Polycarbonate-polyorganosiloxane copolymers

Abstract

The present invention relates to a polycarbonate-polyorganosiloxane copolymer which is a polycarbonate-polyorganosiloxane copolymer (A) that contains a polyorganosiloxane-containing block (A-1) that contains a structural unit represented by general formula (1) and a polycarbonate block (A-2) that contains a structural unit represented by general formula (2). The polycarbonate block (A-2) contains repeating structural units represented by general formula (2), the content of the polyorganosiloxane-containing block (A-1) is 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. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polycarbonate-polyorganosiloxane copolymer, a polycarbonate-based resin composition and a molded product. Background Art

[0002] Polycarbonate resin is an engineering plastic with excellent transparency and mechanical properties and very high impact resistance. It is known that polycarbonate-polyorganosiloxane copolymers obtained by copolymerizing polyorganosiloxane with polycarbonate have excellent low-temperature impact resistance and excellent chemical resistance while maintaining high transparency.

[0003] Generally, as a method for producing a polycarbonate resin, there are known methods of directly reacting an aromatic dihydroxy compound with phosgene (interfacial polycondensation method) or transesterifying an aromatic dihydroxy compound with a carbonic acid diester in a molten state (melt polymerization method).

[0004] Patent Document 1 discloses a method for producing a polycarbonate-polyorganosiloxane copolymer by an interfacial polycondensation method, wherein a diaryl diol compound such as bisphenol is reacted with phosgene in the presence of an organic solvent to produce a polycarbonate oligomer having a reactive chloroformate group, and simultaneously or sequentially with the production of the polycarbonate oligomer, the polycarbonate oligomer, bisphenols and a polyorganosiloxane having hydroxyl-containing aromatic groups at both ends are further brought into contact in a dichloromethane / aqueous medium to produce the polycarbonate-polyorganosiloxane copolymer.

[0005] Usually, in the polymerization reaction, sometimes a self-coupling product formed by bonding the same raw material components to each other is produced, and a part of the raw materials does not participate in the polymerization reaction and produces unreacted raw material components. These components are present in the polymer in a state where they are not uniformly introduced into the polymer main chain, and therefore, the transparency and mechanical properties of the polymer are significantly reduced. In the above-mentioned interfacial polymerization method, there are few situations in which such problems are produced, and a polycarbonate-polyorganosiloxane copolymer with excellent transparency and mechanical properties can be obtained.

[0006] On the other hand, the interfacial polymerization method needs to use phosgene with high toxicity as a carbonate source. In addition, the polymerization reaction system needs to use methylene chloride with large environmental load as a solvent, which requires large-scale degassing equipment and a large amount of energy to remove, which is disadvantageous in terms of economy. In contrast, the manufacture method of polycarbonate-polyorganosiloxane copolymer utilizing melt polymerization method can avoid such problems.

[0007] However, the production method of polycarbonate-polyorganosiloxane copolymers by melt polymerization tends to result in insufficient transparency of the obtained polycarbonate-polyorganosiloxane copolymers, and studies have been conducted to improve them.

[0008] Patent Documents 2 to 4 disclose, as polycarbonate-polyorganosiloxane copolymers that can be produced by a melt polymerization method and have high transparency, a polycarbonate-polyorganosiloxane copolymer comprising a polyorganosiloxane block (A-1) and a specific polycarbonate block (A-2), wherein the polyorganosiloxane block (A-1) comprises a specific structural unit such as a polyol structure.

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Application Publication No. 2015-189953

[0012] Patent Document 2: International Publication No. 2021 / 112257

[0013] Patent Document 3: International Publication No. 2021 / 112259

[0014] Patent Document 4: International Publication No. 2021 / 112260 Summary of the invention

[0015] Problems to be solved by the invention

[0016] Patent Documents 2 to 4 disclose methods for producing polycarbonate-polyorganosiloxane copolymers by melt polymerization, but there is room for improvement in terms of fluidity, impact strength, tensile strength, appearance of injection molded products, and the like.

[0017] An object of the present invention is to obtain a polycarbonate-polyorganosiloxane copolymer having excellent fluidity and excellent impact resistance, tensile elongation and appearance of a molded product.

[0018] Means for solving problems

[0019] The present inventors have conducted intensive studies and have found that a polycarbonate-polyorganosiloxane copolymer having a specific structure can solve the above-mentioned problems. That is, the present invention includes the following.

[0020] <1> A polycarbonate-polyorganosiloxane copolymer, which is a polycarbonate-polyorganosiloxane copolymer (A) comprising a polyorganosiloxane-containing block (A-1) and a polycarbonate block (A-2), wherein the polyorganosiloxane-containing block (A-1) comprises a structural unit represented by the following general formula (1), and the polycarbonate block (A-2) comprises a structural unit represented by the following general formula (2) repeatedly,

[0021] The content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less,

[0022] n bThe average value relative to n a The ratio of the average value of b The average value of a The average value of ()] is greater than or equal to 0.2 and less than or equal to 0.4.

[0023] [Chemical formula 1]

[0024]

[0025] [In the formula, R 1 ~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. 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 -At least one group. 7 and R 8 Each can be the same or different. 7 and R 8 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 -O-, -COO-, -CO-, -S-, -NH-, -NR- in at least one of the main chain and the side chain. 111 -At least one group of R 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 Represents 0 or 1 respectively. a Integer from 2 to 500, n b 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 these groups 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.]

[0026] <2> The polycarbonate-polyorganosiloxane copolymer according to <1> above, wherein in the polycarbonate-polyorganosiloxane copolymer (A), n a The average value is greater than 10 and less than 90.

[0027] <3> The polycarbonate-polyorganosiloxane copolymer according to <1> or <2>, wherein n b The average value relative to the above n a The ratio of the average value of b The average value of a The average value of ()] is greater than 0.2 and less than 0.35.

[0028] <4> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <3>, wherein the polyorganosiloxane-containing block (A-1) is represented by the above general formula (1), the following general formula (1-2), or the following general formula (1-3).

[0029] [Chemical formula 2]

[0030]

[0031] [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 there are multiple of them, 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 halide of a dicarboxylic acid. ]

[0032] <5> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <4>, wherein the polycarbonate block (A-2) comprising the repeating structural unit represented by the general formula (2) comprises a structural unit represented by the following general formula (111).

[0033] [Chemical formula 3]

[0034]

[0035] [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-, -SO2-, -O-, or -CO-. s and t each independently represent an integer of 0 to 4.]

[0036] <6> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <5>, wherein in the general formula (1), R 1 ~R 4 represent methyl groups respectively.

[0037] <7> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <6>, wherein in the general formula (1), R 5 and R 6 They represent trimethylene (-(CH2)3-) respectively.

[0038] <8> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <7>, wherein in the general formula (1), R 7 and R 8 They respectively represent a dimethylene group (-(CH2)2-), a methyl-substituted dimethylene group (-CH2CH(CH3)- or -CH(CH3)CH2-), a trimethylene group (-(CH2)3-), or a tetramethylene group (-(CH2)4-).

[0039] <9> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <8>, wherein the content of the polyorganosiloxane structure (A-3) comprising a repeating structural unit 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.

[0040] [Chemical formula 4]

[0041]

[0042] [In the formula, R 1 ~R 2 Meanings the same as above.]

[0043] <10> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <9>, wherein the viscosity average molecular weight (Mv) is 15,000 to 30,000.

[0044] <11> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <10>, which is obtained by a melt polymerization method.

[0045] <12> The polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <11>, which is obtained using a diol monomer (a1).

[0046] <13> A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to any one of <1> to <12>.

[0047] <14> A molded article formed from the polycarbonate resin composition according to <13>.

[0048] Effects of the Invention

[0049] According to the present invention, a polycarbonate-polyorganosiloxane copolymer having excellent fluidity and excellent impact resistance, tensile elongation and appearance of a molded product can be obtained. DETAILED DESCRIPTION

[0050] The polycarbonate-polyorganosiloxane copolymer of the present invention and the polycarbonate resin composition containing the copolymer are described in detail below. In this specification, any of the provisions considered as preferred can be adopted, and a combination of preferred provisions can be said to be more preferred. In this specification, the description of "XX to YY" means "XX or more and YY or less".

