Polycarbonate resin composition and molded article

Abstract

To provide a polycarbonate resin composition having good molding appearance with reduced black spots and remarkably improved low-temperature impact resistance.SOLUTION: There is provided a polycarbonate resin composition which comprises (B) 0.3 to 2.5 pts.wt. of a fluororesin (B component) containing a polymerization unit represented by the following general formula [4] or a polymerization unit represented by the following general formula [4] and a polymerization unit represented by the following general formula [5] based on (A) 100 pts.wt. of a resin component (A component) comprising (A-1) 1 to 100 pts.wt. of a polycarbonate-polydiorganosiloxane copolymer comprising a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3] and (A-2) 0 to 99 pts.wt. of an aromatic polycarbonate resin comprising a polycarbonate block represented by the following general formula [1].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polycarbonate resin composition and a molded article. More specifically, the present invention relates to a polycarbonate resin composition and a molded article molded therefrom that have a good molded appearance with reduced black spots and dramatically improved low-temperature impact resistance due to the use of a specific polycarbonate-polydiorganosiloxane copolymer and a specific fluororesin. [Background technology]

[0002] Polycarbonate resins are used in a wide range of applications, including machine parts, automobile parts, electrical and electronic components, and office equipment components, due to their excellent properties, such as mechanical strength, dimensional stability, and flame retardancy. Due to their impact resistance, they are often used as housings and exterior components for various devices. However, as their applications expand, their usage environments become more diverse, requiring them to perform satisfactorily outdoors, at temperatures as low as -30°C, and even when exposed to paint or chemicals. For example, they have not achieved sufficient performance as materials for outdoor electrical and electronic storage boxes, such as telecommunications boxes, and solar power generation junction boxes, which require extremely high impact resistance. A polycarbonate-based resin known as a polycarbonate-polydiorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer") exhibits high low-temperature impact resistance (Patent Document 1). Polycarbonate-polydiorganosiloxane copolymers have superior low-temperature impact resistance and flame retardancy compared to conventional polycarbonate resins. Attempts have been made to improve low-temperature impact resistance by appropriately selecting the polydiorganosiloxane (hereinafter sometimes abbreviated as "POS") skeleton and production method used and controlling the POS aggregation domain state (Patent Documents 2 and 3). Methods for improving low-temperature impact resistance by blending a rubber-like elastomer or polyolefin with a PC-POS copolymer have also been disclosed (Patent Documents 4 and 5), but the low-temperature impact resistance remains insufficient. Meanwhile, a polycarbonate-polydiorganosiloxane copolymer using a long-chain POS with a large POS repeat number has been disclosed as a method for improving low-temperature impact resistance (Patent Document 2). However, this often results in poor molded appearance, such as black spots and associated black discoloration, leading to poor aesthetics and uneven coloring, making it difficult to use as an exterior material. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-247195 [Patent Document 2] Special Publication No. 2006-523243 [Patent Document 3] WO91 / 00885 publication [Patent Document 4] Japanese Patent Application Publication No. 4-225060 [Patent Document 5] WO2016 / 088861 publication Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a polycarbonate resin composition and a molded article thereof which have a good molded appearance with reduced black particles and which have significantly improved low-temperature impact resistance. [Means for solving the problem]

[0005] As a result of extensive research to solve the above problems, the present inventors have discovered that the above problems can be solved by the following configuration, and have arrived at the present invention.

[0006] (Configuration 1) (A) A polycarbonate resin composition containing 100 parts by weight of a resin component (A component) consisting of (A-1) 1 to 100 parts by weight of a polycarbonate-polydiorganosiloxane copolymer consisting of a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3] and (A-2) 0 to 99 parts by weight of an aromatic polycarbonate resin consisting of a polycarbonate block represented by the following general formula [1], and (B) 0.3 to 2.5 parts by weight of a fluororesin (B component) containing polymerization units represented by the following general formula [4] or polymerization units represented by the following general formula [4] and polymerization units represented by the following general formula [5]:

[0007] [ka]

[0008] [(In the above general formula [1], R 1 and R 2each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are multiple of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W represents a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]:

[0009] [ka]

[0010] (In the above general formula [2], R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of groups, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7.)

[0011] [ka]

[0012] (In the above general formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number of 50 to 120. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0013] [ka]

[0014] (In the above general formula [4], R f 1 , R f 2 , R f 3 and R f 4 each independently represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except when all of them are fluorine atoms.

[0015] [ka]

[0016] (Configuration 2) The polycarbonate resin composition according to the above-mentioned configuration 1, characterized in that p+q in the above-mentioned formula [3] is 50 to 70.

[0017] (Configuration 3) 3. The polycarbonate resin composition according to the above-mentioned configuration 1 or 2, wherein the content of the polydiorganosiloxane block represented by the above formula [3] in the component A-1 is 4 to 20% by weight.

[0018] (Configuration 4) 4. The polycarbonate resin composition according to any one of the above configurations 1 to 3, wherein the content of the polydiorganosiloxane block represented by the above formula [3] in component A is 2.5 to 6.5% by weight.

[0019] (Configuration 5) 5. The polycarbonate resin composition according to any one of the above configurations 1 to 4, wherein the viscosity average molecular weight of component A-1 is 11,000 to 30,000.

[0020] (Configuration 6) 6. The polycarbonate resin composition according to any one of the above configurations 1 to 5, which satisfies (i) to (iii). (i) In the cross-sectional image of component A observed using an electron microscope, the area is 850 nm square (722,500 nm 2 ) there are 1 to 20 domains with a maximum diameter of 80 nm or more. (ii) The average domain size is 30 to 100 nm. (iii) In the cross-sectional observation images of component A using an electron microscope, all five sample sections had an 850 nm square (722,500 nm 2 ) there are no domains with a maximum diameter of 400 nm or more.

[0021] (Configuration 7) The polycarbonate resin composition according to any one of the above-mentioned configurations 1 to 6, wherein the polydiorganosiloxane block represented by the above-mentioned formula [3] is a polydiorganosiloxane block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane.

[0022] (Configuration 8) R in the above formula [3]3 , R 4 , R 5 , R 6 , R 7 and R 8 8. The polycarbonate resin composition according to any one of the above configurations 1 to 7, wherein is a methyl group.

[0023] (Configuration 9) 9. The polycarbonate resin composition according to any one of the above configurations 1 to 8, wherein the polycarbonate block represented by the above formula [1] is a polycarbonate block derived from 2,2-bis(4-hydroxyphenyl)propane.

[0024] (Configuration 10) 10. The polycarbonate resin composition according to any one of the above configurations 1 to 9, wherein the melting point of component B is 170 to 280°C.

[0025] (Configuration 11) In the above formula [4], R f 1 , R f 2 , R f 3 is a fluorine atom, and R f 4 11. The polycarbonate resin composition according to any one of the above configurations 1 to 10, wherein is a fluoromethyl group.

