Resin Composition, Molded Body, and Method for Improving Characteristics of Resin Composition

Abstract

This resin composition contains: a polycarbonate-polyorganosiloxane copolymer (A) which includes polycarbonate blocks (A-1) formed a repeating unit represented in general formula (I) and polyorganosiloxane blocks (A-2) formed from a repeating unit represented in general formula (II), and carbon fibers (B), wherein the carbon fibers (B) have attached a compound with an epoxy group.

Description

Technical Field

[0001] The present invention relates to a resin composition, a molded article, and a method for improving the properties of the resin composition. Specifically, the present invention relates to a resin composition capable of achieving good balance among fluidity, impact resistance, and elasticity, a molded article, and a method for improving the properties of the resin composition.

Background Art

[0002] Polycarbonate resins have excellent mechanical properties and are widely used industrially in fields such as the automotive, OA, and electrical and electronic industries. Among them, polycarbonate resins reinforced with carbon fibers are used in fields such as OA and electrical and electronic industries, such as the housings of notebook computers and the bodies of single-lens reflex cameras.

[0003] Patent Documents 1 to 4 disclose polycarbonate resins reinforced with carbon fibers.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

[0005] In recent years, products such as the housings of portable electronic devices have been made thinner, and thus, particularly for thin and precision parts, it is required to have excellent various mechanical strengths such as rigidity and impact strength.

[0006] In order to improve the mechanical strength of polycarbonate resins, methods of blending carbon fibers have been proposed. However, since carbon fibers themselves are very hard and brittle, the impact resistance of conventional carbon fiber-reinforced polycarbonate resins has not been sufficient. Furthermore, in recent years, in aircraft and automotive applications, there has been a high need for weight reduction due to the high rigidity of carbon fiber composite materials, and further high-filled carbon fiber-reinforced composite materials are required. In this case, further reduction in fluidity and impact resistance occurs.

[0007] In conventional technologies including Patent Documents 1 to 4, further room for improvement has been found from the viewpoint of solving the above problems.

[0008] One object of the present invention is to provide a resin composition, a molded article, and a method for improving the properties of the resin composition that can achieve good balance among fluidity, impact resistance, and elasticity.

[0009] According to the present invention, the following resin compositions and the like can be provided. 1. A polycarbonate-polyorganosiloxane copolymer (A) containing a polycarbonate block (A-1) composed of repeating units represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing repeating units represented by the following general formula (II), carbon fiber (B), and a resin composition, wherein the carbon fiber (B) is a carbon fiber to which a compound having an epoxy group is attached.

Chemical formula

[0010] According to the present invention, it is possible to provide a resin composition, a molded article, and a method for improving the properties of the resin composition that can achieve good compatibility of fluidity, impact resistance, and elasticity. [Embodiments for Carrying Out the Invention]

[0011] ​Hereinafter, the resin composition of the present invention, the molded article, and the method for improving the properties of the resin composition will be described in detail. In addition, in this specification, "x to y" represents a numerical range of "x or more and y or less". The upper limit value and the lower limit value described for the numerical range can be arbitrarily combined. Moreover, a form in which two or more of the individual forms of the present invention described below are combined is also a form of the present invention.

[0012] 1. Resin composition The resin composition according to one aspect of the present invention includes a polycarbonate block (A-1) composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), and a polycarbonate-polyorganosiloxane copolymer (A), and carbon fiber (B), wherein the carbon fiber (B) is a carbon fiber to which a compound having an epoxy group is attached. [Chemical formula] (In the above formula (I), R 1 and R 2 each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. a and b each independently represent an integer of 0 to 4. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO2-, -O-, or -CO-. In the above formula (II), R 3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

[0013] According to the resin composition according to this aspect, an effect can be obtained in which fluidity, impact resistance, and elasticity can be favorably balanced.

[0014] Hereinafter, each component contained in the resin composition according to this aspect will be described in detail.

[0015] (Polycarbonate-Polyorganosiloxane Copolymer (A)) The polycarbonate-polyorganosiloxane copolymer (A) (hereinafter, also referred to as “component (A)” or “PC-POS copolymer”) includes a polycarbonate block (A-1) composed of repeating units represented by the general formula (I) and a polyorganosiloxane block (A-2) containing repeating units represented by the general formula (II).

[0016] In the general formula (I), R 1 and R 2 Examples of the halogen atom independently represented by each include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0017] R 1 and R 2 Examples of the alkyl group independently represented by each include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups (the “various” means including linear and all branched-chain ones. The same applies hereinafter in the specification), various pentyl groups, and various hexyl groups. Examples of the alkoxy group independently represented by R 1 and R 2 each include those having the alkyl group as the alkyl group moiety.

[0018] a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

[0019] Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a tetramethylene group, a hexamethylene group, etc., and an alkylene group having 1 to 5 carbon atoms is preferred.

[0020] Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group.

[0021] Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group. A cycloalkylene group having 5 to 10 carbon atoms is preferred.

[0022] Examples of the arylene group represented by X include a phenylene group and a naphthylene group. An arylene group having 6 to 10 carbon atoms is preferred.

[0023] Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidene group. A cycloalkylidene group having 5 to 10 carbon atoms is preferred, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferred.

[0024] The number of carbon atoms of the arylalkylene group having 7 to 15 carbon atoms represented by X means the total number of carbon atoms of the aryl moiety and the alkylene moiety. Examples of the aryl moiety of the arylalkylene group represented by X include aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and examples of the alkylene moiety include the above-described alkylene groups.

[0025] The number of carbon atoms of the arylalkylidene group having 7 to 15 carbon atoms represented by X means the total number of carbon atoms of the aryl moiety and the alkylidene moiety. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group, and examples of the alkylidene moiety include the above-described alkylidene groups.

[0026] Among the above, those in which a and b are each 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or those in which a and b are each 0 and X is an alkylene group having 3 carbon atoms, particularly an isopropylidene group, are preferred.

[0027] In general formula (II), R 3 or R 4 Examples of the halogen atom represented by are a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0028] R 3 or R 4 Examples of the alkyl group represented by are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups.