[0051] 〈Polycarbonate-polyorganosiloxane copolymer (A)〉

[0052] The polycarbonate-polyorganosiloxane copolymer (A) of the present invention comprises a polyorganosiloxane-containing block (A-1) and a polycarbonate block (A-2), wherein the polyorganosiloxane-containing block (A-1) comprises a structural unit represented by the following general formula (1), and the polycarbonate block (A-2) comprises a structural unit represented by the following general formula (2) repeatedly.

[0053] The content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less,

[0054] n b The average value relative to n a The ratio of the average value of b The average value of a The average value of ()] is greater than or equal to 0.2 and less than or equal to 0.4.

[0055] [Chemical formula 5]

[0056]

[0057] [In the formula, R 1 ~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. 5 and R 6Each 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 -At least one group. 7 and R 8 Each can be the same or different. 7 and R 8 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 -O-, -COO-, -CO-, -S-, -NH-, -NR- in at least one of the main chain and the side chain. 111 -At least one group of R 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 Represents 0 or 1 respectively. a Integer from 2 to 500, n b 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 these groups 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.]

[0058] 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 a plurality of polyorganosiloxane blocks (A-1). The polyorganosiloxane block (A-1) is more preferably a structural unit represented by the above general formula (1).

[0059] [Chemical formula 6]

[0060]

[0061] [In the formula, R 1 ~R 8 、z 1 、z 2 、u 1 、u 2 、n a and n brepresents the same meaning as above. When there are multiple of them, 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 halide of a dicarboxylic acid. ]

[0062] In the formula, as R 1 ~R 4 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 1 ~R 4 The alkyl group having 1 to 10 carbon atoms shown in the figure includes methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups and various hexyl groups. It should be noted that the term "various" in the present specification means including straight-chain and all branched groups, and the same applies hereinafter.

[0063] As R 1 ~R 4 The alkoxy group having 1 to 10 carbon atoms represented by is exemplified by an alkoxy group having the same alkyl moiety as the above-mentioned alkyl group. 1 ~R 4 The aryl group having 6 to 12 carbon atoms represented by , includes phenyl, naphthyl, and the like. 1 ~R 4 Examples of the alkylarylene group having 7 to 22 carbon atoms include alkylarylene groups in which the alkyl moiety is the same as the above-mentioned alkyl group and the arylene moiety is a divalent group obtained by removing one hydrogen atom from the above-mentioned aryl group.

[0064] R 1 ~R 4 They are 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 still more preferably a methyl group.

[0065] As R 5 and R 6 Examples of the alkylene group having 1 to 3 carbon atoms include methylene, dimethylene, trimethylene, and methyl-substituted dimethylene.

[0066] As R 7 and R 8 The arylene group having 6 to 20 carbon atoms represented by , includes phenylene and naphthylene. 7 and R 8 The alkylene groups having 1 to 10 carbon atoms as shown in R include methylene, dimethylene, trimethylene, methyl-substituted dimethylene, and various butylene groups. The various butylene groups are preferably tetramethylene. 7 and R 8 The alkylarylene group shown in the figure includes an alkylarylene group having the same alkyl moiety as the above-mentioned alkylene group and the same arylene moiety as the above-mentioned arylene group.

[0067] Among them, R 5 , R 6 , R 7 and R 8 At least one of the main chain and the side chain may contain a 111 -At least one group in R 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 include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 111 Examples of the aryl group having 6 to 10 carbon atoms include phenyl and naphthyl.

[0068] R 5 and R 6 Preferably, they are methylene (-(CH2)-), dimethylene (-(CH2)2-) or trimethylene (-(CH2)3-), and more preferably, they are trimethylene (-(CH2)3-).

[0069] R 7 and R 8 Preferably, they are each an alkylene group having 1 to 10 carbon atoms, more preferably, they are each an alkylene group having 1 to 5 carbon atoms, further preferably, they are each a dimethylene group (-(CH2)2-), a methyl-substituted dimethylene group (-CH2CH(CH3)- or -CH(CH3)CH2-), a trimethylene group, or a tetramethylene group (-(CH2)4-), and further preferably, they are each a dimethylene group.

[0070] z 1 、z 2 、u 1 and u 2 Each is 0 or 1.

[0071] z 1 and z 2 Preferably, they are 1, more preferably z 1 and z 2 Both are 1.

[0072] u 1 and u 2 Preferably, they are 1, more preferably u 1 and u 2 Both are 1.

[0073] In the general formula (1), preferably R 1 ~R 4 All are methyl, R 5 and R 6 All are trimethylene, R7 and R 8 All are dimethoxy, z 1 and z 2 All are 1, u 1 and u 2 The polyorganosiloxane block is 1.

[0074] n a represents the chain length of the polyorganosiloxane structure in the general formula (1). In the polycarbonate-polyorganosiloxane copolymer (A), n a It is an integer of 2 to 500, preferably an integer of 10 to 90, more preferably an integer of 20 to 70, further preferably an integer of 30 to 60, and further preferably an integer of 35 to 50.

[0075] n a The average value of, that is, 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, further preferably 30 to 60, further 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 of a molded article can be obtained.

[0076] It should be noted that -SiR in the general formula (1) 1 R 2 The number of repetitions of the -O- structure is n a -1.

[0077] The average chain length of the polyorganosiloxane structure in the general formula (1) is calculated by nuclear magnetic resonance (NMR) measurement.

[0078] n b Indicates -(O) in the general formula (1) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 - Number of repetitions of the structure. n b It is an integer of 2 to 200, preferably an integer of 3 to 40, more preferably an integer of 7 to 30, further preferably an integer of 10 to 25, further preferably an integer of 10 to 20.

[0079] In the polycarbonate-polyorganosiloxane copolymer (A), n b The average value of -(O) in general formula (1) Z 1 -R7 -Structure and -R 8 - (O) Z 2 - The average repetition number of the structure is 2 to 200, preferably 3 to 40, more preferably 7 to 30, further preferably 10 to 25, further preferably 10 to 20. If it is within the above range, it is preferred for the ease of obtaining the raw materials for producing the polycarbonate-polyorganosiloxane copolymer (A). b If n is 10 or more, the balance between the mechanical strength and the mold release property of the obtained polycarbonate-polyorganosiloxane copolymer (A) can be further improved, and thus it is more preferred. b If n is 100 or less, the viscosity and melting point of the polyorganosiloxane during production will be within the appropriate range, and the handling properties will be further improved, which is more preferred. b The ratio is 50 or less because the effect of improving the physical properties of the polycarbonate-polyorganosiloxane copolymer (A) by containing the polyorganosiloxane block is further enhanced, which is more preferred.

[0080] -(O) in the general formula (1) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 The average number of repeats of the structure was calculated by nuclear magnetic resonance (NMR) measurement.

[0081] In the polycarbonate-polyorganosiloxane copolymer (A), n b The average value relative to n a The ratio of the average value of b The average value of a The average value of n is greater than 0.2 and less than 0.4. b The average value relative to n a When the ratio of the average values ​​of is within the above range, a copolymer having excellent fluidity and excellent impact resistance, tensile elongation and appearance of a molded product can be obtained.

[0082] In the polycarbonate-polyorganosiloxane copolymer (A) of the present invention, by making n b The average value relative to n a The ratio of the average value of b The average value of a The reason why a copolymer having excellent fluidity and excellent impact resistance, tensile elongation and appearance of a molded product can be obtained when the average value of ()] is 0.2 or more and 0.4 or less is estimated as follows.

