistance and chemical resistance while maintaining high transparency. Generally, known methods for producing polycarbonate resin include a method in which an aromatic dihydroxy compound is directly reacted with phosgene (interfacial polycondensation method), and a method in which an aromatic dihydroxy compound is subjected to a transesterification reaction with a carbonate diester in a molten state (melt polymerization method).

[0003] Patent Document 1 discloses a method for producing a polycarbonate-polyorganosiloxane copolymer by interfacial polycondensation, in which a diaryldiol compound such as bisphenol is reacted with phosgene in the presence of an organic solvent to produce a polycarbonate oligomer having reactive chloroformate groups, and then, simultaneously with or sequentially after the production of the polycarbonate oligomer, the polycarbonate oligomer, bisphenols, and a polyorganosiloxane having hydroxyl group-containing aryl groups at both ends are contacted in a methylene chloride / water medium. Generally, in a polymerization reaction, homo-coupled products formed by bonding identical raw material components together, or unreacted raw material components may be produced, with some raw materials not participating in the polymerization reaction. These components remain in the polymer without being uniformly incorporated into the polymer main chain, significantly reducing the transparency and mechanical properties of the polymer. The interfacial polymerization method described above rarely causes such problems, resulting in polycarbonate-polyorganosiloxane copolymers with excellent transparency and mechanical properties.

[0004] On the other hand, the interfacial polymerization method requires the use of highly toxic phosgene as a carbonate source. In addition, the polymerization reaction system requires the use of methylene chloride as a solvent, which places a heavy burden on the environment, and its removal requires large degassing equipment and a large amount of energy, making it economically disadvantageous. In contrast, the melt polymerization method for producing polycarbonate-polyorganosiloxane copolymers can avoid these problems. However, the polycarbonate-polyorganosiloxane copolymers produced by the melt polymerization method tend to have insufficient transparency, and improvements are being considered.

[0005] Patent Documents 2 to 4 disclose polycarbonate-polyorganosiloxane copolymers that can be produced by melt polymerization and have high transparency, and that contain a polyorganosiloxane block (A-1) containing a specific structural unit such as a polyol structure, and a specific polycarbonate block (A-2).

[0006] JP 2015-189953 A International Publication No. 2021 / 112257 International Publication No. 2021 / 112259 International Publication No. 2021 / 112260

[0007] Patent Documents 2 to 4 disclose methods for producing polycarbonate-polyorganosiloxane copolymers by melt polymerization, but there is room for improvement in terms of flowability, impact strength, tensile strength, and the appearance of injection-molded articles.

[0008] An object of the present invention is to obtain a polycarbonate-polyorganosiloxane copolymer that has excellent flowability and produces molded articles that are excellent in impact resistance, tensile elongation, and appearance.

[0009] As a result of extensive research, the present inventors have found that a polycarbonate-polyorganosiloxane copolymer having a specific structure can solve the above-mentioned problems. That is, the present invention encompasses the following: <1> A polycarbonate-polyorganosiloxane copolymer (A) comprising a polyorganosiloxane-containing block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) containing repeating structural units represented by the following general formula (2), wherein the content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less, ａ For the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ The polycarbonate-polyorganosiloxane copolymer has a coefficient of elasticity (σ) of 0.2 or more and 0.4 or less.

[0010]

[0011] [In the formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. ５ and R ６ each independently represents an alkylene group having 1 to 3 carbon atoms, and these groups may contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of ７ and R ８ 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 may have —O—, —COO—, —CO—, —S—, —NH—, —NR １１１ - may contain 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. １ , z２ , u １ and u ２ Each represents 0 or 1. ａ represents an integer of 2 to 500, and n ｂ R each independently represents an integer of 2 to 200. 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, and these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms.] <2> In the polycarbonate-polyorganosiloxane copolymer (A), n ａ The polycarbonate-polyorganosiloxane copolymer according to the above item <1>, wherein the average value of n is 10 or more and 90 or less. ａ For the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ <4> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <3> above, wherein the polyorganosiloxane-containing block (A-1) is represented by general formula (1), the following general formula (1-2), or the following general formula (1-3):

[0012] [In the formula, R １ ~R ８ , z １ , z ２ , u １ , u ２ , n ａ , and n ｂrepresents the same meaning as defined above. When a plurality of these are present, they may be the same or different. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.] <5> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <4> above, in which the polycarbonate block (A-2) composed of repeating structural units represented by the general formula (2) above contains a structural unit represented by the following general formula (111):

[0013]

[0014] [In the formula, R ５５ and R ５６ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ２ represents —, —O—, or —CO—, and s and t each independently represent an integer of 0 to 4.] <6> In the general formula (1), R １ ~R ４ <7> The polycarbonate-polyorganosiloxane copolymer according to any one of the above items <1> to <5>, wherein in the general formula (1), R ５ and R ６ are trimethylene groups (-(CH ２ ) ３ <8> The polycarbonate-polyorganosiloxane copolymer according to any one of the above items <1> to <6>, wherein, in the general formula (1), R ７ and R ８ are dimethylene groups (-(CH ２ ) ２ -), methyl-substituted dimethylene group (-CH ２ CH (CH ３ ) - or -CH(CH ３ ) CH ２-), trimethylene group (-(CH ２ ) ３ -), or a tetramethylene group (-(CH ２ ) ４ <9> The polycarbonate-polyorganosiloxane copolymer according to any one of the above <1> to <8>, wherein the content of polyorganosiloxane structures (A-3) comprised of repeating structural units represented by the following general formula (3) contained in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer is 0.1% by mass or more and 30% by mass or less:

[0015]

[0016] [In the formula, R １ ~R ２ has the same meaning as above.] <10> The polycarbonate-polyorganosiloxane copolymer according to any one of the above <1> to <9>, having a viscosity average molecular weight (Mv) of 15,000 or more and 30,000 or less. <11> The polycarbonate-polyorganosiloxane copolymer according to any one of the above <1> to <10>, obtained by a melt polymerization method. <12> The polycarbonate-polyorganosiloxane copolymer according to any one of the above <1> to <11>, obtained using a diol monomer (a1). <13> A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of the above <1> to <12>. <14> A molded article made from the polycarbonate-based resin composition according to the above <13>.

[0017] According to the present invention, it is possible to obtain a polycarbonate-polyorganosiloxane copolymer which has excellent flowability and produces a molded product which is excellent in impact resistance, tensile elongation, and appearance.

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

[0019] <Polycarbonate-Polyorganosiloxane Copolymer (A)> The polycarbonate-polyorganosiloxane copolymer (A) of the present invention comprises a polyorganosiloxane-containing block (A-1) containing a structural unit represented by the following general formula (1) and a polycarbonate block (A-2) containing a repeating structural unit represented by the following general formula (2), wherein the content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less, ａ For the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ The average value of the above values ​​is 0.2 or more and 0.4 or less.

[0020]

[0021] [In the formula, R １ ~R ４ R each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. ５ and R ６ each independently represents an alkylene group having 1 to 3 carbon atoms, and these groups may contain -O-, -COO-, -CO-, -S-, -NH-, and -NR in at least one of the main chain and the side chain. １１１ - may contain at least one group selected from the group consisting of ７ and R ８ 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 may have —O—, —COO—, —CO—, —S—, —NH—, —NR１１１ - may contain 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. １ , z ２ , u １ and u ２ Each represents 0 or 1. ａ represents an integer of 2 to 500, and n ｂ R each independently represents an integer of 2 to 200. 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, and these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.]