[0026] (Configuration 12) In the above formula [4], R f 1 , R f 2 , R f 3 and R f 4 11. The polycarbonate resin composition according to any one of the above configurations 1 to 10, wherein is a hydrogen atom.

[0027] (Configuration 13) The L measured in accordance with JIS Z 8781-4 for molded products obtained by 25 shots of continuous molding at a molding temperature of 280°C. *Maximum color difference ΔL of the value * 13. The polycarbonate resin composition according to any one of the above configurations 1 to 12, wherein the value of [Delta] is 3 or less.

[0028] (Configuration 14) 14. The polycarbonate resin composition according to any one of the above configurations 1 to 13, characterized in that it contains 0.001 to 20 parts by weight of a flame retardant (C) (Component C) per 100 parts by weight of Component A.

[0029] (Configuration 15) 15. The polycarbonate resin composition according to any one of the above configurations 1 to 14, characterized in that it contains 0.01 to 5 parts by weight of (D) a fluorinated anti-dripping agent (Component D) per 100 parts by weight of Component A.

[0030] (Configuration 16) 16. A molded article formed from the polycarbonate resin composition according to any one of the above items 1 to 15. [Effects of the Invention]

[0031] The polycarbonate resin composition of the present invention has excellent low-temperature impact resistance and a molded appearance free from black discoloration due to black particles, and is therefore suitable for use as a material for outdoor structural members for cold climates, various housing members, and automobile-related parts. It is also useful for various electronic and electrical device parts, camera parts, office automation device parts, precision machinery parts, machinery parts, vehicle parts, and other applications, such as agricultural materials, transport containers, play equipment, and miscellaneous goods, and its industrial effects are exceptional. DETAILED DESCRIPTION OF THE INVENTION

[0032] (Component A: resin component) The resin component of the present invention comprises 1 to 100 parts by weight of a polycarbonate-polydiorganosiloxane copolymer (A-1) and 0 to 99 parts by weight of an aromatic polycarbonate resin (A-2).

[0033] (Component A-1: ​​Polycarbonate-polydiorganosiloxane copolymer) In the present invention, the polycarbonate-polydiorganosiloxane copolymer (hereinafter sometimes abbreviated as PC-POS copolymer) is a polycarbonate-polydiorganosiloxane copolymer comprising a polycarbonate block represented by formula [1] and a polydiorganosiloxane block represented by formula [3]. <Polycarbonate block represented by formula [1]> In the present invention, the polycarbonate block is represented by the following formula [1].

[0034] [ka]

[0035] In the above formula [1], R 1 and R 2 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group, and when there are multiple of each, they may be the same or different.

[0036] Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and octoxy groups. Preferred are alkoxy groups having 1 to 6 carbon atoms. Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. Preferred are cycloalkyl groups having 6 to 12 carbon atoms. Examples of cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyloxy groups. Preferred are cycloalkyl groups having 6 to 12 carbon atoms. Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred. Examples of aryl groups having 6 to 14 carbon atoms include phenyl and naphthyl groups. Examples of aryloxy groups having 6 to 14 carbon atoms include phenyloxy and naphthyloxy groups. Examples of aralkyl groups having 7 to 20 carbon atoms include benzyl and phenylethyl groups. Examples of aralkyloxy groups having 7 to 20 carbon atoms include benzyloxy and phenylethyloxy groups. e and f each independently represent an integer of 1 to 4.

[0037] W is a single bond or at least one group selected from the group consisting of groups represented by the following formula [2]:

[0038] [ka]

[0039] In the above formula [2], R 11 , R 12 , R 13 , R 14 , R 15 , R16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.

[0040] Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of aryl groups having 6 to 14 carbon atoms include phenyl and naphthyl groups. These may be substituted. Examples of substituents include alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and butyl groups. Examples of aralkyl groups having 7 to 20 carbon atoms include benzyl and phenylethyl groups.

[0041] R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group, and when there are a plurality of such groups, they may be the same or different.

[0042] Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkyl groups having 1 to 18 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and tetradecyl groups. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. Preferred are alkoxy groups having 1 to 6 carbon atoms. Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. Preferred are cycloalkyl groups having 6 to 12 carbon atoms. Examples of cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyl groups. Preferred are cycloalkyl groups having 6 to 12 carbon atoms. Examples of alkenyl groups having 2 to 10 carbon atoms include methenyl, ethenyl, propenyl, butenyl, and pentenyl groups. Alkenyl groups having 2 to 6 carbon atoms are preferred. Examples of aryl groups having 6 to 14 carbon atoms include phenyl and naphthyl groups. Examples of aryloxy groups having 6 to 14 carbon atoms include phenyloxy and naphthyloxy groups. Examples of aralkyl groups having 7 to 20 carbon atoms include benzyl and phenylethyl groups. Examples of aralkyloxy groups having 7 to 20 carbon atoms include benzyloxy and phenylethyloxy groups.

[0043] g is an integer of 1 to 10, preferably an integer of 1 to 6. h is an integer of 4 to 7, preferably an integer of 4 to 5.

[0044] The polycarbonate block represented by the formula [1] is preferably a polycarbonate block derived from 2,2-bis(4-hydroxyphenyl)propane.

[0045] The length of the polycarbonate block is preferably 10 to 100, more preferably 30 to 100, and even more preferably 50 to 70, in terms of the average number of repeating units of the formula [1].

[0046] The content of the polycarbonate block represented by formula [1] is preferably 50 to 99.9% by weight, more preferably 70 to 99.5% by weight, and even more preferably 80 to 99.0% by weight, based on the total weight of the copolymer.

[0047] <Polydiorganosiloxane block represented by formula [3]> In the present invention, the polydiorganosiloxane block is represented by the following formula [3].

[0048] [ka]

[0049] In the above formula [3], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

[0050] Examples of alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl groups. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of substituted or unsubstituted aryl groups having 6 to 12 carbon atoms include phenyl and naphthyl groups. Examples of substituents include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups. R 3 , R 4 , R 5 , R 6 , R 7 and R 8 is preferably a methyl group.

[0051] R 9 and R 10are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

[0052] Examples of halogen atoms include fluorine atoms, chlorine atoms, and bromine atoms. Examples of alkyl groups having 1 to 10 carbon atoms include methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups, and dodecyl groups. Preferred are alkyl groups having 1 to 6 carbon atoms. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy groups, ethoxy groups, propoxy groups, butoxy groups, pentoxy groups, hexoxy groups, heptoxy groups, and octoxy groups. Preferred are alkoxy groups having 1 to 6 carbon atoms.

[0053] X is a divalent aliphatic group having 2 to 8 carbon atoms. Examples of the divalent aliphatic group include alkylene groups having 2 to 8 carbon atoms. Examples of the alkylene group include an ethylene group, a trimethylene group, and a tetramethylene group.