[0083] It is known that the polyorganosiloxane structure (A-3) comprising a structural unit represented by the following general formula (3) repeatedly contained in the polyorganosiloxane-containing block (A-1) represented by the general formula (1) can impart physical properties such as impact resistance to the polycarbonate-polyorganosiloxane copolymer (A). However, the polyorganosiloxane structure (A-3) is a structure with low polarity, and therefore has insufficient compatibility with the polycarbonate block (A-2) which is a structure with high polarity. It is believed that if the content of the polyorganosiloxane structure (A-3) is too large, the polyorganosiloxane structure (A-3) separates from the polycarbonate block (A-2) to form a phase separation structure, and physical properties such as tensile elongation and the appearance of the molded article may become insufficient.

[0084] [Chemical formula 7]

[0085]

[0086] [In the formula, R 1 ~R 2 Meanings the same as above.]

[0087] On the other hand, the -(O) contained in the polyorganosiloxane-containing block (A-1) represented by the general formula (1) is Z 1 -R 7 -Structure and -R 8 - (O) Z 2 - structures are highly polar structures. Although these structures are highly compatible with the highly polar polycarbonate block (A-2), -(O) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 - structure is relatively soft and therefore has low strength. If the content is too large, it is considered that the physical properties such as impact resistance of the molded article of the polycarbonate-polyorganosiloxane copolymer (A) may become insufficient.

[0088] Therefore, it is considered that by adjusting the average chain length of the polyorganosiloxane structure contained in the polycarbonate-polyorganosiloxane copolymer (A) of the present invention to -(O) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 When the ratio of the average repeating number of the - structure is within a predetermined range, a polycarbonate-polyorganosiloxane copolymer (A) having excellent fluidity and excellent impact resistance, tensile elongation and appearance of a molded article can be obtained.

[0089] The polycarbonate-polyorganosiloxane copolymer (A) of the present invention has a b The average value relative to n a The ratio of the average value of b The average value of a The average value of)] is 0.2 or more, which indicates that the highly polar -(O) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 -structure content is sufficiently large relative to the content of the low-polarity polyorganosiloxane structure (A-3), and the polyorganosiloxane structure (A-3) is sufficiently compatible with the polycarbonate block (A-2). Therefore, it is considered that the polyorganosiloxane-containing block (A-1) does not form a phase separation in the resin structure of the polycarbonate-polyorganosiloxane copolymer (A), and excellent physical properties such as tensile elongation and appearance such as color tone of the molded product can be achieved.

[0090] In addition, the polycarbonate-polyorganosiloxane copolymer (A) of the present invention has n b The average value relative to n a The ratio of the average value of b The average value of a The average value of) is below 0.4, which is considered to be - (O) Z 1 -R 7 -Structure and -R 8 - (O) Z 2 When the content of the - structure is sufficiently small relative to the content of the polyorganosiloxane structure (A-3), the polycarbonate-polyorganosiloxane copolymer (A) can achieve excellent physical properties such as impact resistance of the molded article.

[0091] n b The average value relative to n a The ratio of the average value of b The average value of 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. b The average value relative to n a When the average value ratio of is within the above preferred range, a polycarbonate-polyorganosiloxane copolymer (A) having more excellent fluidity and more excellent impact resistance, tensile elongation and appearance of a molded article can be obtained.

[0092] As R in the above general formula (2) 10The divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms as shown in the formula (A) may include, for example, an ethylene group, a n-propylene group, an isopropylene group, a n-butylene group, an isobutylene group, a n-pentylene group, a n-hexylene group, a n-heptylene group, a n-octylene group, a 2-ethylhexylene group, a n-nonylene group, a n-decylene group, a n-undecylene group, a n-dodecylene group, a n-tridecylene group, a n-tetradecylene group, a n-pentadecanylene group, a n-hexadecylene group, a n-heptadecanylene group, and a n-octadecylene group. These groups may be substituted with a substituent and may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0093] As R in the above general formula (2) 10 The divalent alicyclic hydrocarbon group having 3 to 40 carbon atoms as shown in the formula (a) may include, for example, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclotetradecylene, adamantylene, bicycloheptylene, bicyclodecylene and tricyclodecylene. These groups may be substituted with a substituent and may contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms and halogen atoms.

[0094] As R in the above general formula (2) 10 Examples of the divalent aromatic hydrocarbon group having 6 to 20 carbon atoms include divalent aromatic hydrocarbon groups derived from 2,2-bis(4-hydroxyphenyl)propane (also called bisphenol A), 2,2-bis(4-hydroxy-3-methylphenyl)propane (also called bisphenol C), 1,1-bis(4-hydroxyphenyl)cyclohexane (also called bisphenol Z), 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane (also called bisphenol 3MZ), 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (also called bisphenol HTG), 1,1-bis(4-hydroxyphenyl)cyclododecene, hydroquinone, resorcinol, and catechol. These groups may be substituted with a substituent, and these groups may contain at least one atom selected from oxygen atoms, nitrogen atoms, sulfur atoms, and halogen atoms.

[0095] The polycarbonate block (A-2) comprising a repeating structural unit represented by the general formula (2) preferably comprises a repeating structural unit represented by the general formula (111).

[0096] [Chemical formula 8]

[0097]

[0098] [In the formula, R 55 and R 56Each 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-, -SO2-, -O-, or -CO-. s and t each independently represent an integer of 0 to 4.]

[0099] As R 55 and R 56 The halogen atom shown here includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0100] As R 55 and R 56 Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, various butyl groups, various pentyl groups, and various hexyl groups. 55 and R 56 Examples of the alkoxy group having 1 to 6 carbon atoms include alkoxy groups in which the alkyl moiety is the same as the above-mentioned alkyl group.

[0101] As the alkylene group having 1 to 8 carbon atoms represented by X, methylene, ethylene, trimethylene, tetramethylene and hexamethylene are mentioned, and alkylene groups having 1 to 5 carbon atoms are preferred. As the alkylidene group having 2 to 8 carbon atoms represented by X, ethylidene and isopropylidene are mentioned. As the cycloalkylene group having 5 to 15 carbon atoms represented by X, cyclopentanediyl, cyclohexanediyl and cyclooctanediyl are mentioned, and cycloalkylene groups having 5 to 10 carbon atoms are preferred. As the arylene group having 6 to 20 carbon atoms represented by X, phenylene, naphthylene and biphenylene are mentioned. As the cycloalkylidene group having 5 to 15 carbon atoms represented by X, cyclohexylidene, 3,5,5-trimethylcyclohexylidene and 2-adamantanylidene are mentioned, and cycloalkylidene groups having 5 to 10 carbon atoms are preferred, and cycloalkylidene groups having 5 to 8 carbon atoms are more preferred. Examples of the arylalkylene group having 7 to 15 carbon atoms represented by X include aryl groups having 6 to 14 ring carbon atoms such as phenyl, naphthyl, biphenyl or anthracenyl as the aryl moiety, and arylalkylene groups having the same alkylene moiety as the above alkylene groups as the aryl moiety. Examples of the arylalkylidene group having 7 to 15 carbon atoms represented by X include aryl groups having 6 to 14 ring carbon atoms such as phenyl, naphthyl, biphenyl or anthracenyl as the aryl moiety, and arylalkylidene groups having the same alkylidene moiety as the above alkylidene groups as the aryl moiety.

[0102] s and t each independently represent an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. Among them, it is preferred that s and t are 0 and X represents a single bond or an alkylene group having 1 to 8 carbon atoms, or that s and t are 0 and X represents an alkylidene group, and it is further preferred that s and t are 0 and X represents an isopropylidene group.

[0103] The polycarbonate block (A-2) comprising the structural unit represented by the general formula (2) described above repeatedly may contain a structural unit other than the structural unit represented by the general formula (111). Specifically, the polycarbonate block (A-2) comprising the structural unit represented by the general formula (2) described above repeatedly may further contain a structural unit represented by the general formula (112).

[0104] [Chemical formula 9]

[0105]

[0106] [In the formula, R 100 It 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 a branched structure and a cyclic structure, and may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom.]