[0022] In the polycarbonate-polyorganosiloxane copolymer (A), the polyorganosiloxane block (A-1) is preferably a structural unit represented by any one of the above general formula (1), the following general formula (1-2), or the following general formula (1-3). The polycarbonate-polyorganosiloxane copolymer (A) may contain multiple types of polyorganosiloxane blocks (A-1). The polyorganosiloxane block (A-1) is more preferably a structural unit represented by the above general formula (1).

[0023]

[0024] [In the formula, R １ ~R ８ , z １ , z ２ , u １ , u ２ , n ａ , and n ｂ represents the same meaning as above. When a plurality of these are present, they may be the same or different. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.

[0025] In the formula, R １ ~R ４Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. １ ~R ４ Examples of alkyl groups having 1 to 10 carbon atoms represented by R include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. In this specification, the term "various" refers to both linear and branched groups, and the same applies hereinafter. １ ~R ４ The alkoxy group having 1 to 10 carbon atoms represented by R includes an alkoxy group in which the alkyl group moiety is the same as the alkyl group described above. １ ~R ４ Examples of the aryl group having 6 to 12 carbon atoms represented by R include a phenyl group and a naphthyl group. １ ~R ４ Examples of the alkylarylene group having 7 to 22 carbon atoms represented by R include alkylarylene groups in which the alkyl group moiety is the same as the alkyl group described above and the arylene group moiety is a divalent group obtained by removing one hydrogen atom from the aryl group described above. １ ~R ４ are each preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylarylene group having 7 to 22 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably a methyl group. ５ and R ６ Examples of the alkylene group having 1 to 3 carbon atoms represented by R include a methylene group, a dimethylene group, a trimethylene group, and a methyl-substituted dimethylene group. ７ and R ８ Examples of the arylene group having 6 to 20 carbon atoms represented by R include a phenylene group and a naphthylene group. ７ and R ８ Examples of the alkylene group having 1 to 10 carbon atoms represented by R include a methylene group, a dimethylene group, a trimethylene group, a methyl-substituted dimethylene group, and various butylene groups. The various butylene groups are preferably tetramethylene groups. ７ and R ８The alkylarylene group represented by the formula (I) includes an alkylarylene group in which the alkyl group moiety is the same as the alkylene group described above and the arylene group moiety is the same as the arylene group described above. ５ , R ６ , R ７ , and R ８ contains —O—, —COO—, —OCO—, —CO—, —S—, —NH—, and NR in at least one of the main chain and the side chain. １１１ - may contain 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. １１１ Examples of the alkyl group having 1 to 10 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. １１１ Examples of the aryl group having 6 to 10 carbon atoms represented by R include a phenyl group and a naphthyl group. ５ and R ６ are preferably each a methylene group (-(CH ２ )-), dimethylene group (-(CH ２ ) ２ -), or a trimethylene group (-(CH ２ ) ３ -), and more preferably a trimethylene group (-(CH ２ ) ３ -). R ７ and R ８ are preferably alkylene groups each having 1 to 10 carbon atoms, more preferably alkylene groups each having 1 to 5 carbon atoms, and even more preferably dimethylene groups (-(CH ２ ) ２ -), methyl-substituted dimethylene group (-CH ２ CH (CH ３ ) - or -CH(CH ３ ) CH ２ -), a trimethylene group, or a tetramethylene group (-(CH ２ ) ４ -), and more preferably, each is a dimethylene group.

[0026] z １ , z２ , u １ and u ２ are each 0 or 1. １ and z ２ are each preferably 1, and z １ and z ２ It is more preferable that both are 1. １ and u ２ are each preferably 1, and u １ and u ２ It is more preferable that both are 1.

[0027] In general formula (1), R １ ~R ４ are all methyl groups, and R ５ and R ６ are both trimethylene groups, and R ７ and R ８ are both dimethylene groups, and z １ and z ２ are all 1, and u １ and u ２ A polyorganosiloxane block in which each of the groups is 1 is preferred.

[0028] n ａ represents the chain length of the polyorganosiloxane structure in the general formula (1). ａ is an integer of 2 or more and 500 or less, preferably an integer of 10 or more and 90 or less, more preferably an integer of 20 or more and 70 or less, even more preferably an integer of 30 or more and 60 or less, and still more preferably an integer of 35 or more and 50 or less. ａ The average value of the -SiR in the general formula (1), i.e., the average chain length of the polyorganosiloxane structure in the general formula (1), is 2 to 500, preferably 10 to 90, more preferably 20 to 70, even more preferably 30 to 60, and even more preferably 35 to 50. When the average chain length of the polyorganosiloxane structure in the general formula (1) is within the above range, a copolymer having excellent impact resistance, tensile elongation, and appearance can be obtained as a molded product. １ R ２ The number of repeating —O— structures is nａ The average chain length of the polyorganosiloxane structure in general formula (1) is calculated by nuclear magnetic resonance (NMR) measurement.

[0029] n ｂ represents -(O) in general formula (1). Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ - indicates the number of repeats of the structure. ｂ is an integer of 2 or more and 200 or less, preferably an integer of 3 or more and 40 or less, more preferably an integer of 7 or more and 30 or less, even more preferably an integer of 10 or more and 25 or less, and still more preferably an integer of 10 or more and 20 or less. ｂ That is, the average value of -(O) in the general formula (1) Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ The average number of repeating units of the - structure is 2 or more and 200 or less, preferably 3 or more and 40 or less, more preferably 7 or more and 30 or less, even more preferably 10 or more and 25 or less, and even more preferably 10 or more and 20 or less. The above ranges are preferable in terms of the ease of availability of raw materials for producing the polycarbonate-polyorganosiloxane copolymer (A). ｂ is 10 or more, the balance between the mechanical strength and the mold releasability of the resulting molded article of the polycarbonate-polyorganosiloxane copolymer (A) can be further improved, and ｂ When n is 100 or less, the viscosity and melting point of the polyorganosiloxane during production fall within a suitable range, and handling properties are further improved, which is more preferable. ｂ It is more preferable that the -(O) in the general formula (1) is 50 or less, since the effect of improving the physical properties of the polycarbonate-polyorganosiloxane copolymer (A) by containing the polyorganosiloxane block is further improved. Ｚ １ -R ７ -structure and -R８ -(O) Ｚ ２ The average repeat number of the structure is calculated by nuclear magnetic resonance (NMR) measurement.

[0030] In the polycarbonate-polyorganosiloxane copolymer (A), n ａ For the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ The average value of the above n ａ n for the average value of ｂ If the ratio of the average values ​​of these is within the above range, a copolymer having excellent flowability and having molded articles excellent in impact resistance, tensile elongation and appearance can be obtained.

[0031] In the polycarbonate-polyorganosiloxane copolymer (A) of the present invention, n ａ n for the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ The reason why a copolymer having excellent fluidity and having molded bodies excellent in impact resistance, tensile elongation, and appearance can be obtained by having a value of 0.2 or more and 0.4 or less is presumed to be as follows. The polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the following general formula (3) contained in the polyorganosiloxane-containing block (A-1) represented by the above general formula (1) is known to be able to impart physical properties such as impact resistance to the polycarbonate-polyorganosiloxane copolymer (A). However, since the polyorganosiloxane structure (A-3) has a low polarity, its compatibility with the polycarbonate block (A-2), which has a high polarity, is insufficient. If the content of the polyorganosiloxane structure (A-3) is too high, the polyorganosiloxane structure (A-3) separates from the polycarbonate block (A-2) to form a phase-separated structure, which is thought to result in insufficient physical properties such as tensile elongation and the appearance of the molded body.

[0032]

[0033] [In the formula, R １ ~R ２has the same meaning as above.]