[0054] The polydiorganosiloxane block represented by the formula [3] is preferably a polydiorganosiloxane block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane. That is, in the formula [3], X is a trimethylene group and R 9 and R 10 is a hydrogen atom, or X is a trimethylene group and R 9 and R 10 is preferably a methoxy group.

[0055] The content of the polydiorganosiloxane block represented by the above formula [3] is preferably 4 to 20% by weight, more preferably 8 to 15% by weight, and even more preferably 12 to 15% by weight, based on the total weight of the polycarbonate-polydiorganosiloxane copolymer. If the content is less than the lower limit, maximum domain formation may be insufficient and low-temperature impact resistance may not be achieved. If the content is more than the upper limit, significant problems may arise in terms of production, such as poor polymerization reaction due to a deterioration in the emulsification state or difficulty in granulation due to an excessively low glass transition temperature.

[0056] The viscosity-average molecular weight of component A-1 is preferably 11,000 to 30,000, more preferably 13,000 to 25,000, even more preferably 15,000 to 20,000, and particularly preferably 15,000 to 18,000. If the viscosity-average molecular weight of component A-1 is below the lower limit, it may be difficult to obtain practical mechanical strength in many fields, and the difference in melt viscosity from the polycarbonate resin (component A-2) to be mixed may be large, resulting in poor kneadability. If the viscosity-average molecular weight is above the upper limit, the melt viscosity will be high and high molding temperatures will generally be required, which may result in problems such as thermal degradation of the resin or reduced productivity due to poor separation in the water washing step during production.

[0057] p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number of 50 to 120. The average chain length p+q is preferably a natural number of 50 to 100, more preferably a natural number of 50 to 70, and even more preferably a natural number of 60 to 70. If the average chain length p+q is less than 50, sufficient low-temperature impact resistance is not exhibited, and if it is more than 120, poor marble-like appearance and surface peeling occur.

[0058] (Aromatic polycarbonate resin (A-2)) The aromatic polycarbonate resin (A-2) in the present invention is derived from a dihydric phenol (I) represented by the general formula [6].

[0059] [ka]

[0060] (In the above general formula [6], R 1 , R 2 , e, f and W are the same as in equation [1].) Examples of the dihydric phenol include 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 2,2-bis(4-hydroxy-3,3'-biphenyl)propane, 2,2-bis(4-hydroxy- 2,2-bis(3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) 1,1-bis(4-hydroxyphenyl)methane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl -4,4'-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis(4-hydroxyphenyl)cyclohexane, 1,3-bis(4-hydroxyphenyl)cyclohexane, 4,8-bis(4-hydroxyphenyl)tricyclo[5.2.1.02,6]decane, 4,4'-(1,3-adamantanediyl)diphenol, and 1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

[0061] Among these, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 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)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene are preferred, and 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are particularly preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is the most suitable due to its excellent strength and durability. These may be used alone or in combination of two or more.

[0062] The component A of the present invention comprises 100 to 1 part by weight of a polycarbonate-polydiorganosiloxane copolymer (A-1) and 0 to 99 parts by weight of an aromatic polycarbonate resin (A-2), preferably 90 to 10 parts by weight of component A-1 and 10 to 90 parts by weight of component A-2, and more preferably 50 to 20 parts by weight of component A-1 and 50 to 80 parts by weight of component A-2. If the component A-1 is less than 1 part by weight, sufficient low-temperature impact resistance will not be achieved.

[0063] The content of the polydiorganosiloxane block in the present invention is preferably 2.5 to 6.5% by weight, more preferably 3.0 to 6.0% by weight, and even more preferably 3.5 to 5.5% by weight, based on the total weight of component A. If the content is less than the lower limit, sufficient low-temperature impact resistance may not be exhibited, while if it is more than the upper limit, poor appearance due to black discoloration caused by black particles or a marbled appearance may easily occur, and thermomechanical properties may also be reduced.

[0064] The viscosity average molecular weight of component A is preferably 11,000 to 30,000, and more preferably 12,000 to 25,000. If it is less than 11,000, sufficient low-temperature impact resistance may not be exhibited, and if it is greater than the upper limit, an increase in solution viscosity may result in reduced productivity or insufficient molding flowability.

[0065] (Domain size of polydiorganosiloxane) The PC-POS copolymer of the present invention has an aggregate structure in which polydiorganosiloxane domains are dispersed in a polycarbonate polymer matrix.

[0066] In the present invention, the polydiorganosiloxane domain refers to a domain primarily composed of polydiorganosiloxane dispersed in a polycarbonate matrix, and may contain other components. As described above, the polydiorganosiloxane domain does not necessarily consist of a single component because its structure is formed by phase separation from the polycarbonate matrix.

[0067] The maximum major axis, average domain size, distribution, and dispersion state of the polydiorganosiloxane domains of component A in the present invention were measured using an electron microscope (hereinafter sometimes abbreviated as TEM) to determine the area of ​​850 nm square (722,500 nm 2) is evaluated in a cross-sectional observation image of the resin composition. In the present invention, the terms "maximum major axis of domains" and "average domain size" refer to measurements obtained by cutting thin slices from a 4.0 mm thick molded piece formed by injection molding and observing them with a TEM. The average domain size of polydiorganosiloxane domains refers to the number average value of the individual domain sizes.

[0068] Specifically, a 10mm wide, 80mm long, and 4.0mm thick injection-molded specimen was microtomed at room temperature, 15mm from the gate. The specimen was then observed at 20,000x magnification using a TEM. The resulting TEM images were analyzed using WinROOF Ver. 6.6 (Mitani Corporation) image analysis software to determine the average size and particle size distribution (frequency distribution) of the polydiorganosiloxane domains in the specimen. The maximum major axis (the length between any two points on the particle's outer contour that maximizes the distance between them) was used to determine the size of each domain. Five specimens were analyzed in the same way, and the average was used for each sample.

[0069] The average size of the polydiorganosiloxane domains in the present invention is preferably 30 to 100 nm, more preferably 40 to 80 nm, and even more preferably 50 to 70 nm. If the average size is below the lower limit of this range, impact resistance may not be sufficiently exhibited, while if it exceeds the upper limit of this range, poor appearance due to black discoloration caused by black particles or poor marbled appearance may be more likely to occur.

[0070] In the present invention, in a cross-sectional observation image of component A using a TEM, 2) preferably 1 to 20, more preferably 2 to 20, even more preferably 4 to 20, and particularly preferably 5 to 20 polydiorganosiloxane domains with a maximum diameter of 80 nm or more are present. If there is not even one polydiorganosiloxane domain with a maximum diameter of 80 nm or more, sufficient low-temperature impact resistance may not be exhibited, and if there are more than 20 polydiorganosiloxane domains, poor appearance due to black discoloration or marbled appearance may easily occur. Furthermore, in the present invention, polydiorganosiloxane domains with a maximum diameter of 400 nm or more are present in an area of ​​850 nm square (722,500 nm 2 If one or more polydiorganosiloxane domains having a maximum diameter of 400 nm or more are present, the appearance may be adversely affected by significant black spots, such as black discoloration or marbled appearance.