[0029] R 3 or R 4 Examples of the alkoxy group represented by include the case where the alkyl group moiety is the above alkyl group.

[0030] R 3 or R 4 Examples of the aryl group represented by are a phenyl group, a naphthyl group, etc.

[0031] R 3 and R 4 are both preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more preferably both are a methyl group.

[0032] The polyorganosiloxane block (A-2) containing the repeating unit represented by general formula (II) preferably has repeating units represented by general formulas (II-I) to (II-III) more specifically. [Chemical formula]

[0033] (In the above formulas (II-I) to (II-III), R 3 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and a plurality of R 3~R 6 may be the same as or different from each other. Y is -R 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO-R 9 -O-, or R 7 O-R 10 represents -O-, and a plurality of Ys may be the same as or different from each other. R 7 represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. R 8 represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R 9 represents a diarylene group. R 10 represents a linear, branched or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. n represents the average chain length of the polyorganosiloxane, n-1, and p and q each represent the number of repetitions of the polyorganosiloxane unit, which are integers of 1 or more, and the sum of p and q is n-2. )

[0034] R 3 ~R 6 Examples of the halogen atom independently represented by each of ~R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 3 ~R 6 Examples of the alkyl group independently represented by each of ~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. R 3 ~R 6 Examples of the alkoxy group independently represented by each of ~R include the case where the alkyl group moiety is the above alkyl group. R 3 ~R6 Examples of the aryl groups independently represented by each of them include a phenyl group and a naphthyl group.

[0035] R 3 ~R 6 Each of them is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.

[0036] R in the general formulas (II-I) to (II-III) 3 ~R 6 is preferably a methyl group in each case.

[0037] -R represented by Y 7 O-, -R 7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO-R 9 -O-, or R 7 O-R 10 R in -O- 7 Examples of the linear or branched alkylene group represented by include an alkylene group having 1 to 8 carbon atoms, preferably an alkylene group having 1 to 5 carbon atoms. R 7 Examples of the cyclic alkylene group represented by include a cycloalkylene group having 5 to 15 carbon atoms, preferably a cycloalkylene group having 5 to 10 carbon atoms.

[0038] R 7 When R represents an aryl-substituted alkylene group, the alkylene group is bonded to Si. R 7 Examples of the aryl-substituted alkylene group represented by may have substituents such as an alkoxy group and an alkyl group on the aromatic ring, and its specific structure can be, for example, the structure of the following general formula (i) or (ii) (in the formula, the other substitution position of the phenylene group is not shown).

Chemical formula

[0039] R 7 、R 9 and R 10 The diarylene group represented by R 1 -W-Ar 2 is a group having a structure represented by - here, Ar 1 and Ar 2 each independently represent an arylene group, and W represents a single bond or a divalent organic group. Examples of the divalent organic group represented by W include an isopropylidene group, a methylene group, a dimethylene group, and a trimethylene group. R 7 、Ar 1 and Ar 2 Examples of the arylene group represented by include arylene groups having 6 to 14 ring-forming carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group, and an anthrylene group. These arylene groups may have any substituent such as an alkoxy group or an alkyl group.

[0040] R 8 Examples of the alkyl group represented by include linear or branched ones having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. R 8 Examples of the alkenyl group represented by include linear or branched ones having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. R 8 Examples of the aryl group represented by include a phenyl group and a naphthyl group. R 8 Examples of the aralkyl group represented by include a phenylmethyl group and a phenylethyl group. R 10 The linear, branched or cyclic alkylene group represented by is the same as R 7 .

[0041] Y is preferably -R 7 O-, where R 7 is an aryl-substituted alkylene group, particularly the residue of a phenolic compound having an alkyl group, and an organic residue derived from allylphenol or an organic residue derived from eugenol is preferred.

[0042] Furthermore, for p and q in formula (II-II), it is preferable that p = q.

[0043] β represents a divalent group derived from a diisocyanate compound, a divalent group derived from a dicarboxylic acid, or a divalent group derived from a halide of a dicarboxylic acid. Examples thereof include divalent groups represented by the following general formulas (iii) to (vii).

[0044]

Chemical formula

[0045] The average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is not particularly limited. In one embodiment, the average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) can be 20 or more and 500 or less. In this case, n in formulas (II-I) and (II-III) is 20 or more and 500 or less, and in the case of (II-II), the number obtained by adding 2 to the sum of p and q is within the above range. The above average chain length is calculated by nuclear magnetic resonance (NMR) measurement.

[0046] In one embodiment, the average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) can be 30 or more, 35 or more, 40 or more, 45 or more, 50 or more, 55 or more, 60 or more, 65 or more, 70 or more, 75 or more, 80 or more, or 85 or more, and can also be 400 or less, 300 or less, 200 or less, 150 or less, 100 or less, 95 or less. Also, the average chain length n of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably 40 or more or more than 70. Thereby, the effect of excellent impact properties can be obtained.

[0047] In one embodiment, the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) can be 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 1.5% by mass or more, 2.0% by mass or more, 2.5% by mass or more, 3.0% by mass or more, 3.5% by mass or more, 4.0% by mass or more, 4.5% by mass or more, 5.0% by mass or more, or 5.5% by mass or more, and can also be 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, or 8.0% by mass or less. If the amount of polyorganosiloxane in the PC-POS copolymer (A) is within the above range, the effects of the present invention can be exhibited more favorably. Also, the content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) preferably exceeds 4.0% by mass, more preferably is 5.0% by mass or more, and still more preferably is 5.5% by mass or more. Thereby, the effect of excellent impact properties can be obtained. Note that the content of the polyorganosiloxane block (A-2) is calculated by nuclear magnetic resonance (NMR) measurement.