[0034] On the other hand, the -(O) contained in the polyorganosiloxane-containing block (A-1) represented by the general formula (1) Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ The - structure has high polarity, and these structures have high compatibility with the highly polar polycarbonate block (A-2), but -(O) Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ Since the - structure is a relatively flexible structure and has low strength, if its content is too high, it is thought that the physical properties such as impact resistance of the molded article of the polycarbonate-polyorganosiloxane copolymer (A) may become insufficient. Therefore, it is considered that the average chain length of the polyorganosiloxane structure contained in the polycarbonate-polyorganosiloxane copolymer (A) of the present invention and the -(O) Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ It is believed that by setting the ratio of the average repeating number of - structures within a predetermined range, a polycarbonate-polyorganosiloxane copolymer (A) can be obtained that has excellent flowability and produces molded articles that are excellent in impact resistance, tensile elongation, and appearance.

[0035] The polycarbonate-polyorganosiloxane copolymer (A) of the present invention is ａ n for the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ the ratio of the high polarity -(O) to the content of the low polarity polyorganosiloxane structure (A-3) is 0.2 or more, Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２It is believed that the content of the - structure is sufficiently large, and that the polyorganosiloxane structure (A-3) and the polycarbonate block (A-2) are sufficiently compatible with each other. For this reason, it is believed that the polyorganosiloxane-containing block (A-1) does not form phase separation in the resin structure of the polycarbonate-polyorganosiloxane copolymer (A), and that excellent physical properties such as tensile elongation and appearance such as color tone of the molded article can be achieved. Furthermore, the polycarbonate-polyorganosiloxane copolymer (A) of the present invention has a n ａ n for the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ the average value of (O) is 0.4 or less, Ｚ １ -R ７ -structure and -R ８ -(O) Ｚ ２ The content of the - structure is sufficiently small compared to the content of the polyorganosiloxane structure (A-3), and it is believed that the polycarbonate-polyorganosiloxane copolymer (A) can achieve excellent physical properties such as impact resistance of molded articles.

[0036] n ａ n for the average value of ｂ The ratio of the average values ​​of [(n ｂ Average value of n ａ The average value of n is preferably 0.22 or more and 0.35 or less, and more preferably 0.24 or more and 0.30 or less. ａ n for the average value of ｂ When the ratio of the average values ​​of these is within the above preferred range, it is possible to obtain a polycarbonate-polyorganosiloxane copolymer (A) that is more excellent in flowability and that produces a molded product that is more excellent in impact resistance, tensile elongation, and appearance.

[0037] R in the above general formula (2) １０Examples of the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by the formula (2) include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a 2-ethylhexylene group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group, an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, and an n-octadecylene group. However, these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. １０ Examples of the divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms represented by include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, and a tricyclodecylene group. However, these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0038] R in the above general formula (2) １０Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (I) include divalent aromatic hydrocarbon groups derived from 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, and catechol. However, these groups may be substituted with a substituent and may contain at least one atom selected from the group consisting of oxygen, nitrogen, sulfur, and halogen atoms.

[0039] The polycarbonate block (A-2) consisting of repeating structural units represented by the above general formula (2) preferably contains repeating structural units represented by the general formula (111).

[0040]

[0041] [In the formula, R ５５ and R ５６ each independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, 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 represents -, -O-, or -CO-; and s and t each independently represent an integer of 0 to 4.]

[0042] R ５５ and R ５６ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ５５ and R５６ Examples of the alkyl group having 1 to 6 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. ５５ and R ５６ The alkoxy group having 1 to 6 carbon atoms represented by the formula (I) includes an alkoxy group in which the alkyl group moiety is the same as the alkyl group described above.

[0043] Examples of the alkylene group having 1 to 8 carbon atoms represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, with an alkylene group having 1 to 5 carbon atoms being preferred. Examples of the alkylidene group having 2 to 8 carbon atoms represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group having 5 to 15 carbon atoms represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, with a cycloalkylene group having 5 to 10 carbon atoms being preferred. Examples of the arylene group having 6 to 20 carbon atoms represented by X include a phenylene group, a naphthylene group, and a biphenylene group. Examples of the cycloalkylidene group having 5 to 15 carbon atoms represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group, with a cycloalkylidene group having 5 to 10 carbon atoms being preferred, and a cycloalkylidene group having 5 to 8 carbon atoms being more preferred. Examples of the aryl alkylene group having 7 to 15 carbon atoms represented by X include an aryl alkylene group in which the aryl moiety is an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, or an anthryl group, and the alkylene moiety is the same as the alkylene group. Examples of the aryl alkylidene group having 7 to 15 carbon atoms represented by X include an aryl alkylidene group in which the aryl moiety is an aryl group having 6 to 14 ring carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, or an anthryl group, and the alkylidene moiety is the same as the alkylidene group.

[0044] s and t each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among these, preferably s and t are 0 and X represents a single bond or an alkylene group having 1 to 8 carbon atoms, or preferably s and t are 0 and X represents an alkylidene group, and more preferably s and t are 0 and X represents an isopropylidene group.

[0045] The polycarbonate block (A-2) composed of repeating structural units represented by the general formula (2) above can contain structural units other than the structural unit represented by the general formula (111). Specifically, the polycarbonate block (A-2) composed of repeating structural units represented by the general formula (2) above can further contain a structural unit represented by the general formula (112).

[0046]

[0047] [In the formula, R １００ represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, and the divalent aliphatic hydrocarbon group may contain at least one selected from the group consisting of a branched structure and a cyclic structure, and may contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.]

[0048] R １００ Examples of the divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms represented by the formula (I) include an alkylene group having 2 to 40 carbon atoms, a cycloalkylene group having 4 to 40 carbon atoms, and a divalent saturated heterocyclic group containing 4 to 40 carbon atoms and oxygen or nitrogen. The alkylene group preferably has 2 to 18 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 3 to 6 carbon atoms. The cycloalkylene group preferably has 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms. The divalent saturated heterocyclic group containing oxygen or nitrogen preferably has 4 to 20 carbon atoms, more preferably 5 to 20 carbon atoms. However, these groups may contain at least one structure selected from the group consisting of a branched structure and a cyclic structure, and may also contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0049] Examples of the alkylene group having 2 to 40 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, a 2-ethylhexylene group, an n-nonylene group, an n-decylene group, an n-undecylene group, an n-dodecylene group, an n-tridecylene group, an n-tetradecylene group, an n-pentadecylene group, an n-hexadecylene group, an n-heptadecylene group, and an n-octadecylene group. Examples of the cycloalkylene group having 4 to 40 carbon atoms include a cyclopentylene group, a cyclohexylene group, a cyclooctylene group, a cyclodecylene group, a cyclotetradecylene group, an adamantylene group, a bicycloheptylene group, a bicyclodecylene group, and a tricyclodecylene group. Examples of the divalent heterocyclic group having 4 to 40 carbon atoms and containing oxygen or nitrogen include those containing an oxygen or nitrogen atom in the cycloalkylene group skeleton.

[0050] Specific examples of the structural unit represented by the general formula (112) include structural units represented by the following general formulae (ai) to (a-xiii).

[0051]

[0052]

[0053]

[0054] The polycarbonate block (A-2) composed of repeating structural units represented by general formula (2) preferably contains 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, tricyclodecane dimethanol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3-propanediol, and 1,4-butanediol.

[0055] The polycarbonate block (A-2) preferably contains a structural unit represented by general formula (2) as a main component. The polycarbonate block (A-2) preferably contains the structural unit 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 the polyorganosiloxane-containing block (A-1). More preferably, the polycarbonate block (A-2) consists only of repeating structural units represented by general formula (2). Of these, it is particularly preferred that the polycarbonate block (A-2) consists only of repeating structural units represented by general formula (111).