[0071] (Polydiorganosiloxane) In the present invention, a polydiorganosiloxane having a specific average chain length and represented by the following general formula [7], hydroxyaryl-terminated polydiorganosiloxane (II), is used as a raw material.

[0072] [ka]

[0073] (In the above general formula [7], R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number of 50 to 120. X is a divalent aliphatic group having 2 to 8 carbon atoms.

[0074] The average chain length p+q is preferably a natural number from 50 to 100, more preferably a natural number from 50 to 70, and particularly preferably a natural number from 60 to 70. If the average chain length p+q is less than 50, sufficient low-temperature impact resistance is not achieved, and if it is greater than 120, poor marbled appearance and surface peeling occur. To satisfy this specific chain length range, the composition may be prepared by mixing two or more different hydroxyaryl-terminated polydiorganosiloxane (II) raw materials having average chain lengths p+q. In this case, it is preferable to use as raw materials a polydiorganosiloxane (E-1) having an average chain length p+q of 1 or more but less than 60 and a polydiorganosiloxane (E-2) having an average chain length p+q of 60 or more but less than 200. The polydiorganosiloxane raw material may be prepared by mixing appropriate hydroxyaryl-terminated polydiorganosiloxane raw materials together, or by premixing polydiorganosiloxane precursors having an appropriate average chain length before hydroxyaryl-terminus modification, and then modifying the ends with hydroxyaryl. The average chain length p+q is calculated by nuclear magnetic resonance (NMR) measurement.

[0075] When the polydiorganosiloxane (E-1) and the polydiorganosiloxane (E-2) are mixed, the weight ratio of (E-1):(E-2) is preferably 1:99 to 99:1, and more preferably 10:90 to 90:10.

[0076] It is more preferable to use, as the polydiorganosiloxane raw material, polydiorganosiloxane (E) obtained by previously blending the above-mentioned polydiorganosiloxanes (E-1) and (E-2). The blending ratio is preferably 1:99 to 99:1 by weight, similar to the above-mentioned (E-1):(E-2) weight ratio, and more preferably 10:90 to 90:10.

[0077] When pre-blended, the lower limit of the average chain length p+q of the polydiorganosiloxane (E-1) is preferably 1 or more, more preferably 20 or more, and even more preferably 30 or more, and the upper limit is preferably less than 60, more preferably less than 50, and even more preferably less than 45. The lower limit of the average chain length p+q of the polydiorganosiloxane (E-2) is preferably 60 or more, more preferably 70 or more, and even more preferably 90 or more, and the upper limit is preferably 200 or less, more preferably 100 or less. As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by general formula [7], for example, the following compounds are suitably used.

[0078] [ka]

[0079] The hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, and is easily produced by subjecting the terminal of a polysiloxane chain having a predetermined degree of polymerization to a hydrosilylation reaction with, preferably, vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. Among these, (2-allylphenol)-terminated polydiorganosiloxane and (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane are preferred, and (2-allylphenol)-terminated polydimethylsiloxane and (2-methoxy-4-allylphenol)-terminated polydimethylsiloxane are particularly preferred.

[0080] <Method for producing polycarbonate-polydiorganosiloxane copolymer> The polycarbonate-polydiorganosiloxane copolymer of the present invention can be produced by steps (i) and (ii).

[0081] (Step (i)) Step (i) is a step of reacting a dihydric phenol (I) represented by the following formula [6] with phosgene in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution to prepare a solution containing a carbonate oligomer having a terminal chloroformate group.

[0082] [ka]

[0083] (In the formula, R 1 , R 2 , e, f and W are the same as above.) Preferred examples of the dihydric phenol (I) represented by the formula [6] include 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 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)-3,3,5-trimethylcyclohexane, 4,4'-sulfonyldiphenol, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, and 1,4-bis{2-(4-hydroxyphenyl)propyl}benzene.

[0084] In particular, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane (BPZ), 4,4'-sulfonyldiphenol, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene are preferred. Among these, 2,2-bis(4-hydroxyphenyl)propane is most preferred due to its excellent strength and durability. These may be used alone or in combination.

[0085] The PC-POS copolymer of the present invention can be produced by following known production methods, such as those described in WO 2011 / 013846 and WO 2019 / 124556. However, the following method is particularly suitable for improving low-temperature impact resistance. To form coarse domains of 80 nm or larger, which enhance low-temperature impact resistance, it is effective to react a high concentration of polydiorganosiloxane with a carbonate oligomer having terminal chloroformate groups. This allows for unprecedented dispersion even in regions with low siloxane block content. Furthermore, as described above, a polydiorganosiloxane with a specific average chain length is used as the raw material, and one or more hydroxyaryl-terminated polydiorganosiloxanes (II) may be used. Specifically, a raw material represented by the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [7] above, in which the average chain length p + q is 50 to 120, is used. Furthermore, in order to satisfy this specific chain length range, two or more different types of hydroxyaryl-terminated polydiorganosiloxane (II) raw materials having an average chain length p+q may be mixed and used. In this case, it is preferable to prepare the polydiorganosiloxane (E-1) having an average chain length p+q of 1 or more but less than 60 and a polydiorganosiloxane (E-2) having an average chain length p+q of 60 or more but less than 200 as raw materials, or to premix polydiorganosiloxane precursors having appropriate average chain lengths before the ends are hydroxyaryl-modified, and then use the raw material obtained by modifying the ends with hydroxyaryls. Furthermore, the polydiorganosiloxane (E-1) and the polydiorganosiloxane (E-2) may be blended in advance before reacting with the carbonate precursor and the dihydric phenol, or may be added to the reaction solution in parallel without being blended in advance, or (E-1) and (E-2) may be divided and added successively to the reaction solution to react with the carbonate precursor and the dihydric phenol.More preferably, the polydiorganosiloxane (E-1) is added to the reaction solution, followed by the polydiorganosiloxane (E-2), which is then reacted with the carbonate precursor and dihydric phenol. This is desirable from the perspective of streamlining the manufacturing process and equipment, thereby improving efficiency and cost effectiveness, and favoring the formation of domains of 80 nm or larger, which contributes to improved impact resistance. Adding the polydiorganosiloxane (E-2) alone last facilitates the local incorporation of polydiorganosiloxane blocks with a long average chain length into the polymer chain, which is thought to favor the formation of domains of 80 nm or larger. In either case, it is desirable to add the hydroxyaryl-terminated polydiorganosiloxane (II) to the reaction solution as quickly as possible, and adding it all at once is preferable. By reacting the hydroxyaryl-terminated polydiorganosiloxane (II) at a higher concentration, it is thought that the local incorporation of polydiorganosiloxane blocks with a large average chain length into the polymer chain is facilitated, which is advantageous for the formation of domains of 80 nm or more. The mass ratio of the polydiorganosiloxanes (E-1) and (E-2) used as raw materials is as described above, and the carbonate precursor and dihydric phenol will be described later.