[0048] The viscosity average molecular weight (Mv) of the PC-POS copolymer (A) can be appropriately adjusted by using a molecular weight regulator (end terminator) or the like so as to obtain the target molecular weight according to the intended use and product. The viscosity average molecular weight of the PC-POS copolymer (A) is preferably 9,000 or more and 50,000 or less. If the viscosity average molecular weight is 9,000 or more, sufficient strength of the molded product can be obtained. If the viscosity average molecular weight is 50,000 or less, injection molding or extrusion molding can be performed at a temperature that does not cause thermal degradation. The viscosity average molecular weight of the PC-POS copolymer (A) is more preferably 12,000 or more, still more preferably 14,000 or more, particularly preferably 16,000 or more, more preferably 30,000 or less, still more preferably 25,000 or less, even more preferably 23,000 or less, and particularly preferably 20,000 or less.

[0049] The viscosity-average molecular weight (Mv) is a value calculated from the following Schnell's equation by measuring the intrinsic viscosity [η] of a methylene chloride solution at 20°C. [η]=1.23×10 -5 ×Mv 0.83

[0050] The PC-POS copolymer (A) can be produced by known production methods such as the interfacial polymerization method (phosgene method), the pyridine method, and the transesterification method. In particular, when the interfacial polymerization method is adopted, the separation step between the organic phase containing the PC-POS copolymer and the aqueous phase containing unreacted substances and catalyst residues is easy, and the separation between the organic phase containing the PC-POS copolymer and the aqueous phase in each washing step such as alkali washing, acid washing, and pure water washing is easy. Therefore, the PC-POS copolymer can be obtained efficiently. As a method for producing the PC-POS copolymer, for example, the method described in JP-A-2014-80462 can be referred to.

[0051] Specifically, a previously produced polycarbonate oligomer and a polyorganosiloxane, which will be described later, are dissolved in a water-insoluble organic solvent (such as methylene chloride), an aqueous alkaline compound solution (such as an aqueous sodium hydroxide solution) of a dihydric phenol compound (such as bisphenol A) is added, and a tertiary amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) is used as a polymerization catalyst, and interfacial polycondensation reaction is carried out in the presence of a terminal terminator (a monohydric phenol such as p-tert-butylphenol). Also, the PC-POS copolymer (A) can be produced by copolymerizing a polyorganosiloxane, a dihydric phenol, phosgene, a carbonic acid ester or a chloroformate.

[0052] As the polyorganosiloxane used as a raw material, one or more selected from the group consisting of polyorganosiloxanes represented by the following general formulas (1), (2) and (3) can be used.

Chemical formula

[0053] In Formulas (1) to (3), R 3 ~R 6 , Y, β, n-1, p, and q are as described above, and specific examples and preferred ones are the same.

[0054] Z represents a hydrogen atom or a halogen atom, and a plurality of Zs may be the same as or different from each other.

[0055] For example, as the polyorganosiloxane represented by General Formula (1), compounds of the following General Formulas (1-1) to (1-11) can be mentioned.

[0056]

Chemical formula

[0057] In the above General Formulas (1-1) to (1-11), R 3 ~R 6 , n-1, and R 8 are as defined above, and the preferred ones are the same. c represents a positive integer, usually an integer from 1 to 6. Among these, from the viewpoint of ease of polymerization, the phenol-modified polyorganosiloxane represented by the above General Formula (1-1) is preferred. Also, from the viewpoint of ease of availability, α,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above General Formula (1-2), and α,ω-bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane, which is one of the compounds represented by the above General Formula (1-3), are preferred.

[0058] In addition, as the polyorganosiloxane raw material, those having the following General Formula (4) may also be used.

[0059]

Chemical formula

[0060] When the compound of the above formula (4) is used as a polyorganosiloxane raw material, the polyorganosiloxane block (A-2) preferably has units represented by the following general formulas (II-IV).

[0061]

Chemical formula

[0062] The polyorganosiloxane block (A-2) may have a structure represented by the following general formula (II-V).

Chemical formula

[0063] In the general formula (II-V), examples of the alkyl group having 1 to 13 carbon atoms independently represented by R 18 ~R 21 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, 2-ethylhexyl group, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, and various tridecyl groups. Among them, R 18 ~R 21represents preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably both represent a methyl group.

[0064] R 22 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. R 22 Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 22 Examples of the alkoxy group having 1 to 6 carbon atoms represented by R include cases where the alkyl group moiety is the above alkyl group. R 22 Examples of the aryl group having 6 to 14 carbon atoms represented by R include a phenyl group, a toluyl group, a dimethylphenyl group, and a naphthyl group. Among the above, it is preferable that R 22 represents a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom.

[0065] Q 2 Examples of the divalent aliphatic group having 1 to 10 carbon atoms represented by Q include a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms. The number of carbon atoms of the saturated aliphatic group is preferably 1 to 8, more preferably 2 to 6, even more preferably 3 to 6, and still more preferably 4 to 6. Also, the average chain length n is as described above.

[0066] Preferred embodiments of the constitutional units (II-V) include a structure represented by the following formula (II-VI).

Chemical formula

[0067] The polyorganosiloxane block (A-2) represented by the above general formula (II-V) or (II-VI) can be obtained by using a polyorganosiloxane raw material represented by the following general formula (5) or (6). [Chemical formula] (In formula (5), R 18 ~R 22 , Q 2 , and n - 1 are as described above.) [Chemical formula] (In formula (6), n - 1 is as described above.)

[0068] The method for producing the polyorganosiloxane 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 α,ω-dihydrogen organopentasiloxane, and then, in the presence of a catalyst for hydrosilylation reaction, a phenolic compound (such as 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) is added to the α,ω-dihydrogen organopentasiloxane to obtain a crude polyorganosiloxane. Also, according to the method described in WO 91 / 00885, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst), and the obtained α,ω-dihydrogen organopolysiloxane is added with a phenolic compound or the like in the presence of a catalyst for hydrosilylation reaction in the same manner as above to obtain a crude polyorganosiloxane. In addition, the chain length n of α,ω-dihydrogen organopolysiloxane can be appropriately adjusted according to its polymerization conditions and used, or a commercially available α,ω-dihydrogen organopolysiloxane can also be used. Specifically, those described in JP-A-2016-098292 can be used.