[0056] In the polycarbonate-polyorganosiloxane copolymer (A), the polyorganosiloxane-containing block (A-1) and the polycarbonate block (A-2) are preferably bonded via a carbonate bond (-O-C(=O)-O- group). For example, when the polyorganosiloxane block (A-1) is a structural unit represented by the general formula (1), the structural unit represented by the general formula (1) is directly bonded to the adjacent polycarbonate block (A-2) via a carbonate bond.

[0057] In this specification, structures represented by chemical formulas may exist as optical isomers, stereoisomers, etc. due to the presence of asymmetric centers. In this case, all isomers and mixtures thereof are encompassed. For example, the structural unit represented by the above general formula (a-iii) preferably includes a structural unit represented by the following general formula (a-iii'), and more preferably consists solely of a structural unit represented by the following general formula (a-iii'):

[0058]

[0059] The content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is 2% by mass or more and 30% by mass or less. By having the content of the polyorganosiloxane-containing block (A-1) in the above range, it is possible to obtain a copolymer having excellent fluidity and excellent impact resistance of a molded article. The content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 2.5% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less. By having the content of the polyorganosiloxane-containing block (A-1) in the above preferred range, it is possible to obtain a copolymer having excellent fluidity and having a molded article having excellent impact resistance, tensile elongation, and appearance. In this specification, the "content of polyorganosiloxane-containing block (A-1) in polycarbonate-polyorganosiloxane copolymer (A)" refers to the percentage of the total mass of the structural unit represented by general formula (3) and the structural unit represented by general formula (Y) below relative to the total mass of the polycarbonate block (A-2), the structural unit represented by general formula (3), the structural unit represented by general formula (Y) below, and, if necessary, the terminal structure derived from the terminal terminator contained in the polycarbonate-polyorganosiloxane copolymer (A) described below.

[0060]

[0061] [In the formula, R Ｙ is R ７ or R ８ It is. Ｙ is R８ If z ０ Ga z ２ and R Ｙ is R ７ If z ０ Ga z １ It is. ７ , R ８ , z １ , and z ２ has the same meaning as above.]

[0062] In the polycarbonate-polyorganosiloxane copolymer (A), the content of the polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the general formula (3) contained in the polyorganosiloxane-containing block (A-1) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 15% by mass or less, and even more preferably 1.0% by mass or more and 10% by mass or less. By having the content of the polyorganosiloxane structure in the above preferred range, a copolymer having better impact resistance of a molded body can be obtained. In this specification, "the content of the polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the general formula (3) contained in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)" refers to the polycarbonate block (A-2), the structural unit represented by the general formula (3), the structural unit represented by the general formula (Y), and, if necessary, the polycarbonate-polyorganosiloxane copolymer (A). This is the percentage of the total mass of the structural unit represented by the general formula (3) relative to the total mass of the terminal structure derived from the terminal terminator described below.

[0063] The content of the polycarbonate block (A-2) 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, still more preferably 90% by mass or more, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, even more preferably 99.0% by mass or less, still more preferably 97.0% by mass or less.

[0064] The viscosity average molecular weight of the polycarbonate-polyorganosiloxane copolymer (A) is preferably 15,000 to 30,000, more preferably 17,000 to 27,000, even more preferably 18,000 to 25,000, even more preferably 19,000 to 24,000, and even more preferably 20,500 to 23,000. The viscosity average molecular weight (Mv) herein is a value calculated from the intrinsic viscosity [η] of a methylene chloride solution (concentration: g / L) at 20°C using the following Schnell formula: [η] = 1.23 × 10 －５ Mv ０．８３

[0065] <Method for Producing Polycarbonate-Polyorganosiloxane Copolymer (A)> The polycarbonate-polyorganosiloxane copolymer (A) of the present invention can be produced, for example, by using a diol monomer (a1) and a polyorganosiloxane (a2) as raw material monomers.

[0066] <<Diol Monomer (a1)>> The diol monomer (a1) is not particularly limited as long as it has a structure represented by the following general formula (a1): As the diol monomer (a1), an aromatic dihydroxy compound or an aliphatic dihydroxy compound can be used.

[0067]

[0068] R in the above general formula (a1) １０ are as described above, and the preferred ones are also the same.

[0069] <<Polyorganosiloxane (a2)>> The polyorganosiloxane (a2) preferably has a structure represented by any one of the following general formulas (a2-1) to (a2-3).

[0070] [In the formula, R １ ~R ８ , z １ , z ２ , u １ , u ２ , n ａ n ｂ , and β have the same meanings as above.]

[0071] The method for producing the polyorganosiloxane (a2) is not particularly limited. For example, according to the method described in JP-A-11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize an α,ω-dihydrogenorganopentasiloxane, and then, in the presence of a hydrosilylation catalyst, the α,ω-dihydrogenorganopentasiloxane is subjected to an addition reaction with an oligomer or polymer (e.g., polyalkylene ether, polyester, polycarbonate, etc.) modified at one end with an allyl group, thereby obtaining a polyorganosiloxane. According to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (an acidic catalyst), and the resulting α,ω-dihydrogenorganopolysiloxane is subjected to an addition reaction with an oligomer or polymer, one end of which is modified with an allyl group, in the presence of a hydrosilylation catalyst, to obtain a polyorganosiloxane. The average repeat number n of the α,ω-dihydrogenorganopolysiloxane can be varied depending on the polymerization conditions. ａ Alternatively, commercially available α,ω-dihydrogenorganopolysiloxanes may be used. In addition, the average repeat number n of an oligomer modified with an allyl group at one end can be adjusted by changing the polymerization conditions. ｂ may be used by appropriately adjusting the amount, or a commercially available oligomer modified with an allyl group at one end may be used. Among the oligomers modified with an allyl group at one end, polyethylene glycol modified with an allyl group at one end can be produced by referring to Japanese Patent No. 5652691, etc. In addition, examples of commercially available allyl-modified polyethylene glycols include UNIOX PKA-5001, UNIOX PKA-5002, UNIOX PKA-5003, UNIOX PKA-5004, and UNIOX PKA-5005 manufactured by NOF Corporation.

[0072] The polycarbonate-polyorganosiloxane copolymer (A) can be produced by polymerizing raw material monomers by interfacial polymerization or melt polymerization (transesterification). The polycarbonate-polyorganosiloxane copolymer (A) is preferably obtained by melt polymerization. When producing the polycarbonate-polyorganosiloxane copolymer (A) by interfacial polymerization, for example, a method described in JP 2014-80462 A can be adopted. The polycarbonate-polyorganosiloxane copolymer (A) can be produced by reacting the raw material monomers polyorganosiloxane (a2), diol monomer (a1), and a carbonate ester compound by melt polymerization, preferably in the presence of a basic catalyst. At this time, a terminal terminator may be further added to carry out the polymerization reaction. Therefore, the present invention also provides a method for producing a polycarbonate-polyorganosiloxane copolymer (A), which includes a step of reacting a polyorganosiloxane (a2), a diol monomer (a1), and a carbonate ester compound by melt polymerization. The melt polymerization reaction step is preferably carried out in the presence of a basic catalyst. The melt polymerization method is preferable from the standpoint of environmental impact and economic efficiency because it does not require solvents such as methylene chloride, which tend to be environmentally hazardous and expensive. Furthermore, it is also preferable from the standpoint of safety during production because it does not use highly toxic phosgene as a carbonate source. The melt polymerization method is environmentally and economically advantageous because it does not require solvents such as methylene chloride, which are required in interfacial polymerization. In addition, it is advantageous from the standpoint of production because it does not use highly toxic phosgene, which is used as a carbonate source in interfacial polymerization.