[0107] As R 100 The divalent aliphatic hydrocarbon group having 2 to 40 carbon atoms shown in the formula (a) may include an alkylene group having 2 to 40 carbon atoms, a cycloalkylene group having 4 to 40 carbon atoms, a divalent saturated heterocyclic group containing oxygen or nitrogen having 4 to 40 carbon atoms, and the like. The carbon number of the alkylene group is preferably 2 to 18, more preferably 2 to 10, and further preferably 3 to 6. The carbon number of the cycloalkylene group is preferably 4 to 20, more preferably 5 to 20. The carbon number of the divalent saturated heterocyclic group containing oxygen or nitrogen is preferably 4 to 20, more preferably 5 to 20. These groups may contain at least one selected from a branched structure and a cyclic structure, and may also contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0108] As the above-mentioned alkylene groups having 2 to 40 carbon atoms, there can be mentioned 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-pentadecanylene, n-hexadecylene, n-heptadecylene and n-octadecylene. As the above-mentioned cycloalkylene groups having 4 to 40 carbon atoms, there can be mentioned cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclotetradecylene, adamantylene, bicycloheptylene, bicyclodecylene and tricyclodecylene. As the above-mentioned divalent heterocyclic groups containing oxygen or nitrogen having 4 to 40 carbon atoms, there can be mentioned groups containing oxygen or nitrogen atoms in the above-mentioned cycloalkylene skeleton.

[0109] 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).

[0110] [Chemical formula 10]

[0111]

[0112] [Chemical formula 11]

[0113]

[0114] [Chemical formula 12]

[0115]

[0116] The polycarbonate block (A-2) comprising a repeating structural unit represented by the general formula (2) preferably comprises a structural unit derived from at least one compound selected from 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.

[0117] The polycarbonate block (A-2) preferably contains a structural unit represented by the general formula (2) as a main component. The polycarbonate block (A-2) preferably contains 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and further preferably 98% by mass or more of the structural unit represented by the general formula (2) relative to the block (A-1) containing polyorganosiloxane. It is further preferred that the polycarbonate block (A-2) only contains the structural unit represented by the general formula (2) in a repeated manner. Among them, it is particularly preferred that the structural unit only contains the structural unit represented by the general formula (111) in a repeated manner.

[0118] In the polycarbonate-polyorganosiloxane copolymer (A), the polyorganosiloxane-containing block (A-1) is preferably bonded to the polycarbonate block (A-2) via a carbonate bond (-OC(=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.

[0119] In the present specification, the structure represented by the chemical formula may exist in optical isomers, stereoisomers, etc. due to the presence of an asymmetric center. In this case, all isomers and mixtures thereof are included.

[0120] For example, the structural unit represented by the general formula (a-iii) above preferably includes a structural unit represented by the following general formula (a-iii′), and more preferably includes only a structural unit represented by the following general formula (a-iii′).

[0121] [Chemical formula 13]

[0122]

[0123] 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 setting the content of the polyorganosiloxane-containing block (A-1) to be within the above range, a copolymer having excellent fluidity and excellent impact resistance of a molded product can be obtained.

[0124] 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 further preferably 3% by mass or more and 10% by mass or less. By setting the content of the polyorganosiloxane-containing block (A-1) to be within the above preferred range, a copolymer having better fluidity and better impact resistance, tensile elongation and appearance of a molded article can be obtained.

[0125] In the present specification, the “content of the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)” means the percentage of the total mass of the structural unit represented by the above general formula (3) and the structural unit represented by the following general formula (Y) relative to the total mass of the polycarbonate block (A-2), the structural unit represented by the above general formula (3), the structural unit represented by the following general formula (Y), and the terminal structure derived from the terminal blocking agent described below contained in the polycarbonate-polyorganosiloxane copolymer (A) as required.

[0126] [Chemical formula 14]

[0127]

[0128] [In the formula, R Y For R 7 or R 8 In R Y For R 8 In the case of 0 For z 2 , in R Y For R 7 In the case of 0 For z 1 . R 7 , R 8 、z 1 and z2 Meanings the same as above.]

[0129] The content of the polyorganosiloxane structure (A-3) comprising the structural unit represented by the general formula (3) repeated in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A) is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 15% by mass, and even more preferably 1.0% by mass to 10% by mass. By setting the content of the polyorganosiloxane structure to the preferred range, a copolymer having a more excellent impact resistance of a molded article can be obtained.

[0130] In the present specification, the “content of the polyorganosiloxane structure (A-3) comprising repeated structural units represented by the general formula (3) contained in the polyorganosiloxane-containing block (A-1) in the polycarbonate-polyorganosiloxane copolymer (A)” means the percentage of the total mass of the structural units represented by the general formula (3) relative to the total mass of the polycarbonate block (A-2), the structural units represented by the general formula (3), the structural units represented by the general formula (Y), and, if necessary, the terminal structure derived from the terminal blocking agent described later contained in the polycarbonate-polyorganosiloxane copolymer (A).

[0131] 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, further preferably 80% by mass or more, further preferably 90% by mass or more, and is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, further preferably 99.0% by mass or less, further preferably 97.0% by mass or less.

[0132] 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, further preferably 18,000 to 25,000, further preferably 19,000 to 24,000, further preferably 20,500 to 23,000.

[0133] The viscosity average molecular weight (Mv) in this specification is a value calculated by measuring the intrinsic viscosity [η] of a dichloromethane solution (concentration: g / L) at 20° C. and using the following Schnell's equation.

[0134] [η] = 1.23 × 10 -5 Mv 0.83

[0135] <Method for producing polycarbonate-polyorganosiloxane copolymer (A)>

[0136] 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.

[0137] <<Diol monomer (a1)>>

[0138] 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.

[0139] [Chemical formula 15]

[0140]

[0141] In the above general formula (a1), R 10 The preferred groups are the same as described above.

[0142] 〈〈Polyorganosiloxane (a2)〉〉

[0143] The polyorganosiloxane (a2) preferably has a structure represented by any one of the following general formulae (a2-1) to (a2-3).

[0144] [Chemical formula 16]

[0145]

[0146] [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.]

[0147] The method for producing the polyorganosiloxane (a2) is not particularly limited. For example, according to the method described in Japanese Patent Application Laid-Open No. 11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α,ω-dihydroorganopentasiloxane, and then, in the presence of a catalyst for a hydrosilylation reaction, the α,ω-dihydroorganopentasiloxane is subjected to an addition reaction with an oligomer or polymer (such as polyalkylene ether, polyester, polycarbonate, etc.) modified at one end with an allyl group, thereby obtaining the polyorganosiloxane. In addition, according to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the obtained α,ω-dihydroorganopolysiloxane is subjected to addition reaction with an oligomer or polymer modified at one end with an allyl group in the presence of a catalyst for hydrosilylation reaction in the same manner as above, thereby obtaining polyorganosiloxane. It should be noted that the average repeating number n of α,ω-dihydroorganopolysiloxane can also be adjusted by its polymerization conditions. a Commercially available α,ω-dihydroorganopolysiloxane can also be used after appropriate adjustment. In addition, oligomers modified at one end with an allyl group can also be used to adjust the average repeating number n by adjusting the polymerization conditions. b After appropriate adjustment, commercially available single-end allyl-modified oligomers can also be used. The single-end allyl-modified polyethylene glycol among the single-end allyl-modified oligomers can be manufactured with reference to Japanese Patent No. 5652691. In addition, commercially available allyl-modified polyethylene glycols can include Uniox PKA-5001, Uniox PKA-5002, Uniox PKA-5003, Uniox PKA-5004, Uniox PKA-5005, etc. manufactured by NOF Corporation.

[0148] The polycarbonate-polyorganosiloxane copolymer (A) can be produced by polymerizing raw material monomers by an interfacial polymerization method or a melt polymerization method (ester exchange method).

[0149] The polycarbonate-polyorganosiloxane copolymer (A) is preferably obtained by melt polymerization. When the polycarbonate-polyorganosiloxane copolymer (A) is produced by interfacial polymerization, for example, the method described in Japanese Patent Publication No. 2014-80462 can be used. Preferably, the polycarbonate-polyorganosiloxane copolymer (A) can be produced by reacting the polyorganosiloxane (a2), the diol monomer (a1) and the carbonate compound as raw material monomers by melt polymerization in the presence of a basic catalyst. At this time, a terminal blocking agent can be further added to carry out polymerization reaction.