[0069] The polycarbonate oligomer can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene, or chloroform. When producing the polycarbonate oligomer using the transesterification method, it can also be produced by reacting a dihydric phenol with a carbonate precursor such as diphenyl carbonate. As the dihydric phenol, it is preferable to use a dihydric phenol represented by the following general formula (viii). [Chemical formula] (In formula (viii), R 1 , R 2 , a, b, and X are as described above.)

[0070] Examples of the dihydric phenol represented by the general formula (viii) include bis(hydroxyphenyl)alkane-based compounds such as 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 4,4'-dihydroxydiphenyl; bis(4-hydroxyphenyl)cycloalkane; bis(4-hydroxyphenyl)oxide; bis(4-hydroxyphenyl)sulfide; bis(4-hydroxyphenyl)sulfone; bis(4-hydroxyphenyl)sulfoxide; and bis(4-hydroxyphenyl)ketone. These dihydric phenols may be used alone or in combination of two or more. Among these, bis(hydroxyphenyl)alkane-based dihydric phenols are preferable, and bisphenol A is more preferable. When bisphenol A is used as the dihydric phenol, in the above general formula (i), X is an isopropylidene group, and a PC-POS copolymer in which a = b = 0 is obtained.

[0071] Examples of the diphenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, dihydroxydiaryl sulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, and the like. These diphenols may be used alone or in combination of two or more.

[0072] Examples of the bis(hydroxyaryl)alkanes include bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, bis(4-hydroxyphenyl)naphthylmethane, 1,1-bis(4-hydroxy-3-tert-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and the like.

[0073] Examples of the bis(hydroxyaryl)cycloalkanes include 1,1-bis(4-hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane, 2,2-bis(4-hydroxyphenyl)norbornane, 1,1-bis(4-hydroxyphenyl)cyclododecane, and the like. Examples of the dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, and the like.

[0074] Examples of the dihydroxydiaryl sulfides include 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, and the like. Examples of the dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and the like. Examples of the dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and the like.

[0075] Examples of the dihydroxydiphenyls include 4,4'-dihydroxydiphenyl and the like. Examples of the dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, and the like. Examples of the dihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane, 2,2-bis(4-hydroxyphenyl)adamantane, 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane, and the like.

[0076] Examples of the diphenols other than those described above include 4,4'-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane, and the like.

[0077] To adjust the molecular weight of the resulting PC-POS copolymer, a terminal terminator (molecular weight regulator) can be used. Examples of the terminal terminator include monohydric phenols such as phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. These monohydric phenols may be used alone or in combination of two or more.

[0078] After the above interfacial polycondensation reaction, it is appropriately allowed to stand and separated into an aqueous phase and an organic solvent phase [separation step], the organic solvent phase is washed (preferably washed in the order of a basic aqueous solution, an acidic aqueous solution, and water) [washing step], the obtained organic phase is concentrated [concentration step], and dried [drying step] to obtain a PC-POS copolymer (A).

[0079] (Carbon fiber (B)) The carbon fiber (B) (hereinafter, also referred to as the “component (B)”) is a carbon fiber to which a compound having an epoxy group is attached.

[0080] The type of the carbon fiber (B) is not particularly limited, and for example, various carbon fibers such as PAN-based using polyacrylonitrile as a raw material, pitch-based using coal tar pitch in petroleum or coal as a raw material, and phenol-based using a thermosetting resin such as a phenol resin as a raw material, and rayon-based can all be used. Further, the carbon fiber (B) may be obtained by a vapor phase growth method or may be recycled carbon fiber (RCF). Thus, the carbon fiber (B) is not particularly limited, but preferably contains one or more selected from the group consisting of PAN-based carbon fiber, pitch-based carbon fiber, thermosetting carbon fiber, phenol-based carbon fiber, vapor grown carbon fiber, and recycled carbon fiber (RCF).

[0081] The tensile strength of the carbon fiber (B) is not particularly limited, and for example, it can be 1000 MPa or more or 3000 MPa or more.

[0082] The tensile elastic modulus of carbon fiber (B) is not particularly limited and can be, for example, 50 GPa or more, or 200 GPa or more.

[0083] It is preferable to use chopped fibers for the shape of carbon fiber (B). Both single fibers and fiber bundles may be mixed in carbon fiber (B). When using chopped fibers, the average fiber length can be 0.1 mm or more and can be 50 mm or less. The number of single fibers in each fiber bundle may be substantially uniform or different in each fiber bundle. The fiber diameter of carbon fiber is not particularly limited and can be, for example, 3 μm or more, or 4 μm or more, and can also be 20 μm or less, 15 μm or less, 10 μm or less, or 8 μm or less. Incidentally, the average fiber length and fiber diameter of carbon fiber can be measured using an electron microscope.

[0084] The compound having an epoxy group can be one imparted to carbon fiber as a sizing agent. The compound having an epoxy group can cover part or all of the surface of carbon fiber. The compound having an epoxy group imparted to carbon fiber as a sizing agent does not necessarily have to be entirely in a state of adhering to carbon fiber, and part of it may be detached from carbon fiber and dispersed in the resin composition.

[0085] Examples of commercially available products of carbon fiber (B) coated with a compound having an epoxy group include Tenax (registered trademark) chopped fiber HTC261 manufactured by Teijin Limited, Pyrofil (registered trademark) chopped fiber TR066A manufactured by Mitsubishi Chemical Corporation (both treated with an epoxy-based sizing agent), etc. Also, Pyrofil (registered trademark) chopped fiber TR06Q manufactured by Mitsubishi Chemical Corporation (treated with a special epoxy-based sizing agent) may be used.

[0086] In one embodiment, the content of component (B) in the resin composition can be, for example, 5 parts by mass or more, 10 parts by mass or more, 15 parts by mass or more, 20 parts by mass or more, 22 parts by mass or more, or 25 parts by mass or more with respect to 100 parts by mass of component (A), and can also be 500 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 100 parts by mass or less, 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, or 67 parts by mass or less. Also, in one embodiment, the blending ratio ((A):(B)) based on the mass of the PC-POS copolymer (A) and the carbon fiber (B) in the resin composition can be 95 to 35:5 to 65, 90 to 40:10 to 60, 85 to 40:15 to 60, 85 to 55:15 to 45, or 80 to 60:20 to 40.