[0086] In order to form coarse domains of 80 nm or more, in the interfacial polycondensation method for obtaining the PC-POS copolymer of the present invention, the amount of the water-insoluble organic solvent per mole of the total amount of the dihydric phenols represented by the formulas [6] and [7] is preferably 8 moles or more and less than 11 moles, more preferably 8 to 9.5 moles.

[0087] Here, the total amount of dihydric phenols refers to the total amount of bisphenols and polydiorganosiloxane monomers, which are raw materials for polycarbonate.

[0088] The amount of the insoluble organic solvent is the total amount used up to the point at which the catalyst is added and the polycondensation reaction is initiated, and is the total amount of the amount used in producing the polycarbonate oligomer, the amount used to dissolve the polydiorganosiloxane monomer and the terminal terminator, and the amount added to adjust the emulsified state during the interfacial polycondensation reaction.

[0089] In the interfacial polycondensation method for obtaining the PC-POS copolymer of the present invention, if the amount of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by formulas [6] and [7] is less than the lower limit, the emulsion state during polymerization deteriorates, resulting in reduced polymer quality and a high solution viscosity, which reduces productivity. If the amount exceeds the upper limit, domains of 80 nm or larger are not formed sufficiently, resulting in a failure to exhibit cryogenic impact resistance. Furthermore, the water-insoluble organic solvent may be added immediately after the reaction of the carbonate precursor, dihydric phenol, and polydiorganosiloxane proceeds. Specifically, it is desirable to add at least 2 moles of water-insoluble organic solvent per mole of the total amount of dihydric phenols represented by formulas [6] and [7] when the proportion of unreacted polydiorganosiloxane in the reaction solution reaches 10% or less. This ensures sufficient reaction progress while also reducing the risk of precipitation of polymer components due to high concentration.

[0090] Furthermore, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) can be used in combination in an amount of up to 10% by weight based on the total weight of the copolymer, provided that the comonomer does not interfere with the production method of the present invention.

[0091] In the production method of the present invention, a mixed solution containing an oligomer having a terminal chloroformate group is prepared in advance by reacting a dihydric phenol (I) with a carbonate ester-forming compound in a mixed solution of a water-insoluble organic solvent and an alkaline aqueous solution.

[0092] In producing an oligomer of the dihydric phenol (I), the entire amount of the dihydric phenol (I) used in the method of the present invention may be converted into an oligomer at once, or a part of the oligomer may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the subsequent stage. The post-added monomer is added to rapidly proceed with the polycondensation reaction in the subsequent stage, and there is no need to add it if it is not necessary.

[0093] The method for this oligomer formation reaction is not particularly limited, but it is usually preferable to carry out the reaction in a solvent in the presence of an acid binder.

[0094] The proportion of the carbonate ester-forming compound used may be adjusted appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction. When a gaseous carbonate ester-forming compound such as phosgene is used, it is preferable to blow it into the reaction system.

[0095] Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures of these.

[0096] The proportion of the acid binder used may be determined appropriately in consideration of the stoichiometric ratio (equivalents) of the reaction, as described above. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid binder relative to the number of moles of the dihydric phenol (I) used to form the oligomer (usually 1 mole corresponds to 2 equivalents).

[0097] The solvent may be any of various inert solvents used in the production of known polycarbonates, either singly or in combination. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0098] The reaction pressure for oligomer formation is not particularly limited and may be normal, elevated, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50°C, and since heat is often generated during polymerization, water or ice cooling is desirable. The reaction time depends on other conditions and cannot be specified in general, but is usually 0.2 to 10 hours.

[0099] The pH range of the oligomer formation reaction is the same as that of known interfacial reactions, and the pH is always adjusted to 10 or higher.

[0100] In the present invention, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having terminal chloroformate groups in this manner, the hydroxyaryl-terminated polydiorganosiloxane (II) is added to the dihydric phenol (I) while stirring the mixed solution, and the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer are subjected to interfacial polycondensation to obtain a polycarbonate-polydiorganosiloxane copolymer.

[0101] When carrying out the interfacial polycondensation reaction, an acid binder may be added as appropriate, taking into account the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders that can be used include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Specifically, when the hydroxyaryl-terminated polydiorganosiloxane (II) used, or a portion of the dihydric phenol (I) as described above, is added to this reaction stage as a post-added monomer, it is preferable to use 2 equivalents or more of alkali relative to the total moles of the post-added dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) (usually 1 mole corresponds to 2 equivalents).

[0102] The polycondensation by interfacial polycondensation reaction between the oligomer of dihydric phenol (I) and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the mixture.

[0103] In such polymerization reactions, a terminal terminator or a molecular weight modifier is usually used. Examples of terminal terminators include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, p-cumylphenol, tribromophenol, etc., as well as long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxyphenyl alkyl acid esters, and alkyl ether phenols. The amount used is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol of the total dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

[0104] To accelerate the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt may be added.

[0105] The reaction time for this polymerization reaction must be relatively long to reduce the amount of unreacted polydiorganosiloxane components, preferably 30 minutes or more, more preferably 50 minutes or more. On the other hand, since stirring the reaction solution for a long period of time can cause polymer precipitation, the reaction time is preferably 180 minutes or less, more preferably 90 minutes or less.

[0106] If desired, a small amount of an antioxidant such as sodium sulfite or hydrosulfide may be added.

[0107] The polycarbonate resin composition of the present invention can be made into a branched polycarbonate by using a branching agent in combination with the above-mentioned dihydric phenol compound. Examples of trifunctional or higher polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucside, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2,2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-[4-[1,1-bis(4- Examples of the 4-hydroxyphenyl ether include trisphenols such as {4-hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof. Among these, 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0108] The reaction pressure can be reduced, normal, or increased, but is usually preferably normal pressure or the inherent pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and in many cases, water or ice cooling is desirable because heat is generated during polymerization. The reaction time cannot be generally determined because it varies depending on other conditions such as the reaction temperature, but is usually 0.5 to 10 hours.

[0109] In some cases, the obtained polycarbonate copolymer may be subjected to a suitable physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η SP It can also be obtained as a polycarbonate copolymer of [(2-hydroxybenzoyl)-2-propanol / c].