[0150] Therefore, the present invention also provides a method for producing a polycarbonate-polyorganosiloxane copolymer (A), comprising a step of reacting a polyorganosiloxane (a2), a diol monomer (a1) and a carbonate compound by melt polymerization. The step of reacting by melt polymerization is preferably carried out in the presence of a basic catalyst.

[0151] Melt polymerization method is owing to not needing environmental load height, the methylene dichloride etc. solvents of high price trend, so is preferred from the viewpoint of environmental load and economy.In addition, owing to not using the high phosgene of toxicity as carbonate source, so is also preferred from the viewpoint of safety when manufacturing.

[0152] The melt polymerization method is advantageous in terms of environmental protection and economy because it does not require solvents such as methylene chloride required in the interfacial polymerization method. In addition, the highly toxic phosgene used as a carbonate source in the interfacial polymerization method is not used, so it is also advantageous in terms of manufacturing.

[0153] (Carbonate compounds)

[0154] Examples of the carbonate compound include diaryl carbonate compounds, dialkyl carbonate compounds, and alkyl aryl carbonate compounds.

[0155] Examples of the diaryl carbonate compound include a compound represented by the following general formula (11) and a compound represented by the following general formula (12).

[0156] [Chemical formula 17]

[0157]

[0158] [In formula (11), Ar 1 and Ar 2 represent aryl groups, and may be the same or different from each other. 3 and Ar 4 They represent aryl groups, which may be the same or different from each other. 1 It represents the residue obtained by removing two hydroxyl groups from the above aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0159] 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).

[0160] [Chemical formula 18]

[0161]

[0162] [In formula (13), R 21 and R 22Each of them 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. 23 and R 24 Each of them 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 It represents the residue obtained by removing two hydroxyl groups from the above aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0163] 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).

[0164] [Chemical formula 19]

[0165]

[0166] [In formula (15), Ar 5 Represents 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 Represents an aryl group, R 26 represents an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms, D 1 It represents the residue obtained by removing two hydroxyl groups from the above aromatic dihydroxy compound or aliphatic dihydroxy compound.]

[0167] Examples of the diaryl carbonate compound include diphenyl carbonate, ditolyl carbonate, di(chlorophenyl) carbonate, di(m-tolyl) carbonate, dinaphthyl carbonate, di(biphenyl) carbonate, and bisphenol A bisphenyl carbonate.

[0168] Examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and bisphenol A dimethyl carbonate.

[0169] Examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, and bisphenol A methyl phenyl carbonate.

[0170] A preferred carbonate compound is diphenyl carbonate.

[0171] In the production of the polycarbonate-polyorganosiloxane copolymer (A), one or two or more carbonate compounds may be used.

[0172] (Capping agent)

[0173] When the polycarbonate-polyorganosiloxane copolymer (A) is produced, an end-capping agent may be used as required. As the end-capping agent, any known end-capping agent 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.

[0174] (Branching Agent)

[0175] When the polycarbonate-polyorganosiloxane copolymer (A) is produced, a branching agent may be used. Examples of the branching agent include phloroglucinol, 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).

[0176] Specifically, for example, the polycarbonate-polyorganosiloxane copolymer (A) can be produced by the following steps by a melt polymerization method.

[0177] The diol monomer (a1), the polyorganosiloxane (a2) and the carbonate compound are subjected to an ester exchange reaction. The amount of the carbonate compound relative to the diol monomer is preferably 0.9 to 1.2 times by mole, and more preferably 0.98 to 1.02 times by mole.

[0178] In the above-mentioned transesterification reaction, if the amount of the end-capping agent is in the range of 0.05 to 10 mol% relative to the total amount of the diol monomer (a1) and the polyorganosiloxane (a2), the hydroxyl terminal of the obtained polycarbonate-polyorganosiloxane copolymer is sufficiently capped, which is preferred from the viewpoint of obtaining a polycarbonate resin with excellent heat resistance and water resistance. The amount of the end-capping agent is more preferably 1 to 6 mol% relative to the total amount of the diol monomer (a1) and the polyorganosiloxane (a2). The end-capping agent may be added to the reaction system in total in advance, or a portion may be added to the reaction system in advance and the rest may be added as the reaction proceeds.

[0179] It is preferred that an antioxidant is simultaneously introduced into a reactor together with the diol monomer (a1), the polyorganosiloxane (a2) and the carbonate compound, and the transesterification reaction is carried out in the presence of the antioxidant. This can reduce, for example, the degradation of the diol monomer caused by heat, oxidation, etc. in the heating and melting process before adding the catalyst, and the degradation of the diol monomer and the obtained polycarbonate-polyorganosiloxane copolymer caused by heat, oxidation, etc. in the polymerization process after adding the catalyst. This can obtain a polycarbonate-polyorganosiloxane copolymer with a more excellent appearance such as color tone, and can also obtain effects such as reducing the generation of undesirable gel components.

[0180] When the transesterification reaction is carried out, the reaction temperature is not particularly limited, and can be, for example, 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. In addition, a method of gradually raising the temperature from 180° C. to 300° C. in accordance with the progress of the reaction is preferred. If the temperature of the transesterification reaction is 100° C. or higher, the reaction rate is sufficiently high, while if it is 330° C. or lower, a large amount of side reactions will not occur, and it is not easy to cause the problem of poor appearance such as coloration of the generated polycarbonate-polyorganosiloxane copolymer.

[0181] The reaction pressure is set according to the vapor pressure of the monomer used and the reaction temperature. There is no particular limitation as long as the reaction is carried out efficiently. For example, it is preferred that the reaction pressure be set to an atmospheric pressure (normal pressure) or a pressurized state of 1 to 50 atm (760 to 38,000 torr) in the initial stage of the reaction, and to a reduced pressure state in the later stage of the reaction, and finally to 1.33 to 1.33×10 4 Pa (0.01~100torr).

[0182] The reaction time may be carried out until the target molecular weight is reached, and is, for example, 0.2 to 10 hours.

[0183] The above-mentioned transesterification reaction is carried out, for example, in the absence of an inert solvent. If necessary, it can be carried out in the presence of 1 to 150 parts by mass of an inert solvent relative to 100 parts by mass of the obtained polycarbonate resin. Examples of the inert solvent include aromatic compounds such as diphenyl ether, halogenated diphenyl ether, benzophenone, polyphenylene ether, dichlorobenzene and methylnaphthalene; and tricyclic [5.2.1.0 2，6 ]Cycloalkanes such as decane, cyclooctane and cyclodecane, etc.

[0184] If necessary, the reaction may be carried out in an inert gas atmosphere. Examples of the inert gas include various gases such as argon, carbon dioxide, nitrous oxide, nitrogen, chlorofluorocarbons, alkanes such as ethane and propane, and olefins such as ethylene and propylene.

[0185] In the melt polymerization method, a basic catalyst is preferably used as a catalyst. As the basic catalyst, at least one selected from metal catalysts such as alkali metal compounds and alkaline earth metal compounds, nitrogen-containing compounds, organic catalysts such as quaternary phosphonium salts containing aromatic groups, and metal compounds can be cited. These compounds can be used alone or in combination.

[0186] As the basic catalyst, organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals or alkaline earth metals; quaternary ammonium hydroxides; quaternary phosphonium salts containing an aryl group, etc. The basic catalyst may be used alone or in combination of two or more.

[0187] Examples of the alkali metal compound 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, dicesium salt, dilithium salt of bisphenol A, and sodium salt, potassium salt, cesium salt, lithium salt of phenol.

[0188] Examples of the alkaline earth metal compound include magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium diacetate, calcium diacetate, strontium diacetate, and barium diacetate.

[0189] Examples of nitrogen-containing compounds include quaternary ammonium hydroxides having an alkyl group, an aryl group, and the like such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide. In addition, examples include tertiary amines such as triethylamine, dimethylbenzylamine, and triphenylamine, and imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole. In addition, examples include alkalis or basic salts such as ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetraphenylammonium tetraphenylborate.