[0073] (Carbonate Compound) Examples of the carbonate compound include diaryl carbonate compounds, dialkyl carbonate compounds, and alkylaryl carbonate compounds. Examples of the diaryl carbonate compound include compounds represented by the following general formula (11) and compounds represented by the following general formula (12).

[0074]

[0075] [In formula (11), Ar １ and Ar２ Each of Ar represents an aryl group, and may be the same or different. ３ and Ar ４ each represents an aryl group, and may be the same or different; D １ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0076] Examples of the dialkyl carbonate compound include a compound represented by the following general formula (13) and a compound represented by the following general formula (14).

[0077]

[0078] [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 may be the same or different. ２３ and R ２４ each represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, which may be the same or different from each other; D ２ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0079] Examples of the alkyl aryl carbonate compound include a compound represented by the following general formula (15) and a compound represented by the following general formula (16).

[0080]

[0081] [In formula (15), Ar ５ is an aryl group, R ２５ represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. ６ is an aryl group, R ２６ is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms; D １ represents a residue obtained by removing two hydroxyl groups from the aromatic dihydroxy compound or aliphatic dihydroxy compound.

[0082] Examples of diaryl carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl)carbonate, bis(m-cresyl)carbonate, dinaphthyl carbonate, bis(diphenyl)carbonate, and bisphenol A bisphenyl carbonate. Examples of dialkyl carbonate compounds include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A bismethyl carbonate. Examples of alkyl aryl carbonate compounds include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate. A preferred carbonate ester compound is diphenyl carbonate. One or more carbonate ester compounds can be used to produce the polycarbonate-polyorganosiloxane copolymer (A).

[0083] (Terminator) When producing the polycarbonate-polyorganosiloxane copolymer (A), a terminal terminator can be used as needed. As the terminal terminator, a known terminal terminator used in the production of polycarbonate resins may be used, and specific examples thereof include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0084] (Branching Agent) A branching agent can also be used in producing the polycarbonate-polyorganosiloxane copolymer (A). Examples of branching agents include phloroglucin, trimellitic acid, 1,1,1-tris(4-hydroxyphenyl)ethane, 1-[α-methyl-α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene, α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, and isatin bis(o-cresol).

[0085] Specifically, polycarbonate-polyorganosiloxane copolymer (A) can be produced by melt polymerization, for example, according to the following procedure. Diol monomer (a1), polyorganosiloxane (a2), and a carbonate ester compound are subjected to a transesterification reaction. The ratio of the carbonate ester compound to the diol monomer is preferably 0.9 to 1.2 times by mole, more preferably 0.98 to 1.02 times by mole. In the above transesterification reaction, if the amount of end-capping agent present is in the range of 0.05 to 10 mol% relative to the total amount of diol monomer (a1) and polyorganosiloxane (a2), this is preferred from the viewpoint of obtaining a polycarbonate resin with excellent heat resistance and water resistance, since the hydroxyl group terminals of the resulting polycarbonate-polyorganosiloxane copolymer are sufficiently blocked. The amount of end-capping agent present relative to the total amount of diol monomer (a1) and polyorganosiloxane (a2) is more preferably 1 to 6 mol%. The entire amount of the terminal terminator may be added to the reaction system in advance, or a portion may be added to the reaction system in advance, with the remainder added as the reaction progresses. It is preferable to simultaneously charge an antioxidant into a reactor along with the diol monomer (a1), polyorganosiloxane (a2), and carbonate ester compound, and carry out the transesterification reaction in the presence of the antioxidant. This can reduce, for example, deterioration of the diol monomer due to heat, oxidation, etc. in the heat-melting step before catalyst addition, as well as deterioration of the diol monomer and the resulting polycarbonate-polyorganosiloxane copolymer due to heat, oxidation, etc. in the polymerization step after catalyst addition. This can result in a polycarbonate-polyorganosiloxane copolymer with even better appearance, such as color tone, and also provides effects such as reducing the formation of undesirable gel components.

[0086] The reaction temperature for carrying out the transesterification reaction is not particularly limited, and may be, for example, in the range of 100 to 330°C, preferably 180 to 300°C, and more preferably 200 to 240°C. A method in which the temperature is gradually increased from 180°C to 300°C as the reaction progresses is also preferred. If the temperature of the transesterification reaction is 100°C or higher, the reaction rate is sufficiently fast, while if the temperature is 330°C or lower, side reactions do not occur frequently, and the resulting polycarbonate-polyorganosiloxane copolymer is less likely to suffer from poor appearance, such as discoloration.

[0087] The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. There are no particular limitations as long as it is set so that the reaction proceeds efficiently. For example, in the early stage of the reaction, the pressure is set to atmospheric pressure (normal pressure) or a pressurized state of 1 to 50 atm (760 to 38,000 torr), and in the later stage of the reaction, the pressure is set to a reduced pressure, and finally to 1.33 to 1.33 × 10 ４ The reaction time may be such that the reaction is continued until the target molecular weight is achieved, and is, for example, 0.2 to 10 hours.

[0088] The above transesterification reaction is carried out, for example, in the absence of an inert solvent, but may be carried out, if necessary, in the presence of 1 to 150 parts by mass of an inert solvent per 100 parts by mass of the resulting polycarbonate resin. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenyl ether, dichlorobenzene, and methylnaphthalene; and tricyclo[5.2.1.0] ２，６ ] cycloalkanes such as decane, cyclooctane, and cyclodecane. If necessary, the reaction may be carried out in an inert gas atmosphere, and examples of the inert gas include argon, carbon dioxide, nitrous oxide, nitrogen, and other gases, chlorofluorohydrocarbons, alkanes such as ethane and propane, and alkenes such as ethylene and propylene.

[0089] In the melt polymerization method, it is preferable to use a basic catalyst as the catalyst. Examples of the basic catalyst include at least one selected from the group consisting of metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing an aryl group, and metal compounds. These compounds can be used alone or in combination. Examples of the basic catalyst that are preferably used include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; and quaternary phosphonium salts containing an aryl group. The basic catalysts can be used alone or in combination.

[0090] Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt, lithium salt of phenol, etc. 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, barium diacetate, etc.

[0091] Examples of the nitrogen-containing compound include quaternary ammonium hydroxides having an alkyl or aryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. Other examples include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. Further examples include bases or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0092] Examples of the metal compound include zinc aluminum compounds, germanium compounds, organotin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0093] Specific examples of quaternary phosphonium salts containing an aryl group include tetra(aryl or alkyl)phosphonium hydroxides such as tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, and tetrabutylphosphonium hydroxide; tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-t-butylphenyl)phosphonium diphenylphosphate, triphenylbutylphosphonium phenolate, and triphenylbutylphosphonium tetraphenylborate. The quaternary phosphonium salt containing an aryl group is preferably combined with a nitrogen-containing organic basic compound, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0094] The amount of the basic catalyst used is preferably 1×10 relative to 1 mole of the diol monomer (a1). －９ ~1 x 10 －２ mole, preferably 1 x 10 －８ ~1 x 10 －２ mole, more preferably 1 x 10 －７ ~1 x 10 －３ You can choose from a range of moles.

[0095] A catalyst deactivator may be added in the latter stage of the reaction. Known catalyst deactivators are effectively used as the catalyst deactivator. Examples of catalyst deactivators include ammonium salts of sulfonic acid and phosphonium salts of sulfonic acid.