[0110] The resulting reaction product (crude product) can be subjected to various post-treatments such as known separation and purification methods to recover a polycarbonate-polydiorganosiloxane copolymer of the desired purity (degree of purification).

[0111] (Component B: Fluorine resin) The resin composition of the present invention contains, as component B, a fluororesin having a specific structure. The inventors conducted a detailed analysis of the black discoloration and poor appearance caused by black particles in a specific PC-POS copolymer, and discovered that a component contained in the PC-POS copolymer exhibits adhesiveness when melted in a molding machine, scraping off carbonized layers and corroded metals adhering to the inner walls and screw of the molding machine. After extensive research aimed at solving this problem, they discovered for the first time that the fluororesin has the effect of reducing the adhesiveness of the PC-POS copolymer or forming a lubricant layer on the inner walls and cylinder of the molding machine, thereby suppressing the black discoloration and poor appearance caused by black particles.

[0112] The fluororesin in the present invention is a fluororesin containing a polymer unit represented by the formula [4] or a polymer unit represented by the formula [4] and a polymer unit represented by the formula [5].

[0113] [ka]

[0114] (In formula [4], R f 1 , R f 2 , R f 3 and R f 4 each independently represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except when all of them are fluorine atoms.

[0115] [ka]

[0116] If fluororesins other than those mentioned above are used, it will be impossible to prevent the occurrence of black discoloration and poor appearance due to black spots. In addition, compounds with fluoroalkyl groups containing more than five carbon atoms are in limited supply, which leads to unstable supply and high costs.

[0117] Examples of the polymerized unit represented by the above formula [4] include polymerized units derived from ethylene, hexafluoropropylene, octafluoro-1-butene, decafluoro-1-pentene, octafluoroisobutylene, perfluorobutylethylene, etc., and among these, polymerized units derived from ethylene, hexafluoropropylene, and perfluorobutylethylene are preferred, with polymerized units derived from hexafluoropropylene and ethylene being more preferred. These polymerized units may be used alone or in combination of two or more.

[0118] In particular, R f 1 , R f 2 , R f 3 is a fluorine atom, and R f 4 is a fluoromethyl group, or R f 1 , R f 2 , R f 3 , R f 4 is preferably a hydrogen atom.

[0119] Specifically, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-hexafluoropropylene copolymer (EFEP), and polyvinylidene fluoride (PVDF) are more preferred, and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) and ethylene-tetrafluoroethylene copolymer (ETFE) are particularly preferred.

[0120] The fluororesin of the present invention includes examples in which a modified fluororesin is used alone or in which a fluororesin and a modified fluororesin are used in combination. The modified fluororesin is a fluororesin in which some of the carbon-hydrogen bonds contained therein have been modified to have polar groups. The modified polar groups are at least one functional group selected from the group consisting of acid groups such as epoxy groups, glycidyl groups, and carboxy groups, and acid derivatives such as acid anhydride groups. Specifically, the above-mentioned fluororesins are preferably copolymerized with monomers containing polar groups such as epoxy groups, carboxy groups, and acid anhydride groups, and more preferably graft-copolymerized with the above-mentioned fluororesins. Preferred examples of monomers containing epoxy groups include glycidyl methacrylate, butyl glycidyl maleate, butyl glycidyl fumarate, propyl glycidyl fumarate, glycidyl acrylate, and N-(4-(2,3-epoxy)-3,5-dimethyl)acrylamide. Examples of monomers containing carboxy groups include acrylic acid, methacrylic acid, and maleic acid. Examples of the monomer containing an acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, etc. Among the above-mentioned monomers having a polar group, acrylic acid and maleic anhydride are preferred in terms of reactivity and availability.

[0121] Examples of the fluororesin in the present invention include "NEOFLON (trade name) manufactured by Daikin Corporation," "TEFZEL (trade name) manufactured by Mitsui-DuPont Fluorochemicals Co., Ltd.," "TEFLON (registered trademark) (trade name) FEP manufactured by Mitsui-Chemours Fluoroproducts Co., Ltd.," "FLUON (trade name) ETFE manufactured by AGC Inc.," "SOLEF (trade name) manufactured by Solvay Japan K.K.," "DYNEON (trade name) manufactured by 3M Japan Ltd.," "KYNAR (trade name) manufactured by Arkema K.K.," and "KF Polymer manufactured by Kureha Corporation."

[0122] The melting point of the fluororesin is preferably 170 to 280°C, more preferably 200 to 280°C. If the melting point is below this preferred range, the occurrence of black discoloration and poor appearance due to black particles may not be prevented, and if the melting point is above the upper limit, the occurrence of black discoloration and poor appearance may not be prevented, and compatibility with polycarbonate may be poor, resulting in a marbled appearance. The melting point is measured in accordance with JIS K 7121. Specifically, it is measured by differential scanning calorimetry (DSC) as the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10°C / min.

[0123] The content of Component B is 0.3 to 2.5 parts by weight, preferably 0.5 to 1.5 parts by weight, and more preferably 0.8 to 1.2 parts by weight, per 100 parts by weight of Component A. If the content is less than 0.3 parts by weight, the occurrence of black discoloration and poor appearance due to black particles cannot be prevented, and if it exceeds 2.5 parts by weight, poor marble-like appearance and surface peeling occur.

[0124] (Component C: flame retardant) The resin composition of the present invention can contain a flame retardant. Various compounds conventionally known as flame retardants for thermoplastic resins, particularly aromatic polycarbonate resins, can be used as flame retardants. However, more preferred are (i) organometallic salt-based flame retardants (e.g., organic alkali (earth) metal sulfonates, metal borate-based flame retardants, and metal stannate-based flame retardants), (ii) organophosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), and (iii) silicone-based flame retardants consisting of silicone compounds. The incorporation of compounds used as flame retardants not only improves flame retardancy, but also, depending on the properties of each compound, improves antistatic properties, fluidity, rigidity, and thermal stability, for example.

[0125] The content of Component C is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, and even more preferably 0.05 to 10 parts by weight, per 100 parts by weight of Component A. If the content of Component C is less than 0.001 part by weight, flame retardancy may not be maintained, and if it exceeds 20 parts by weight, impact resistance and flame retardancy may not be satisfactory.

[0126] (organic metal salt flame retardant) Organic metal salt flame retardants are advantageous in that they maintain heat resistance to a large extent. The organic metal salt flame retardants most advantageously used in the present invention are alkali (earth) metal salts of sulfonates. Among them, alkali (earth) metal salts of fluorine-substituted organic sulfonic acids are preferred, and alkali (earth) metal salts of sulfonic acids having a perfluoroalkyl group are particularly preferred. Here, the number of carbon atoms in the perfluoroalkyl group is preferably in the range of 1 to 18, more preferably in the range of 1 to 10, and even more preferably in the range of 1 to 8.