[0087] (Antioxidant (C)) The resin composition according to this aspect may or may not further contain an antioxidant (C) (hereinafter also referred to as "component (C)"). By including the antioxidant (C), the resin composition according to this aspect can suppress oxidative degradation during melting of the resin composition and can suppress coloring and the like due to oxidative degradation.

[0088] As the antioxidant (C), for example, one or more selected from the group consisting of phosphorus-based antioxidants and phenolic antioxidants can be used.

[0089] Examples of phenolic antioxidants include hindered phenols such as n-octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,6-di-tert-butyl-4-methylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. Among these antioxidants, those having a pentaerythritol diphosphite structure such as bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and triphenylphosphine are preferred.

[0090] Examples of commercially available phenolic antioxidants include Irganox 1010 (manufactured by BASF Japan Ltd., "Irganox" is a registered trademark), Irganox 1076 (manufactured by BASF Japan Ltd.), Irganox 1330 (manufactured by BASF Japan Ltd.), Irganox 3114 (manufactured by BASF Japan Ltd.), Irganox 3125 (manufactured by BASF Japan Ltd.), BHT (manufactured by Takeda Pharmaceutical Company Limited, "BHT" is a registered trademark), Cyanox 1790 (manufactured by Cyanamid, "Cyanox" is a registered trademark), and Sumilizer GA-80 (manufactured by Sumitomo Chemical Company Limited, "Sumilizer" is a registered trademark).

[0091] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl nonyl phosphite, diphenyl (2-ethylhexyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, diphenyl isooctyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono(tridecyl) phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, tris(2-ethylhexyl) phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 4,4'-isopropylidenediphenol dodecyl phosphite, 4,4'-isopropylidenediphenol tridecyl phosphite, 4,4'-isopropylidenediphenol tetradecyl phosphite, 4,4'-isopropylidenediphenol pentadecyl phosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenyl) ditridecyl phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-tert-butylphenyl) butane, 3,4,5,6-dibenzo-1,Examples include 2-oxaphospholane, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris(p-tolyl)phosphine, tris(p-nonylphenyl)phosphine, tris(naphthyl)phosphine, diphenyl(hydroxymethyl)phosphine, diphenyl(acetoxymethyl)phosphine, diphenyl(β-ethylcarboxyethyl)phosphine, tris(p-chlorophenyl)phosphine, tris(p-fluorophenyl)phosphine, benzyldiphenylphosphine, diphenyl(β-cyanoethyl)phosphine, diphenyl(p-hydroxyphenyl)phosphine, diphenyl(1,4-dihydroxyphenyl)-2-phosphine, phenylnaphthylbenzylphosphine, etc.

[0092] Examples of commercially available phosphorus-based antioxidants include Irgafos 168 (manufactured by BASF Japan Ltd., "Irgafos" is a registered trademark), Irgafos 12 (manufactured by BASF Japan Ltd.), Irgafos 38 (manufactured by BASF Japan Ltd.), Adeka Stab 2112 (manufactured by ADEKA Corporation, "Adeka Stab" is a registered trademark), Adeka Stab C (manufactured by ADEKA Corporation), Adeka Stab 329K (manufactured by ADEKA Corporation), Adeka Stab PEP36 (manufactured by ADEKA Corporation), JC263 (manufactured by Johoku Chemical Industry Co., Ltd., "JC263" is a registered trademark), Sandstab P-EPQ (manufactured by Clariant, "Sandstab" is a registered trademark), Weston 618 (manufactured by GE, "Weston" is a registered trademark), Weston619G (manufactured by GE), Weston 624 (manufactured by GE), Doverphos S-9228PC (manufactured by Dover Chemical, "Doverphos" is a registered trademark), etc.

[0093] In one embodiment, the content of component (C) can be 0.001 part by mass or more, 0.01 part by mass or more, or 0.05 part by mass or more, and can also be 1.0 part by mass or less, 0.5 part by mass or less, 0.4 part by mass or less, or 0.3 part by mass or less, based on 100 parts by mass of component (A). The larger the blending amount is above 0.001 part by mass, the more sufficient the antioxidant effect can be obtained. Also, the smaller the blending amount is below 1.0% by mass, the more the mold contamination during molding can be suppressed.

[0094] (Other components) The resin composition according to this aspect can contain other components other than the above-mentioned components (A) to (C) as long as the effects of the present invention are not impaired.

[0095] Examples of other components include rubber-like elastomers, mold release agents, hydrolysis-resistant agents, ultraviolet absorbers, flame retardants, flame retardant aids, reinforcing materials, fillers, dyes, and the like. In addition, the resin composition according to this aspect can contain an aromatic polycarbonate different from the component (A). The aromatic polycarbonate is produced, for example, by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor and a viscosity average molecular weight regulator, or by a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate. As the dihydric phenol, 2,2-bis(4-hydroxyphenyl)propane [commonly known as bisphenol A] is used, and it is preferable to contain a non-copolymerized homopolycarbonate obtained by using p-tert-butylphenol as the viscosity average molecular weight regulator because it is less likely to cause a decrease in the strength of the molded product due to the occurrence of weld lines during injection molding.

[0096] The resin composition according to this aspect may or may not contain a rubber-like elastomer as other components. Examples of the rubber-like elastomer include styrene-based thermoplastic elastomers. Examples of the styrene-based thermoplastic elastomers include styrene-ethylene·butylene-styrene copolymer, styrene-ethylene·propylene-styrene copolymer, styrene-ethylene·ethylene·propylene-styrene copolymer, styrene-butadiene-styrene triblock copolymer, styrene-isoprene-styrene triblock copolymer, styrene-hydrogenated butadiene diblock copolymer, styrene-hydrogenated isoprene diblock copolymer, styrene-butadiene diblock copolymer, styrene-isoprene diblock copolymer, and the like.