[0190] Examples of the metal compound include zinc-aluminum compounds, germanium compounds, organic tin compounds, antimony compounds, manganese compounds, titanium compounds, and zirconium compounds.

[0191] Specific examples of the quaternary phosphonium salt containing an aryl group include tetraphenylphosphonium hydroxide, tetranaphthylphosphonium hydroxide, tetra(chlorophenyl)phosphonium hydroxide, tetra(biphenyl)phosphonium hydroxide, tetratolylphosphonium hydroxide, tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrabutylphosphonium hydroxide and the like tetra(aryl or alkyl)phosphonium hydroxides, tetramethylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium phenolate, tetraphenylphosphonium tetraphenylborate, methyltriphenylphosphonium tetraphenylborate, benzyltriphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, tetratolylphosphonium tetraphenylborate, tetraphenylphosphonium phenolate, tetra(p-tert-butylphenyl)phosphonium diphenyl phosphate, triphenylbutylphosphonium phenolate, triphenylbutylphosphonium tetraphenylborate and the like.

[0192] The quaternary phosphonium salt containing an aromatic group is preferably combined with a nitrogen-containing organic basic compound, for example, a combination of tetramethylammonium hydroxide and tetraphenylphosphonium tetraphenylborate is preferred.

[0193] The amount of the basic catalyst used is preferably 1×10 -9 ~1×10 -2 mole, preferably 1×10 -8 ~1×10 -2 mole, more preferably 1×10 -7 ~1×10 -3 Select from the range of moles.

[0194] A catalyst deactivator may be added at the later stage of the reaction. As the catalyst deactivator used, a known catalyst deactivator can be effectively used. Examples of the catalyst deactivator include ammonium salts of sulfonic acid and phosphonium salts of sulfonic acid.

[0195] 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 mol, more preferably 0.5 to 10 mol, and even more preferably 0.8 to 5 mol, relative to 1 mol of the catalyst.

[0196] It is preferred to add a catalyst deactivator and mix an antioxidant after the polymerization reaction is completed. By mixing an antioxidant after the polymerization reaction is completed and then taking out the obtained polycarbonate-polyorganosiloxane copolymer from the reactor, it is possible to reduce the degradation of the polycarbonate-polyorganosiloxane copolymer caused by heat, oxygen, etc. in the subsequent compounding process and the process of obtaining a molded body. As a result, resin pellets and molded bodies with better appearance such as color tone and surface appearance can be obtained, and effects such as reducing the generation of undesirable gel components can also be obtained.

[0197] The reaction in the melt polymerization method can be carried out in any of a continuous method and an intermittent method. The reaction device used in the melt polymerization can be a vertical reaction device equipped with an anchor stirring paddle, a maximum blade type (MAXBLEND) stirring paddle or a helical ribbon type (HELICALRIBBON) stirring paddle, or a horizontal reaction device equipped with a paddle type paddle, a grid type paddle (Japanese original: lattice wing) or a glasses type paddle, etc. In addition, it can also be an extruder type equipped with a screw. In the case of a continuous method, it is preferred to use these reaction devices in appropriate combination.

[0198] <Polycarbonate resin composition>

[0199] The polycarbonate-based resin composition of the present invention contains the above-mentioned polycarbonate-polyorganosiloxane copolymer (polycarbonate-polyorganosiloxane copolymer (A)).

[0200] The polycarbonate resin composition of the present invention may contain known additives within a range that does not impair the properties of the polycarbonate-polyorganosiloxane copolymer (A).

[0201] (additive)

[0202] The polycarbonate resin composition of the present invention may be formulated with known additives according to the application and needs. Examples of the additives include various fillers, antioxidants, heat stabilizers, plasticizers, light stabilizers, polymer metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, and mold release agents.

[0203] The antioxidant can suppress the decomposition of the resin during production and molding of the thermoplastic resin composition.

[0204] The method for producing the polycarbonate resin composition of the present invention is not particularly limited as long as it has a step of mixing the polycarbonate-polyorganosiloxane copolymer and the optional additive. For example, the polycarbonate-polyorganosiloxane copolymer and the optional additive can be mixed using a mixer or the like, and melt-kneaded to produce the composition. The melt-kneading can be carried out by a commonly used method, such as a method using a ribbon mixer, a Henschel mixer, a Banbury mixer, a drum mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, etc. The heating temperature during the melt-kneading is usually appropriately selected in the range of about 150 to 300° C., preferably about 220 to 300° C.

[0205] [molded body]

[0206] The molded body of the present invention comprises the polycarbonate resin composition of the present invention. The molded body can be manufactured by injection molding, injection compression molding, extrusion molding, blow molding, stamping molding, vacuum forming, foaming, etc. using a melt-kneaded product of the polycarbonate resin composition or pellets obtained by melt-kneading as a raw material. In particular, it is preferred to manufacture the molded body by injection molding or injection compression molding using the obtained pellets.

[0207] The thickness of the molded body can be arbitrarily set according to the application. In particular, when the transparency of the molded body is required, it is preferably 0.2 to 4.0 mm, more preferably 0.3 to 3.0 mm, and further preferably 0.3 to 2.0 mm. If the thickness of the molded body is 0.2 mm or more, warping will not occur and good mechanical strength can be obtained. In addition, if the thickness of the molded body is 4.0 mm or less, high transparency can be obtained.

[0208] If necessary, a hard coat film, an antifogging film, an antistatic film, or an antireflection film may be formed on the molded article, and a composite film of two or more may be formed.

[0209] Among them, a coating having a hard coating film is particularly preferred from the perspective of good weather resistance and the ability to prevent wear of the molded body surface over time. The material of the hard coating film is not particularly limited, and known materials such as acrylate hard coating agents, silicone hard coating agents, and inorganic hard coating agents can be used.

[0210] The molded article comprising the polycarbonate resin of the present invention can be suitably used for members requiring transparency and rigidity as well as scratch resistance and weather resistance, for example: 1) automotive parts such as sunroofs, door visors, rear windows, and side windows; 2) architectural parts such as architectural glass, soundproof walls, carports, sunrooms, and grilles; 3) windows for railway vehicles and ships; 4) various parts for televisions, radio-recorders, cameras, video recorders, audio players, DVD players, telephones, monitors, computers, cash registers, copiers, printers, fax machines, and various parts for electrical equipment such as outer panels and housings; 5) precision equipment parts such as shells and covers of precision machinery such as mobile phones, PDAs, cameras, slide projectors, clocks, calculators, measuring instruments, and display devices; 6) agricultural parts such as plastic greenhouses and greenhouses; 7) furniture parts such as lighting covers, blinds, and interior decoration appliances.

[0211] Example

[0212] Hereinafter, the present invention will be further described in detail by way of examples, but the present invention is not limited to these examples.

[0213] [1. Production of terminal-modified polyorganosiloxane]

[0214] Synthesis Example 1: Preparation of PDMS-1

[0215] In a nitrogen atmosphere, in 100 g of an α,ω-dihydrogen organopolysiloxane having an average chain length of 45 represented by the following formula,

[0216] [Chemical formula 20]

[0217]

[0218] 35.3 g (twice the molar amount based on the polyorganosiloxane) of a single-terminal allyl-modified polyethylene glycol having an average repeating number of 12 ethylene oxide units represented by the following formula was added.

[0219] [Chemical formula 21]

[0220]

[0221] After adding 338 g of toluene as a solvent (2.5 parts relative to the total mass of polyorganosiloxane and polyethylene glycol), the mixture was stirred thoroughly 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) as a hydrosilylation catalyst was added in an amount such that the mass of platinum atoms relative to the total mass of siloxane units (-[Si(CH3)2O]-) was 5 ppm by mass, and the mixture was stirred at a reaction temperature of 110°C for 10 hours. Toluene and the platinum catalyst were removed from the obtained mixture to obtain a modified polyorganosiloxane PDMS-1.