[0096] When at least one polymerization catalyst selected from alkali metal compounds and alkaline earth metal compounds is used, the catalyst deactivator can be used in an amount of preferably 0.5 to 50 moles per mole of the catalyst, more preferably 0.5 to 10 moles, and even more preferably 0.8 to 5 moles. It is preferable to add the catalyst deactivator and mix in an antioxidant after completing the polymerization reaction. By mixing in an antioxidant after completing the polymerization reaction and then removing the resulting polycarbonate-polyorganosiloxane copolymer from the reactor, it is possible to reduce degradation of the polycarbonate-polyorganosiloxane copolymer due to heat, oxygen, etc. in the subsequent compounding process and the process for obtaining a molded product. This allows for the production of resin pellets and molded products with even more excellent appearances, such as color tone and surface appearance, and also provides the effect of reducing the production of undesirable gel components.

[0097] The melt polymerization reaction may be carried out either continuously or batchwise. The reaction apparatus used for melt polymerization may be a vertical reaction apparatus equipped with an anchor-type impeller, a Maxblend impeller, or a helical ribbon impeller, or a horizontal reaction apparatus equipped with a paddle impeller, a lattice impeller, or a spectacle impeller. It may also be an extruder equipped with a screw. In the case of a continuous reaction, it is preferable to use an appropriate combination of such reaction apparatuses.

[0098] <Polycarbonate Resin Composition> The polycarbonate resin composition of the present invention contains the above-mentioned polycarbonate-polyorganosiloxane copolymer (polycarbonate-polyorganosiloxane copolymer (A)). Well-known additives can be used in the polycarbonate resin composition of the present invention as long as the properties of the polycarbonate-polyorganosiloxane copolymer (A) are not impaired.

[0099] (Additives) Known additives can be blended into the polycarbonate resin composition of the present invention depending on the intended use and needs. Examples of additives include various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymerized metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, UV absorbers, and mold release agents. Antioxidants can suppress decomposition of resins during the production and molding of the thermoplastic resin composition.

[0100] The method for producing the polycarbonate-based resin composition of the present invention is not particularly limited as long as it includes a step of mixing a polycarbonate-polyorganosiloxane copolymer with optional additives. For example, the polycarbonate-based resin composition can be produced by mixing the polycarbonate-polyorganosiloxane copolymer with optional additives using a mixer or the like, followed by melt-kneading. Melt-kneading can be carried out by a commonly used method, such as a method using a ribbon blender, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, or multi-screw extruder. The heating temperature during melt-kneading is typically selected from the range of 150 to 300°C, preferably from about 220 to 300°C.

[0101] [Molded Article] The molded article of the present invention contains the polycarbonate resin composition of the present invention. The molded article can be produced by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc. using a melt-kneaded product of the polycarbonate resin composition or pellets obtained through melt-kneading as a raw material. In particular, it is preferable to produce the molded article by injection molding or injection compression molding using the obtained pellets.

[0102] The thickness of the molded article can be set arbitrarily depending on the application, and when transparency of the molded article is particularly required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and even more preferably 0.3 to 2.0 mm. If the thickness of the molded article is 0.2 mm or more, no warping occurs and good mechanical strength is obtained. Furthermore, if the thickness of the molded article is 4.0 mm or less, high transparency is obtained.

[0103] The molded article may be coated with a hard coat film, an anti-fogging film, an antistatic film, or an anti-reflection film as needed, or may be coated with a composite of two or more types of films. Among these, it is particularly preferable to form a hard coat film because it has good weather resistance and can prevent wear of the molded article 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.

[0104] Molded articles containing the polycarbonate resin according to the present invention can be suitably used for components requiring transparency and rigidity, as well as scratch resistance and weather resistance, such as: 1) automobile parts such as sunroofs, door visors, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms, and gratings; 3) windows for railway cars and ships; 4) electrical equipment parts such as various parts, outer panels, and housings for televisions, radio cassette players, video cameras, video tape recorders, audio players, DVD players, telephones, displays, computers, cash registers, copiers, printers, and facsimiles; 5) precision equipment parts such as cases and covers for precision equipment such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as vinyl greenhouses and greenhouses; and 7) furniture parts such as lighting covers, blinds, and interior fixtures.

[0105] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0106] [1. Production of Terminally Modified Polyorganosiloxane] Synthesis Example 1: Production of PDMS-1 Under a nitrogen atmosphere,

[0107]

[0108] To 100 g of an α,ω-dihydrogenorganopolysiloxane having an average chain length of 45 represented by the following formula:

[0109]

[0110] To the mixture was added 35.3 g (twice the molar amount relative to the polyorganosiloxane) of polyethylene glycol modified with an allyl group at one end and having an average repeating number of oxyethylene units of 12, as represented by the formula (1). 338 g of toluene (2.5 parts relative to the total mass of the polyorganosiloxane and polyethylene glycol) was added as a solvent, and the mixture was thoroughly stirred while maintaining the temperature at 80°C. Next, a toluene solution of a platinum vinylsiloxane complex (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added as a hydrosilylation catalyst, and the mass of the platinum atom was adjusted to the siloxane unit (-[Si(CH ３ ) ２ The resulting mixture was stirred for 10 hours at a reaction temperature of 110° C. Toluene and the platinum catalyst were removed from the resulting mixture to obtain a modified polyorganosiloxane PDMS-1.

[0111] Synthesis Example 2: Production of PDMS-2

[0123] Modified polyorganosiloxane PDMS-2 was obtained in the same manner as in Synthesis Example 1, except that 100 g of an α,ω-dihydrogenorganopolysiloxane having an average chain length of 61 was used instead of the α,ω-dihydrogenorganopolysiloxane having an average chain length of 45, and 31.4 g of a one-terminal allyl group-modified polyethylene glycol having an average repeat number of oxyethylene units of 15 was used instead of the one-terminal allyl group-modified polyethylene glycol having an average repeat number of oxyethylene units of 12.

[0112] Synthesis Example 3: Production of PDMS-3 Modified polyorganosiloxane PDMS-3 was obtained in the same manner as in Synthesis Example 1, except that an α,ω-dihydrogenorganopolysiloxane having an average chain length of 24 and 63.8 g of a one-terminal allyl group-modified polyethylene glycol having an average repeating number of oxyethylene units of 12 were used instead of the α,ω-dihydrogenorganopolysiloxane having an average chain length of 45.

[0113] Modified polyorganosiloxane PDMS-4 was obtained in the same manner as in Synthesis Example 1, except that a polyorganosiloxane having an average chain length of 30 was used instead of the α,ω-dihydrogenorganopolysiloxane having an average chain length of 45, and 8.9 g of ethylene glycol monoallyl ether was used instead of the one-terminal allyl group-modified polyethylene glycol having an average repeat number of oxyethylene units of 12. The ethylene glycol monoallyl ether had one oxyethylene unit.

[0114] Synthesis Example 5: Production of PDMS-5 Modified polyorganosiloxane PDMS-5 was obtained in the same manner as in Synthesis Example 1, except that 24.2 g of a one-terminal allyl group-modified polyethylene glycol having an average repeat number of 8 oxyethylene units (manufactured by NOF Corporation, Uniox PK-5002) was used instead of the one-terminal allyl group-modified polyethylene glycol having an average repeat number of 12 oxyethylene units.

[0115] Synthesis Example 6: Production of PDMS-6

[0123] Modified polyorganosiloxane PDMS-6 was obtained in the same manner as in Synthesis Example 1, except that 102.0 g of a one-terminal allyl group-modified polyethylene glycol having an average repeat number of 38 oxyethylene units (UNIOX PK-5005, manufactured by NOF Corporation) was used instead of the one-terminal allyl group-modified polyethylene glycol having an average repeat number of 12 oxyethylene units.