[0127] The metals constituting the metal ions of the alkali (earth) metal salt of fluorine-substituted organic sulfonic acid are alkali metals or alkaline earth metals. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium, and examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkali metals are more preferred. Therefore, alkali metal salts of perfluoroalkyl sulfonic acid are preferred. Among these alkali metals, rubidium and cesium are preferred when higher transparency is required. However, they are not widely used and are difficult to purify, which can result in cost disadvantages. On the other hand, while lithium and sodium are advantageous in terms of cost and flame retardancy, they can be disadvantageous in terms of transparency. Taking these factors into consideration, the alkali metals in the alkali metal salt of perfluoroalkyl sulfonic acid can be selected appropriately, but potassium salt of perfluoroalkyl sulfonic acid, which has an excellent balance of properties in all respects, is most preferred. Such potassium salts can also be used in combination with alkali metal salts of perfluoroalkyl sulfonic acid composed of other alkali metals.

[0128] Examples of such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethanesulfonate, sodium perfluorobutanesulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethanesulfonate, lithium perfluorobutanesulfonate, lithium perfluoroheptanesulfonate, cesium trifluoromethanesulfonate, cesium perfluorobutanesulfonate, cesium perfluorooctane sulfonate, cesium perfluorohexanesulfonate, rubidium perfluorobutanesulfonate, and rubidium perfluorohexanesulfonate, and these can be used alone or in combination of two or more.Among these, potassium perfluorobutanesulfonate is particularly preferred.

[0129] The fluoride ion content of the above-mentioned organometallic salt flame retardant, as measured by ion chromatography, is preferably 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be set to essentially 0, but in terms of balancing the refining process and effectiveness, a practical value of about 0.2 ppm is preferred. A perfluoroalkylsulfonic acid alkali metal salt having such a fluoride ion content can be purified, for example, as follows: The perfluoroalkylsulfonic acid alkali metal salt is dissolved in ion-exchanged water in an amount 2 to 10 times the weight of the metal salt at a temperature in the range of 40 to 90°C (more preferably 60 to 85°C). The alkali metal perfluoroalkylsulfonate is produced by neutralizing a perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or by neutralizing a perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide (preferably the latter method). The ion-exchanged water is particularly preferably water with an electrical resistance of 18 MΩ·cm or more. The solution containing the metal salt is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. The solution is then cooled to a temperature range of 0 to 40°C, more preferably 10 to 35°C. Crystals precipitate upon cooling. The precipitated crystals are then filtered out. This produces a suitable purified alkali metal perfluoroalkylsulfonate.

[0130] When a fluorine-substituted organic sulfonic acid alkali (earth) metal salt is used as the flame retardant, the content thereof is preferably 0.01 to 1.0 part by weight, more preferably 0.05 to 0.8 part by weight, and even more preferably 0.08 to 0.6 part by weight, per 100 parts by weight of component A. When the content is within this preferred range, the effects expected from the inclusion of a fluorine-substituted organic sulfonic acid alkali (earth) metal salt (for example, flame retardancy, antistatic properties, etc.) may be exhibited.

[0131] As the organic metal salt-based flame retardant other than the fluorine-substituted alkali (earth) metal salt of an organic sulfonic acid, a metal salt of an organic sulfonic acid that does not contain a fluorine atom is suitable. Examples of such metal salts include alkali metal salts of aliphatic sulfonic acids, alkaline earth metal salts of aliphatic sulfonic acids, alkali metal salts of aromatic sulfonic acids, and alkaline earth metal salts of aromatic sulfonic acids (all of which do not contain a fluorine atom).

[0132] Preferred examples of aliphatic sulfonate metal salts include alkali (earth) metal alkylsulfonates, which can be used alone or in combination of two or more (here, the term "alkali (earth) metal salt" is used to mean both alkali metal salts and alkaline earth metal salts). Preferred examples of alkanesulfonic acids used in such alkali (earth) metal alkylsulfonates include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, and octanesulfonic acid, which can be used alone or in combination of two or more.

[0133] The aromatic sulfonic acid used in the alkali (earth) metal salt of aromatic sulfonate may be at least one acid selected from the group consisting of sulfonic acids of monomeric or polymeric aromatic sulfides, sulfonic acids of aromatic carboxylic acids and esters, sulfonic acids of monomeric or polymeric aromatic ethers, sulfonic acids of aromatic sulfonates, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, sulfonic acids of aromatic ketones, heterocyclic sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensates of aromatic sulfonic acids with methylene bonds, and these may be used alone or in combination of two or more.

[0134] Specific examples of the alkali (earth) metal salts of aromatic sulfonates include disodium diphenyl sulfide-4,4'-disulfonate, dipotassium diphenyl sulfide-4,4'-disulfonate, potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, polysodium polyethylene terephthalate polysulfonate, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly(2,6-dimethylphenylene oxide) polysulfonate, polysodium poly(1,3-phenylene oxide) polysulfonate, polysodium poly(1,4-phenylene oxide) polysulfonate, polypotassium poly(2,6-diphenylphenylene oxide) polysulfonate, lithium poly(2-fluoro-6-butylphenylene oxide) polysulfonate, potassium sulfonate of benzenesulfonate, sodium benzenesulfonate, and benzenesulfonic acid Examples of suitable sulfonates include strontium, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, calcium biphenyl-3,3'-disulfonate, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate, dipotassium diphenylsulfone-3,4'-disulfonate, sodium α,α,α-trifluoroacetophenone-4-sulfonate, dipotassium benzophenone-3,3'-disulfonate, disodium thiophene-2,5-disulfonate, dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophenesulfonate, potassium diphenylsulfoxide-4-sulfonate, a formalin condensate of sodium naphthalenesulfonate, and a formalin condensate of sodium anthracenesulfonate.

[0135] Among the metal salts of fluorine-free organic sulfonic acids, alkali (earth) metal salts of aromatic sulfonates are preferred, and potassium salts are particularly suitable. When such alkali (earth) metal salts of aromatic sulfonates are used as flame retardants, the content thereof is preferably 0.01 to 1 part by weight, more preferably 0.05 to 0.8 parts by weight, and even more preferably 0.08 to 0.6 parts by weight, per 100 parts by weight of Component A.

[0136] (organophosphorus flame retardant) Phosphate compounds, particularly aryl phosphate compounds, are suitable as organophosphorus flame retardants of the present invention. Phosphate compounds are effective in improving flame retardancy, and because phosphate compounds have a plasticizing effect, they are advantageous in that they improve the molding processability of the resin composition of the present invention, although they may result in a decrease in heat resistance. While various phosphate compounds known as conventional flame retardants can be used, more preferred phosphate compounds include one or more phosphate compounds represented by the following general formula [8]:

[0137] [ka]

[0138] [In the above general formula [8], Y is a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of hydroquinone, resorcinol, bis(4-hydroxydiphenyl)methane, bisphenol A, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3-methylcyclohexane, dihydroxydiphenyl, dihydroxynaphthalene, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)ketone, and bis(4-hydroxyphenyl)sulfide; g, h, i, and j each independently represent 0 or 1; n represents an integer of 0 to 5, or, in the case of a mixture of phosphate esters with different n's, represents the average value thereof; R 21 , R 22 , R23 , and R 24 are each independently a monohydric phenol residue derived from an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol.