[0222] Synthesis Example 2: Preparation of PDMS-2

[0223] Modified polyorganosiloxane PDMS-2 was obtained in the same manner as in Synthesis Example 1, except that 100 g of α,ω-dihydroorganopolysiloxane having an average chain length of 61 was used instead of α,ω-dihydroorganopolysiloxane having an average chain length of 45, and 31.4 g of single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 15 was used instead of single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 12.

[0224] Synthesis Example 3: Preparation of PDMS-3

[0225] Modified polyorganosiloxane PDMS-3 was obtained in the same manner as in Synthesis Example 1 except that α,ω-dihydroorganopolysiloxane having an average chain length of 24 was used instead of α,ω-dihydroorganopolysiloxane having an average chain length of 45 and 63.8 g of single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 12 was used.

[0226] Synthesis Example 4: Preparation of PDMS-4

[0227] 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-dihydroorganopolysiloxane having an average chain length of 45, and 8.9 g of ethylene glycol monoallyl ether was used instead of the single-terminal allyl-modified polyethylene glycol having an average repeating number of 12 ethylene oxide units.

[0228] In addition, ethylene glycol monoallyl ether has one oxyethylene unit.

[0229] Synthesis Example 5: Preparation of PDMS-5

[0230] Modified polyorganosiloxane PDMS-5 was obtained in the same manner as in Synthesis Example 1 except that 24.2 g of a single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 8 (UNIOX PK-5002 manufactured by NOF Corporation) was used instead of the single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 12.

[0231] Synthesis Example 6: Preparation of PDMS-6

[0232] Modified polyorganosiloxane PDMS-6 was obtained in the same manner as in Synthesis Example 1 except that 102.0 g of a single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 38 (UNIOX PK-5005 manufactured by NOF Corporation) was used instead of the single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 12.

[0233] Synthesis Example 7: Preparation of PDMS-7

[0234] 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-dihydroorganopolysiloxane having an average chain length of 45, and 21.2 g of a single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 15 was used instead of the single-terminal allyl-modified polyethylene glycol having an average repeating number of oxyethylene units of 12.

[0235] Synthesis Example 8: Preparation of PDMS-8

[0236] In a nitrogen atmosphere, in 100 g of a polyorganosiloxane having an average chain length of 39 represented by the following formula,

[0237] [Chemical formula 22]

[0238]

[0239] After adding 9.1 g of 2-allylphenol (twice the molar amount relative to the polyorganosiloxane), the mixture was stirred thoroughly 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 in an amount such that the mass of platinum atoms relative to the siloxane unit (-[Si(CH3)2O]-) was 5 ppm by mass, and the mixture was stirred at a reaction temperature of 100°C for 10 hours. Toluene and the platinum catalyst were removed from the obtained mixture to obtain a modified polyorganosiloxane PDMS-8.

[0240] The outlines of Synthesis Examples 1 to 8 are shown in Table 1 below.

[0241] [Table 1]

[0242]

[0243] Example 1

[0244] The polycarbonate-polyorganosiloxane copolymer was produced using the following raw materials and conditions.

[0245] Into a 10 L stainless steel reactor equipped with a stirring device, a nitrogen inlet pipe, a heater, a trap for capturing distilled phenol, and a pressure reducing device, bisphenol A (BisP-A; 2489.9 g) as a diol monomer and diphenyl carbonate (DPC; 2500 g) as a carbonate 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 were charged, and these raw material monomers were completely melted at 150°C, and then the inside of the reactor was replaced with nitrogen.

[0246] 1.64 mL of 0.01 mol / L sodium hydroxide (1.5 × 10 molar mass relative to the total diol monomer) was added as a catalyst. -6 The temperature in the reactor was raised to 180°C in about 60 minutes, and the pressure in the reactor was reduced to 200 mmHg (26.6 kPa). The reaction conditions were maintained until the phenol distillation amount reached 0.2 L.

[0247] Next, the temperature in the reactor was raised to 240°C over about 120 minutes, and the reaction conditions were maintained until 1.5 L of phenol was distilled out. Next, the temperature in the reactor was raised to 280°C over about 120 minutes, and the pressure in the reactor was reduced to less than 1 mmHg (0.1 kPa), and more than 2 L of phenol was distilled out, and the reaction was continued until the specified stirring torque was reached.

[0248] Then, nitrogen was introduced to increase the pressure to normal pressure, and 0.037 g (10 times the molar amount of the sodium hydroxide added) of butyl p-toluenesulfonate was added as a catalyst deactivator.

[0249] In addition, the following antioxidant 1 and antioxidant 2 were added to the reactor in an amount of 0.05 parts by mass, respectively, relative to the theoretical yield of the polycarbonate-polyorganosiloxane copolymer, and stirred sufficiently. Then, high-pressure nitrogen was introduced into the reactor to extrude strands of the molten polycarbonate-polyorganosiloxane copolymer from the bottom of the reactor. The obtained strands were cut with a pelletizer to obtain pellets of the polycarbonate-polyorganosiloxane copolymer PC-POS1.

[0250] The raw materials used in the production are as follows.

[0251] ・Bisphenol A (BisP-A) [Manufactured by Idemitsu Kosan Co., Ltd.]

[0252] ・Diphenyl carbonate (DPC) [manufactured by Mitsui Fine Chemical Co., Ltd.]

[0253] ・0.01 mol / L sodium hydroxide aqueous solution [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]

[0254] ・Antioxidant (C):

[0255] Antioxidant 1: tris(2,4-di-tert-butylphenyl)phosphite [manufactured by BASF Japan, Irgafos168]

[0256] Antioxidant 2: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] [manufactured by BASF Japan, Irganox 1010]

[0257] Example 2

[0258] A pellet of a polycarbonate-polyorganosiloxane copolymer was produced in the same manner as in Example 1 except that 179.7 g of the modified polyorganosiloxane PDMS-1 was used.

[0259] Example 3

[0260] A pellet of a polycarbonate-polyorganosiloxane copolymer was produced in the same manner as in Example 1 except that 244.8 g of the modified polyorganosiloxane PDMS-1 was used.

[0261] Example 4

[0262] 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.

[0263] Example 5

[0264] A pellet of a polycarbonate-polyorganosiloxane copolymer was produced in the same manner as in Example 1 except that 179.7 g of PDMS-2 was used as the modified polyorganosiloxane.

[0265] Example 6

[0266] 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.

[0267] Example 7

[0268] Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 179.7 g of PDMS-1 as a modified polyorganosiloxane was used and the reaction was continued for 30 minutes even after the predetermined torque was reached.

[0269] Example 8

[0270] Pellets of a polycarbonate-polyorganosiloxane copolymer were produced in the same manner as in Example 1 except that 117.3 g of PDMS-2 as a modified polyorganosiloxane was used and the reaction was continued for 30 minutes even after the predetermined torque was reached.

[0271] Comparative Example 1

[0272] 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.

[0273] Comparative Example 2

[0274] 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.

[0275] Comparative Example 3

[0276] 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.

[0277] Comparative Example 4

[0278] 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.

[0279] Comparative Example 5

[0280] 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.

[0281] Comparative Example 6

[0282] 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.

[0283] Comparative Example 7

[0284] 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.

[0285] Comparative Example 8

[0286] 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.

[0287] [evaluate]

[0288] The following evaluations were performed on the pellets of the polycarbonate-polyorganosiloxane copolymers produced in Examples 1 to 8 and Comparative Examples 1 to 8.

[0289] (1) 1 H-NMR measurement

[0290] Based on 1 The average chain length of the polyorganosiloxane structure, the average number of repetitions of the polyether structure, the content of the polyorganosiloxane-containing block (A-1), and the content of the polyorganosiloxane structure (A-3) were calculated from the integrated values ​​of the peaks derived from the following specific structures obtained by H-NMR measurement.

[0291] NMR equipment: ECA-500 manufactured by JEOL Resonance Co., Ltd.