[0097] Due to the low content of the rubber-like elastomer in the resin composition according to this aspect, and further due to the substantial absence of the rubber-like elastomer, the effect of suppressing the decrease in rigidity and heat resistance is achieved. Such an effect is more significantly exhibited when the content of the styrene-ethylene / butylene-styrene block copolymer as the rubber-like elastomer is low, and further when the styrene-ethylene / butylene-styrene block copolymer is substantially absent.

[0098] In one embodiment, when the total of component (A) and component (B) is 100 parts by mass, the content of the rubber-like elastomer in the resin composition is less than 1.0 part by mass, 0.9 part by mass or less, 0.8 part by mass or less, 0.7 part by mass or less, 0.6 part by mass or less, 0.5 part by mass or less, less than 0.5 part by mass, or the resin composition substantially does not contain the rubber-like elastomer. Note that in the case of "substantially does not contain", it is possible to contain as unavoidable impurities.

[0099] In one embodiment, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, 99% by mass or more, 99.5% by mass or more or substantially 100% by mass of the resin composition is component (A) and component (B), or component (A), component (B) and component (C). In the case of "substantially 100% by mass", unavoidable impurities may be included.

[0100] The resin composition according to one aspect of the present invention can be obtained by blending and kneading the above-described respective components. The blending and kneading can be carried out by preliminarily mixing with commonly used equipment, for example, a ribbon blender, a drum tumbler, etc., and then using a method using a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a conical kneader, etc. The heating temperature during kneading is usually appropriately selected in the range of 240°C or higher and 320°C or lower. As this melt kneading, it is preferable to use an extruder, particularly a vented extruder. The resin composition can be in the form of, for example, pellets.

[0101] 2. Molded article The molded article according to one aspect of the present invention contains the resin composition according to one aspect of the present invention. Using the resin composition according to one aspect of the present invention (for example, in the form of pellets, etc.) as a raw material, various molded articles can be manufactured by injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, etc. In particular, it can be suitably used for manufacturing injection molded articles by injection molding and injection compression molding using pellets obtained by melt kneading.

[0102] Such molded articles can be suitably used, for example, as the exteriors and internal parts of parts for electric and electronic devices such as televisions, radios, cameras, video cameras, audio players, DVD players, air conditioners, mobile phones, smartphones, transceivers, displays, computers, tablet terminals, portable game devices, stationary game devices, wearable electronic devices, registers, calculators, copiers, printers, facsimiles, communication base stations, batteries, robots, etc., and as the exteriors and internal parts of automobiles, railways, ships, aircraft, space industry equipment, medical equipment, and parts of building materials.

[0103] 3. Method for improving the properties of the resin composition The method for improving the properties of the resin composition according to one aspect of the present invention is a method for improving the properties of a resin composition containing a polycarbonate block (A-1) composed of a repeating unit represented by the general formula (I) described above and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), wherein carbon fiber (B) having a compound having an epoxy group attached thereto is used as the carbon fiber (B).

[0104] In this aspect, for the resin composition, the description of the resin composition according to one aspect of the present invention is incorporated by reference.

[0105] The properties of the resin composition improved by this aspect can be one or more selected from the group consisting of, for example, flow length, Charpy impact strength, and flexural modulus. Preferably, all of the flow length, Charpy impact strength, and flexural modulus are improved. Since the required ranges of these properties can vary depending on the application, a method for improving the properties according to the application is required. By the method for improving the properties of the resin composition according to one aspect of the present invention, it becomes possible to adjust the balance of the properties required for various applications. Specifically, depending on the blending ratio of the resin, which is a PC-POS copolymer, and carbon fiber, the balance of these properties can be adjusted in a state where the flow length (fluidity), Charpy impact strength, and flexural modulus are favorably balanced. The blending ratio ((A):(B)) based on the mass of the PC-POS copolymer (A) and carbon fiber (B) in the resin composition can be 95 to 35:5 to 65, 90 to 40:10 to 60, 85 to 40:15 to 60, 85 to 55:15 to 45, or 80 to 60:20 to 40. By setting it within this range, the flow length (fluidity), Charpy impact strength, and flexural modulus can be favorably balanced, and the properties can be further improved according to the application.

[0106] In this aspect, "the flow length is improved" means that the flow length measured by the method described in the examples becomes larger. "The Charpy impact strength is improved" means that the Charpy impact strength measured by the method described in the examples becomes larger. "The flexural modulus is improved" means that the flexural modulus measured by the method described in the examples becomes larger.

Examples

[0107] Examples of the present invention will be described below, but the present invention is not limited to such examples. In the following description, polydimethylsiloxane may sometimes be referred to as "PDMS".

[0108] 1. Measurement method The property values in each example were measured according to the following procedure.

[0109] (1) Average chain length n and content of polyorganosiloxane block (A-2) The average chain length n and content of the polyorganosiloxane block (A-2) were calculated by the integral value ratio of the methyl groups of polydimethylsiloxane through NMR measurement. This will be described in detail below.

[0110] <Quantification method for average chain length n of polyorganosiloxane block (A-2)> 1 H-NMR measurement conditions NMR apparatus: ECA-500 manufactured by JEOL RESONANCE, Ltd. Probe: 50TH5AT / FG2 Observation range: -5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° NMR sample tube: 5φ Sample amount: 30 - 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature Number of integrations: 256 times In the case of allylphenol-terminated polydimethylsiloxane A: Integral value of the methyl groups of the dimethylsiloxane part observed around δ -0.02 to 0.5 B: Integral value of the methylene groups of allylphenol observed around δ 2.50 to 2.75 Average chain length n of polydimethylsiloxane = (A / 6) / (B / 4) In the case of eugenol-terminated polydimethylsiloxane A: Integral value of the methyl groups of the dimethylsiloxane part observed around δ -0.02 to 0.5 B: Integral value of the methylene groups of eugenol observed around δ 2.40 to 2.70 Average chain length n of polydimethylsiloxane = (A / 6) / (B / 4)