[0116] Synthesis Example 7: Production of PDMS-7

[0123] Modified polyorganosiloxane PDMS-7 was obtained in the same manner as in Synthesis Example 1, except that 100 g of a polyorganosiloxane having an average chain length of 88 was used instead of the α,ω-dihydrogenorganopolysiloxane having an average chain length of 45, and 21.2 g of a one-terminal allyl group-modified polyethylene glycol having an average repeat number of oxyethylene units of 15 was used instead of the one-terminal allyl group-modified polyethylene glycol having an average repeat number of oxyethylene units of 12.

[0117] Synthesis Example 8: Preparation of PDMS-8

[0118] Under a nitrogen atmosphere, the following formula:

[0119] 9.1 g of 2-allylphenol (twice the molar amount relative to the polyorganosiloxane) was added to 100 g of polyorganosiloxane having an average chain length of 39, and then the mixture was thoroughly stirred while maintaining the temperature at 100°C. Next, a toluene solution of a platinum vinylsiloxane complex (platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) was added as a platinum catalyst to a toluene solution containing 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in which the mass of the platinum atom was 100% of the siloxane unit (-[Si(CH ３ ) ２ O]-), and the mixture was stirred for 10 hours at a reaction temperature of 100° C. Toluene and the platinum catalyst were removed from the resulting mixture, yielding a modified polyorganosiloxane PDMS-8.

[0120] An overview of Synthesis Examples 1 to 8 is shown in Table 1 below.

[0121]

[0122] Example 1 A polycarbonate-polyorganosiloxane copolymer was produced using the following raw materials and conditions. A 10 L stainless steel reactor equipped with a stirrer, a nitrogen inlet tube, a heater, a trap for capturing distilled phenol, and a pressure reducing device was charged with bisphenol A (BisP-A; 2,489.9 g) as a diol monomer and diphenyl carbonate (DPC; 2,500 g) as a carbonate ester compound (molar ratio of each raw material: BisP-A / DPC = 100 / 107), and 87.1 g of the modified polyorganosiloxane PDMS-1 obtained in Synthesis Example 1. These raw material monomers were completely melted at 150 °C, and then the inside of the reactor was purged with nitrogen. 1.64 mL of 0.01 mol / L sodium hydroxide (1.5 × 10 relative to the number of moles of all diol monomers) was added as a catalyst. －６Polymerization was initiated by adding 200 ml of toluenesulfonate (amount equivalent to 100%), followed by heating to 180°C over approximately 60 minutes, reducing the pressure in the reactor to 200 mmHg (26.6 kPa), and maintaining these reaction conditions until the amount of phenol distilled reached 0.2 L. Next, the temperature in the reactor was raised to 240°C over approximately 120 minutes, and these reaction conditions were maintained until 1.5 L of phenol was distilled. Subsequently, the temperature in the reactor was raised to 280°C over approximately 120 minutes, reducing the pressure in the reactor to 1 mmHg (0.1 kPa) or less, distilling 2 L or more of phenol, and the reaction was continued until a predetermined stirring torque was reached. Thereafter, nitrogen was introduced, and the pressure was increased to atmospheric pressure, and 0.037 g of butyl p-toluenesulfonate (10 times the amount relative to the number of moles of sodium hydroxide added) was added as a catalyst deactivator.

[0123] Furthermore, antioxidant 1 and antioxidant 2 shown below were added to the reactor in amounts of 0.05 parts by mass each relative to the theoretical yield of polycarbonate-polyorganosiloxane copolymer, and the mixture was thoroughly stirred. High-pressure nitrogen was then introduced into the reactor, and strands of the molten polycarbonate-polyorganosiloxane copolymer were extruded from the bottom of the reactor. The resulting strands were cut with a pelletizer to obtain pellets of polycarbonate-polyorganosiloxane copolymer PC-POS1.

[0124] The raw materials used in the production are as follows: Bisphenol A (BisP-A) [manufactured by Idemitsu Kosan Co., Ltd.] Diphenyl carbonate (DPC) [manufactured by Mitsui Fine Chemicals, Inc.] 0.01 mol / L aqueous sodium hydroxide solution [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] Antioxidants (C): Antioxidant 1: tris(2,4-di-tert-butylphenyl)phosphite [manufactured by BASF Japan Ltd., Irgafos 168] Antioxidant 2: pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate][manufactured by BASF Japan Ltd., Irganox 1010]

[0125] Example 2 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of the modified polyorganosiloxane PDMS-1 was used.

[0126] Example 3 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 244.8 g of the modified polyorganosiloxane PDMS-1 was used.

[0127] Example 4 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 117.3 g of PDMS-2 obtained in Synthesis Example 2 was used as the modified polyorganosiloxane.

[0128] Example 5 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-2 was used as the modified polyorganosiloxane.

[0129] Example 6 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 244.8 g of PDMS-2 was used as the modified polyorganosiloxane.

[0130] Example 7 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-1 was used as the modified polyorganosiloxane and the reaction was continued for 30 minutes after the predetermined torque was reached.

[0131] Example 8 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 117.3 g of PDMS-2 was used as the modified polyorganosiloxane and the reaction was continued for 30 minutes after the predetermined torque was reached.

[0132] Comparative Example 1 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-3 was used as the modified polyorganosiloxane.

[0133] Comparative Example 2 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-4 was used as the modified polyorganosiloxane.

[0134] Comparative Example 3 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-5 was used as the modified polyorganosiloxane.

[0135] Comparative Example 4 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 312.8 g of PDMS-5 was used as the modified polyorganosiloxane.

[0136] Comparative Example 5 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-6 was used as the modified polyorganosiloxane.

[0137] Comparative Example 6 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-7 was used as the modified polyorganosiloxane.

[0138] Comparative Example 7 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 179.7 g of PDMS-8 was used as the polyether-modified polyorganosiloxane.

[0139] Comparative Example 8 Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1, except that 8.4 g of PDMS-1 was used as the modified polyorganosiloxane.

[0140] [Evaluation] The polycarbonate-polyorganosiloxane copolymer pellets produced in Examples 1 to 8 and Comparative Examples 1 to 8 were evaluated as follows: (1) １ H-NMR measurement １Based on the integrated value of the peak derived from the following specific structure obtained by H-NMR measurement, the average chain length of the polyorganosiloxane structure, the average repeating number of the polyether structure, the content of the polyorganosiloxane-containing block (A-1), and the content of the polyorganosiloxane structure (A-3) were calculated. NMR apparatus: ECA-500 manufactured by JEOL RESONANCE Co., Ltd. Probe: TH5 compatible with 5φ NMR sample tube Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of accumulations: 256 NMR sample tube: 5φ Sample amount: 30 to 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature A: Peak integral value of the meta position of the phenyl moiety observed around δ 7.3 to 7.5 B: Peak integral value of the methylene group of the PEG moiety observed around δ 3.3 to 4.5 C: Peak integral value of the methyl group of the bisphenol A moiety observed around δ 1.50 to 2.00 D: Peak integral value of the methyl group of the dimethylsiloxane moiety observed around δ -0.02 to 0.4 E: Peak integral of the methylene group at the terminal of dimethylsiloxane observed at around δ 0.52 F: Peak integral of the methylene group at the terminal of polyethylene glycol connected to a carbonate bond observed at around δ 4.3 a = A / 2 b = B / 4 c = (C-e x 2) / 6 d = D / 6 e = E / 2 f = F / 2 T = a + b + c + d h = a / T x 100 i = b / T x 100 j = c / T x 100 k = d / T x 100 TW = h x 93 + i x 44 + j x 254 + k x 74.1