[0292] Probe: TH5 corresponds to 5φNMR sample tube

[0293] Observation range: -5~15ppm

[0294] Observation center: 5ppm

[0295] Pulse repetition time: 9 seconds

[0296] Pulse width: 45°

[0297] Total times: 256 times

[0298] NMR sample tube: 5φ

[0299] Sample amount: 30-40 mg

[0300] Solvent: deuterated chloroform

[0301] Measurement temperature: room temperature

[0302] A: Integrated value of the peak at the meta position of the phenyl moiety observed around δ7.3 to 7.5

[0303] B: Peak integration value of the methylene group of the PEG moiety observed around δ 3.3 to 4.5

[0304] C: Peak integration value of the methyl group of bisphenol A observed around δ1.50 to 2.00

[0305] D: Peak integration value of the methyl group of the dimethylsiloxane moiety observed around δ-0.02 to 0.4

[0306] E: Peak integration value of the methylene group at the end of dimethylsiloxane observed at around δ0.52

[0307] F: Peak integral value of the terminal methylene group of polyethylene glycol linked to the carbonate bond observed at around δ4.3

[0308] a=A / 2

[0309] b=B / 4

[0310] c=(Ce×2) / 6

[0311] d=D / 6

[0312] e=E / 2

[0313] f=F / 2

[0314] T=a+b+c+d

[0315] h=a / T×100

[0316] i=b / T×100

[0317] j=c / T×100

[0318] k=d / T×100

[0319] TW=h×93+i×44+j×254+k×74.1

[0320] ・Average chain length of polyorganosiloxane structure

[0321] n a The average value of = d / (e / 2)

[0322] ・Average number of repeating polyether structures

[0323] n b The average value of = b / e

[0324] ・Content of polyorganosiloxane-containing block (A-1)

[0325] Content of (A-1) [mass %] = (i × 44 + k × 74.1) / TW × 100

[0326] ・Content of polyorganosiloxane structure (A-3)

[0327] Content of (A-3) [mass %] = (k × 74.1) / TW × 100

[0328] (2) Determination method of viscosity average molecular weight

[0329] The viscosity of a dichloromethane solution (concentration: g / L) at 20°C was measured using an Ubbelohde viscometer to determine the intrinsic viscosity [η], and the viscosity average molecular weight (Mv) was calculated using the following formula (Schnell formula). The results are shown in Tables 2 and 3.

[0330] [η] = 1.23 × 10 -5 Mv 0.83

[0331] (3) Fluidity: Q value determination method

[0332] The Q value is measured by the following method in accordance with JIS K7210-1:2014.

[0333] The pellets prepared 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 was measured at 280°C and a pressure of 160 kg (×10 -2 The results are shown in Tables 2 and 3.

[0334] Q value (flow value)〔Unit: 10 -2 mL / sec] represents the outflow rate per unit time. The higher the value, the better the fluidity.

[0335] (4) Impact resistance: Charpy impact strength measurement method

[0336] 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 pieces for mechanical property evaluation (total length: 169 mm, length / width of the narrow parallel part: 80 mm / 10 mm, length / width of the wide parallel part: 35 mm / 20 mm, thickness: 3 mm). A strip-shaped test piece with a length of 80 mm, a width of 10 mm, and a thickness of 3 mm was cut from the horizontal and vertical parts. Furthermore, a notch (r = 0.25 mm ± 0.05 mm) was given by post-processing to obtain a test piece. The Charpy impact strength at 23°C, 0°C, and -20°C was measured using a Charpy impact tester (Charpy impact tester, model 611, manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with ISO 179-1:2010. The results are shown in Tables 2 and 3.

[0337] (5) Determination method of tensile elongation

[0338] 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 pieces for mechanical property evaluation (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 test pieces were used for measurement in accordance with ISO527-1, 2: 2012. The results are shown in Tables 2 and 3.

[0339] (6) Evaluation method of molded body appearance

[0340] The pellets produced above were dried at 100°C for 5 hours and then injection molded at a barrel temperature of 280°C and a mold temperature of 80°C to obtain dumbbell test pieces for mechanical property evaluation (total length: 169 mm, length / width of the narrow parallel portion: 80 mm / 10 mm, length / width of the wide parallel portion: 35 mm / 20 mm, thickness: 4 mm). The wide parallel portion of the test piece was clamped and bent, and the presence of surface peeling of the narrow parallel portion was visually evaluated when the distance between the end portions (width 20 mm) was 140 mm.

[0341] A: There is surface peeling

[0342] B: No surface peeling

[0343] The results are shown in Tables 2 and 3.

[0344] [Table 2]

[0345]

[0346] [Table 3]

[0347]

Claims

1. A polycarbonate-polyorganosiloxane copolymer, which is a polycarbonate-polyorganosiloxane copolymer (A) comprising a polyorganosiloxane-containing block (A-1) and a polycarbonate block (A-2), wherein the polyorganosiloxane-containing block (A-1) comprises a structural unit represented by the following general formula (1), and the polycarbonate block (A-2) comprises a structural unit represented by the following general formula (2) repeatedly, The content of the polyorganosiloxane-containing block (A-1) is 2% by mass or more and 30% by mass or less, n b The average value relative to n a The ratio of the average values ​​of b The average value of a The average value of ) is 0.2 or more and 0.4 or less, In the formula, R 1 ~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, and R 5 and R 6 Each independently represents an alkylene group having 1 to 3 carbon atoms, and these groups may contain a group selected from -O-, -COO-, -CO-, -S-, -NH- and -NR in at least one of the main chain and the side chain. 111 -at least one group, Multiple R 7 and R 8 Each of them can be the same or different, multiple R 7 and R 8 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 -O-, -COO-, -CO-, -S-, -NH-, -NR in at least one of the main chain and the side chain. 111 - at least one group, 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 Represents 0 or 1, n a Integer from 2 to 500, n b Each independently represents an integer from 2 to 200, R 10 It 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 these groups may contain at least one atom selected from an oxygen atom, a nitrogen atom, a sulfur atom and a halogen atom.

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

3. The polycarbonate-polyorganosiloxane copolymer according to claim 1 or 2, wherein n b The average value relative to the n a The ratio of the average values ​​of b The average value of a The average value of ) is greater than 0.2 and less than 0.

35.

4. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 3, 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), 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, and when there are two or more of them, they may be the same or different, and β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid.

5. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 4, wherein The polycarbonate block (A-2) comprising the repeated structural unit represented by the general formula (2) comprises the structural unit represented by the following general formula (111): 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-, -SO2-, -O- or -CO-, and s and t each independently represent an integer of 0 to 4.

6. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 5, wherein In the general formula (1), R 1 ~R 4 represent methyl groups respectively.

7. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 6, wherein In the general formula (1), R 5 and R 6 They represent trimethylene -(CH2)3- respectively.

8. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 7, wherein In the general formula (1), R 7 and R 8 They respectively represent a dimethylene group -(CH2)2-, a methyl-substituted dimethylene group, i.e. -CH2CH(CH3)- or -CH(CH3)CH2-, a trimethylene group -(CH2)3-, or a tetramethylene group -(CH2)4-.

9. The polycarbonate-polyorganosiloxane copolymer according to any one of claims 1 to 8, wherein In the polycarbonate-polyorganosiloxane copolymer, the content of the polyorganosiloxane structure (A-3) comprising a repeating structural unit represented by the following general formula (3) contained in the polyorganosiloxane-containing block (A-1) is 0.1% by mass or more and 30% by mass or less, In the formula, R 1 ~R 2 Means the same as above. 10 . The polycarbonate-polyorganosiloxane copolymer according to claim 1 , which has a viscosity average molecular weight Mv of 15,000 or more and 30,000 or less. 11 . The polycarbonate-polyorganosiloxane copolymer according to claim 1 , which is obtained by a melt polymerization method. 12 . The polycarbonate-polyorganosiloxane copolymer according to claim 1 , which is obtained using the diol monomer a1. 13 . A polycarbonate-based resin composition comprising the polycarbonate-polyorganosiloxane copolymer according to claim 1 . 14 . A molded article formed from the polycarbonate resin composition according to claim 13 .

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