[0111] <Quantification method for content of polyorganosiloxane block (A-2)> Quantification method of the amount of polydimethylsiloxane copolymerized in p-tert-butylphenol (PTBP) - terminated polycarbonate copolymerized with allylphenol - terminated polydimethylsiloxane NMR apparatus: ECA - 500 manufactured by JEOL RESONANCE Co., Ltd. Probe: 50TH5AT / FG2 Observation range: - 5 to 15 ppm Observation center: 5 ppm Pulse repetition time: 9 seconds Pulse width: 45° Number of integrations: 256 times NMR sample tube: 5φ Sample amount: 30 - 40 mg Solvent: deuterated chloroform Measurement temperature: room temperature A: Integration value of the methyl group of the BPA part observed around δ1.5 - 1.9 B: Integration value of the methyl group of the dimethylsiloxane part observed around δ - 0.02 - 0.3 C: Integration value of the butyl group of the p - tert - butylphenyl part observed around δ1.2 - 1.4 a = A / 6 b = B / 6 c = C / 9 T = a + b + c f = a / T×100 g = b / T×100 h = c / T×100 TW = f×254 + g×74.1 + h×149 PDMS (mass%) = g×74.1 / TW×100

[0112] (2) Viscosity - average molecular weight The viscosity - average molecular weight (Mv) was measured by using an Ubbelohde viscometer to measure the viscosity of a methylene chloride solution at 20°C, and the intrinsic viscosity [η] was obtained therefrom and calculated by the following formula (Schnell formula). [η]=1.23×10 -5 ×Mv 0.83

[0113] (3) Flow length (flow characteristics) The pellets obtained in each example were used to produce spiral molded products with a wall thickness of 2 mm and a width of 10 mm using an injection molding machine at a cylinder temperature of 320 °C, a mold temperature of 95 °C, and an injection pressure of 80 Mpa, and the flow length (spiral flow length) was measured. A larger numerical value indicates better fluidity.

[0114] (4) Charpy impact strength Using the pellets obtained in each example, notched and unnotched test pieces with a wall thickness of 4 mm were produced, and the Charpy impact strength of each test piece was measured in accordance with ISO 179-1:2010. A larger numerical value indicates better impact strength.

[0115] (5) Flexural modulus Using the pellets obtained in each example, test pieces with a wall thickness of 4 mm were produced, a flexural test was performed in accordance with ISO 178:2001, and the flexural modulus was measured. A larger numerical value indicates better flexural properties.

[0116] 2. Components The components used in each example are as follows.

[0117] (1) Resin A1: Polycarbonate - polyorganosiloxane copolymer produced by Production Examples 1 and 2 described below A’1: Homopolycarbonate (“Tafron FN1700” manufactured by Idemitsu Kosan Co., Ltd., homopolycarbonate produced from bisphenol A, viscosity average molecular weight = 17,700) A’2: Homopolycarbonate (“Tafron FN2200” manufactured by Idemitsu Kosan Co., Ltd., homopolycarbonate produced from bisphenol A, viscosity average molecular weight = 21,300)

[0118] (2) Carbon fiber B1: Carbon fiber treated (coated) with an epoxy (special epoxy) - based sizing agent (“Pyrofil (registered trademark) Chopped Fiber TR06Q” manufactured by Mitsubishi Rayon Co., Ltd.) B2: Carbon fibers treated (coated) with an epoxy sizing agent (Mitsubishi Rayon Co., Ltd.'s "Pyrofil (registered trademark) Chopped Fiber TR066A") B’1: Carbon fibers treated (coated) with a urethane sizing agent (Mitsubishi Rayon Co., Ltd.'s "Pyrofil (registered trademark) Chopped Fiber TR06U") B’2: Carbon fibers treated (coated) with a polyamide sizing agent (Mitsubishi Rayon Co., Ltd.'s "Pyrofil (registered trademark) Chopped Fiber TR06NE")

[0119] (3) Antioxidant Phosphorus-based antioxidant ("Doverphos (registered trademark) S9228PC" manufactured by Dover Chemical Co.)

[0120] (Production Example 1) Production of polycarbonate oligomer Sodium dithionite at 2000 ppm was added to an aqueous sodium hydroxide solution of 5.6 mass%. BPA was dissolved therein so that the BPA concentration became 13.5 mass% to prepare an aqueous sodium hydroxide solution of BPA.

[0121] This aqueous sodium hydroxide solution of BPA, methylene chloride at 15 L / hr, and phosgene at 4.0 kg / hr were continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 L / hr. The tubular reactor had a jacket part, and cooling water was passed through the jacket to keep the temperature of the reaction solution at 40°C or lower. The reaction solution exiting the tubular reactor was continuously introduced into a baffled tank reactor with an internal volume of 40 L equipped with a retreating blade, and an aqueous sodium hydroxide solution of BPA at 2.8 L / hr, a 25 mass% aqueous sodium hydroxide solution at 0.07 L / hr, water at 17 L / hr, and a 1 mass% aqueous triethylamine solution at 0.64 L / hr were further added thereto to conduct the reaction. The reaction solution overflowing from the tank reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.

[0122] The polycarbonate oligomer thus obtained had a concentration of 341 g / L and a chloroformate group concentration of 0.71 mol / L.

[0123] (Production Example 2) Production of polycarbonate-polyorganosiloxane copolymer (A1) Into a 50 L tank-type reactor equipped with a baffle plate, paddle-type stirring blades, and a cooling jacket, 15 L of the polycarbonate oligomer solution produced in Production Example 1 above, 10.1 L of methylene chloride, 407 g of o-allylphenol-terminated polydimethylsiloxane (PDMS) with an average chain length n of 88 of polydimethylsiloxane (polyorganosiloxane block (A-2)), and 8.4 mL of triethylamine were charged. With stirring, 1065 g of an aqueous sodium hydroxide solution prepared by dissolving 85 g of sodium hydroxide in 980 mL of pure water was added thereto, and the reaction between the polycarbonate oligomer and allylphenol-terminated PDMS was carried out for 20 minutes.