[0141] Average chain length of polyorganosiloxane structure n ａ Average value of the polyether structure = d / (e / 2) Average repeat number of the polyether structure n ｂ = b / e Content of polyorganosiloxane-containing block (A-1) Content of (A-1) [mass%] = (i × 44 + k × 74.1) / TW × 100 Content of polyorganosiloxane structure (A-3) Content of (A-3) [mass%] = (k × 74.1) / TW × 100

[0142] (2) Method for Measuring Viscosity-Average Molecular Weight Using an Ubbelohde viscometer, the viscosity of a methylene chloride solution (concentration: g / L) at 20°C was measured, and the intrinsic viscosity [η] was calculated from this, and the viscosity-average molecular weight (Mv) was calculated using the following formula (Schnell's formula). The results are shown in Tables 2 and 3. [η] = 1.23 × 10 －５ Mv ０．８３

[0143] (3) Fluidity: Method for Measuring Q Value The Q value was measured in accordance with JIS K7210-1:2014 by the following method. The pellets produced above were placed in an elevated flow tester, and the amount of molten resin flowing out of a nozzle with a diameter of 1 mm and a length of 10 mm at 280°C and a pressure of 160 kg was measured (×10 －２ The Q value (flow value) [unit: 10 mL / sec] was measured. The results are shown in Tables 2 and 3. －２ mL / sec] represents the outflow amount per unit time, and the higher the value, the better the fluidity.

[0144] (4) Impact Resistance: Measurement of Charpy Impact Strength: The pellets prepared above were dried at 100°C for 5 hours, and then injection-molded at a cylinder temperature of 280°C and a mold temperature of 80°C to obtain dumbbell test specimens for evaluating mechanical properties (total length: 169 mm, narrow parallel portion length / width: 80 mm / 10 mm, wide parallel portion length / width: 35 mm / 20 mm, thickness: 3 mm). Strip-shaped test specimens measuring 80 mm in length, 10 mm in width, and 3 mm in thickness were cut from the orthogonal portion of the dumbbell test specimens. Furthermore, the test specimens were post-processed to give them a notch (r = 0.25 mm ± 0.05 mm). The Charpy impact strength was measured at 23°C, 0°C, and -20°C using a Charpy impact tester (Charpy Impact Tester, Model 611, manufactured by Toyo Seiki Seisakusho, Ltd.) in accordance with ISO 179-1:2010. The results are shown in Tables 2 and 3.

[0145] (5) Measurement method of tensile elongation The pellets produced above were dried at 100°C for 5 hours, and then injection-molded at a cylinder temperature of 280°C and a mold temperature of 80°C to prepare dumbbell test pieces for evaluating mechanical properties (total length: 169 mm, narrow parallel portion length / width: 80 mm / 10 mm, wide parallel portion length / width: 35 mm / 20 mm, thickness: 4 mm). Measurements were performed in accordance with ISO 527-1,2:2012. The results are shown in Tables 2 and 3.

[0146] (6) Evaluation method for molded article appearance The pellets produced above were dried at 100°C for 5 hours, and then injection-molded at a cylinder temperature of 280°C and a mold temperature of 80°C to obtain dumbbell test pieces for evaluating mechanical properties (total length: 169 mm, length / width of narrow parallel part: 80 mm / 10 mm, length / width of wide parallel part: 35 mm / 20 mm, thickness: 4 mm). The wide parallel part of each test piece was gripped and bent to a distance of 140 mm between the ends (width 20 mm). The presence or absence of surface peeling in the narrow parallel part was evaluated visually. A: Surface peeling present B: No surface peeling The results are shown in Tables 2 and 3.

[0147]

[0148]

Claims

1. A polyorganosiloxane-containing block (A-1) containing a constituent unit represented by the following general formula (1), A polycarbonate-polyorganosiloxane copolymer (A) comprising a polycarbonate block (A-2) containing repeating structural units represented by the following general formula (2), The polyorganosiloxane-containing block (A-1) has a content of 2% by mass or more and 30% by mass or less. n ａ n relative to the mean ｂ Ratio of the mean values ​​[(n ｂ (Average value of) / (n ａ A polycarbonate-polyorganosiloxane copolymer having an average value of 0.2 or more and 0.4 or less. 【Chemistry 1】 [wherein, R １ to R ４ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkylaryl group having 7 to 22 carbon atoms. R ５ and R ６ each independently represents an alkylene group having 1 to 3 carbon atoms, and these groups may contain at least one group selected from the group consisting of -O-, -COO-, -CO-, -S-, -NH-, and -NR １１１ -. A plurality of R ７ and R ８ may be the same or different and each 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 may contain at least one group selected from the group consisting of -O-, -COO-, -CO-, -S-, -NH-, -NR １１１ -. R １１１ represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms. z １ , z ２ , u １ and u ２ each represents 0 or 1. n ａ represents an integer of 2 to 500, and n ｂ each independently represents an integer of 2 to 200. R １０ represents a divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and these groups may be substituted by substituents and may also contain at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.]

2. In the polycarbonate-polyorganosiloxane copolymer (A), n ａ The polycarbonate-polyorganosiloxane copolymer according to claim 1, wherein the average value is 10 or more and 90 or less.

3. The aforementioned n ａ n relative to the mean ｂ Ratio of the mean values ​​[(n ｂ (Average value of) / (n ａ The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the average value of [value] is 0.2 or more and 0.35 or less.

4. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the polyorganosiloxane-containing block (A-1) is represented by the general formula (1), the following general formula (1-2), or the following general formula (1-3). 【Chemistry 2】 [In the formula, R １ ~R ８ , z １ , z ２ u １ u ２ , n ａ , and n ｂ The above has the same meaning. If multiple of these exist, they may be the same or different. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a dicarboxylic acid halide.

5. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the polycarbonate block (A-2), which consists of repeating constituent units represented by the general formula (2), includes a constituent unit represented by the following general formula (111). 【Transformation 3】 [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 C5-C15 cycloalkylidene group, a fluoroorangeyl group, a C7-C15 arylalkylene group, a C7-C15 arylalkylidene group, -S-, -SO-, -SO ２ This represents -, -O-, or -CO-. s and t each independently represent integers from 0 to 4.

6. In the above general formula (1), R １ ~R ４ The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein each of the groups represents a methyl group.

7. In the above general formula (1), R ５ and R ６ Each of these is a trimethylene group (-(CH ２ ) ３ A polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the coefficient of polycarbonate is 0.

8. In the above general formula (1), R ７ and R ８ Each of these is a dimethylene group (-(CH ２ ) ２ -), methyl-substituted dimethylene group (-CH ２ CH (CH ３ ) - or - CH (CH ３ )CH ２ -), trimethylene group (-(CH ２ ) ３ -), or tetramethylene group (-(CH ２ ) ４ A polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the coefficient of polycarbonate is 0.

9. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the polyorganosiloxane-polyorganosiloxane copolymer contains a polyorganosiloxane structure (A-3) consisting of repeating structural units represented by the following general formula (3) in the polyorganosiloxane-polyorganosiloxane-containing block (A-1), with a content of 0.1% by mass or more and 30% by mass or less. 【Chemistry 4】 [In the formula, R １ ~R ２ This expresses the same meaning as above.

10. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein the viscosity-average molecular weight (Mv) is 15,000 or more and 30,000 or less.

11. A polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, obtained by a melt polymerization method.

12. A polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, obtained using a diol monomer (a1).

13. A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer described in claim 1 or 2.

14. A molded article comprising the polycarbonate resin composition described in claim 13.

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