[0124] To this polymerization solution, a methylene chloride solution of p-tert-butylphenol (PTBP) (prepared by dissolving 70.4 g of PTBP in 1.0 L of methylene chloride) and an aqueous sodium hydroxide solution of bisphenol A (prepared by dissolving 1093 g of bisphenol A in an aqueous solution prepared by dissolving 618 g of sodium hydroxide and 2.1 g of sodium dithionite in 9.0 L of pure water) were added, and a polymerization reaction was carried out for 40 minutes.

[0125] For dilution, 13 L of methylene chloride was added and stirred for 20 minutes. Then, it was separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer (PC-PDMS copolymer) and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was isolated.

[0126] The methylene chloride solution of the PC-PDMS copolymer thus obtained was successively washed with a 15% by volume aqueous solution of 0.03 mol / L sodium hydroxide and 0.2 mol / L hydrochloric acid, and then washed repeatedly with pure water until the electrical conductivity in the aqueous phase after washing became 5 μS / cm or less.

[0127] The methylene chloride solution of the PC-PDMS copolymer obtained by washing was concentrated and pulverized, and the resulting flakes were dried at 120 °C under reduced pressure to produce a PC-PDMS copolymer (A1).

[0128] The content of the PDMS block (polyorganosiloxane block (A-2)) determined by nuclear magnetic resonance (NMR) of the obtained PC-PDMS copolymer (A1) was 6.0% by mass, and the viscosity average molecular weight Mv was 17,700.

[0129] 3. Resin composition (Examples 1, 2 and Comparative Examples 1 to 5) The above-mentioned components were blended in the blending amounts shown in Table 1, and pellets of the resin composition were produced at a cylinder temperature of 300 °C using a twin-screw extruder (ZSK type twin-screw extruder manufactured by Coperion). Using the obtained pellets, the above-mentioned respective characteristic values were measured. The results are shown in Table 1.

[0130]

Table 1

[0131] <Evaluation> From Table 1, it can be seen that according to the resin composition according to the examples, the flow length (fluidity), Charpy impact strength, and flexural modulus can be favorably balanced.

[0132] (Examples 3 to 5) Blending ratio of resin and carbon fiber The above-mentioned components were blended in the blending amounts shown in Table 2, and pellets of the resin composition were produced at a cylinder temperature of 300 °C using a twin-screw extruder (TEM-37SS manufactured by Shibaura Machine Co., Ltd.). Using the obtained pellets, the above-mentioned respective characteristic values were measured. The results, together with the results of Example 1, are shown in Table 2.

[0133]

Table 2

[0134] <Evaluation> From Table 2, according to the resin composition according to the examples, it can be seen that by the blending ratio of the resin which is a PC-POS copolymer and carbon fiber, the balance of these properties can be adjusted in a state where the flow length (fluidity), Charpy impact strength and flexural modulus are favorably balanced. Specifically, it can be seen that by increasing the blending amount of carbon fiber with respect to the resin, although the flow length (fluidity) and Charpy impact strength decrease, the flexural modulus can be further improved. Also, from another point of view, it can be seen that by decreasing the blending amount of carbon fiber with respect to the resin, although the flexural modulus decreases, the flow length (fluidity) and Charpy impact strength can be further improved.

[0135] Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art can easily make many changes to these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. Therefore, many of these changes are included in the scope of the present invention. All of the documents described in this specification and the contents of the application that form the basis of the priority under the Paris Convention of this application are incorporated by reference.

Claims

1. A polycarbonate - polyorganosiloxane copolymer (A) comprising a polycarbonate block (A - 1) composed of repeating units represented by the following general formula (I) and a polyorganosiloxane block (A - 2) containing repeating units represented by the following general formula (II), carbon fiber (B), and the resin composition, wherein the carbon fiber (B) is a carbon fiber to which a compound having an epoxy group is attached, the resin composition, wherein 80% by mass or more of the resin composition is the polycarbonate - polyorganosiloxane copolymer (A) and the carbon fiber (B). 【Chemical formula 16】 (In the above formula (I), R １ and R ２ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. a and b each independently represent an integer of 0 to 4. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ２ -, -O- or -CO-. In the above formula (II), R ３ and R ４ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.)

2. The resin composition according to claim 1, comprising 10 to 200 parts by mass of the carbon fiber (B) with respect to 100 parts by mass of the polycarbonate - polyorganosiloxane copolymer (A).

3. The resin composition according to claim 1 or 2, further comprising an antioxidant (C).

4. The resin composition according to claim 3, comprising at least one selected from the group consisting of a phosphorus-based antioxidant and a phenol-based antioxidant as the antioxidant (C).

5. The resin composition according to claim 3 or 4, comprising 0.001 part by mass to 1.0% by mass of the antioxidant (C) with respect to 100 parts by mass of the polycarbonate-polyorganosiloxane copolymer (A).

6. The resin composition according to any one of claims 1 to 5, wherein the average chain length n of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 20 to 500.

7. The resin composition according to any one of claims 1 to 6, wherein the content of the polyorganosiloxane block (A-2) in the polycarbonate-polyorganosiloxane copolymer (A) is 0.1 to 45% by mass.

8. A molded article comprising the resin composition according to any one of claims 1 to 7.

9. A polycarbonate-polyorganosiloxane copolymer (A) comprising a polycarbonate block (A-1) composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II), carbon fiber (B), and A method for improving the properties of a resin composition, comprising: using carbon fiber with a compound having an epoxy group attached thereto as the carbon fiber (B), and a method wherein 80% by mass or more of the resin composition is the polycarbonate-polyorganosiloxane copolymer (A) and the carbon fiber (B). 【Chemical Formula 17】 (In the above formula (I), R １ and R ２ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. a and b each independently represent an integer from 0 to 4. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ２ -, -O- or -CO-. In the formula (II), R ３ and R ４ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. ) Claim 10 The property is one or more selected from the group consisting of flow length, Charpy impact strength and flexural modulus, and the method according to claim 9.

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