[0139] The phosphate compound of the above formula [8] may be a mixture of compounds having different n numbers. In the case of such a mixture, the average n number is preferably in the range of 0.5 to 1.5, more preferably 0.8 to 1.2, even more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14.

[0140] Preferred specific examples of the dihydric phenol from which Y in the above formula [8] is derived include resorcinol, bisphenol A, and dihydroxydiphenyl, and among these, resorcinol and bisphenol A are preferred.

[0141] R in the above formula [8] 21 , R 22 , R 23 , and R 24 Preferred examples of the monohydric phenol from which the formula (I) is derived include phenol, cresol, xylenol, and 2,6-dimethylphenol, and among these, phenol and 2,6-dimethylphenol are preferred.

[0142] Specific examples of the phosphate compound of the above formula [8] include monophosphate compounds such as triphenyl phosphate and tri(2,6-xylyl)phosphate, as well as phosphate oligomers based on resorcinol bis(di(2,6-xylyl)phosphate), phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphoric acid ester oligomers based on bisphenol A bis(diphenyl phosphate), and among these, phosphate oligomers based on resorcinol bis(di(2,6-xylyl)phosphate), phosphate oligomers based on 4,4-dihydroxydiphenyl bis(diphenyl phosphate), and phosphoric acid ester oligomers based on bisphenol A bis(diphenyl phosphate) are preferred.

[0143] Another example of an organic phosphorus flame retardant is phosphazene. Phosphazene contains phosphorus and nitrogen atoms in the molecule, which can impart flame retardancy to a resin composition. The phosphazene is not particularly limited as long as it does not contain halogen atoms and has a phosphazene structure in the molecule. The phosphazene structure referred to here is a structure represented by the formula: -P(R)=N- [wherein R is an organic group]. Phosphazene compounds are represented by the general formulas [9] and

[10] .

[0144] [ka]

[0145] [ka]

[0146] (In the above general formulas [9] and

[10] , R 25 , R 26 , R 27 and R 28 represents an organic group that does not contain hydrogen, a hydroxyl group, an amino group, or a halogen atom, and n represents an integer of 3 to 10. In the above formulas [9] and

[10] , examples of the organic group not containing a halogen atom include an alkoxy group, a phenyl group, an amino group, and an allyl group. Among them, cyclic phenoxyphosphazenes represented by the following general formula

[11] are preferred.

[0147] [ka]

[0148] [In the above general formula

[11] , n represents an integer of 3 to 10.] When an organic phosphorus flame retardant is used as the flame retardant, the content thereof is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight, and even more preferably 3 to 10 parts by weight, per 100 parts by weight of component A. When the content is within this preferred range, the effects (e.g., flame retardancy) expected from the inclusion of the organic phosphorus flame retardant may be exhibited.

[0149] (silicone compounds) The silicone compound of the present invention is not particularly limited as long as it can achieve the flame retardancy and transparency desired by the present invention. However, a silicone compound having an aromatic group is preferred, and a viscosity of 300 cSt or less at 25°C is also preferred. High viscosity can result in reduced transparency of molded articles. Furthermore, for a silicone compound to efficiently exert its flame retardant effect, its dispersion state during the combustion process is important. Viscosity is an important factor determining this dispersion state. This is thought to be because if the silicone compound is too volatile during the combustion process, i.e., if the silicone compound has too low a viscosity, the amount of silicone remaining in the system during combustion is diluted, making it difficult to form a uniform silicone structure during combustion. From this perspective, the viscosity at 25°C is more preferably 10 to 300 cSt, even more preferably 15 to 200 cSt, and most preferably 20 to 170 cSt.

[0150] The aromatic group in silicone compounds is bonded to the silicone atom, which contributes to improving compatibility with polycarbonate resins and maintaining transparency, and is also advantageous in preventing the formation of a charred film during combustion, thereby contributing to the development of flame retardant effects.If the compound does not contain an aromatic group, it tends to be difficult to obtain transparency in molded products and to achieve high levels of flame retardancy.

[0151] The silicone compound of the present invention is preferably a silicone compound containing an Si-H group. In particular, it is a silicone compound containing an Si-H group and an aromatic group in the molecule, (1) the amount of Si-H groups contained (Si-H amount) is 0.1 to 1.2 mol / 100 g, (2) the proportion of aromatic groups represented by the following general formula

[12] contained (aromatic group amount) is 10 to 70 wt %:

[0152] [ka]

[0153] (In formula

[12] , X's each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have an OH group or a heteroatom-containing functional group. m1 represents an integer of 0 to 5. Furthermore, when m1 is 2 or more in formula

[12] , each X may be different from the others.) In addition, (3) at least one silicone compound selected from silicone compounds having an average degree of polymerization of 3 to 150 is more preferable.

[0154] More preferably, the silicone compound is at least one selected from silicone compounds containing, as the Si-H group-containing unit, a structural unit represented by at least one of the following general formulas

[13] and

[14] :

[0155] [ka]

[0156] [ka]

[0157] (In Equation

[13] and Equation

[14] , Z 1 ~Z 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom-containing functional group, or a compound represented by the following general formula

[15] . α1 to α3 each independently represent 0 or 1. m2 represents an integer of 0 or 1 or greater. Furthermore, in formula

[13] , when m2 is 2 or greater, the repeating unit can be a plurality of repeating units which are different from each other.

[0158] [ka]

[0159] (In formula

[15] , Z 4 ~Z 8 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a hydrogen atom or a heteroatom-containing functional group. α4 to α8 each independently represent 0 or 1. m3 represents an integer of 0 or 1 or greater. Furthermore, in formula

[15] , when m3 is 2 or greater, the repeating unit may be a plurality of mutually different repeating units. More preferably, when M is a monofunctional siloxane unit, D is a difunctional siloxane unit, and T is a trifunctional siloxane unit, the silicone compound is composed of MD units or MDT units.

[0160] Z of the structural units represented by the above general formulas

[13] ,

[14] and

[15] 1 ~Z 8Examples of the hydrocarbon group having 1 to 20 carbon atoms and optionally having a heteroatom-containing functional group for X in general formula

[12] include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, and decyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl and allyl, aryl groups such as phenyl and tolyl, and aralkyl groups, and these groups may further contain various functional groups such as epoxy, carboxy, carboxylic anhydride, amino, and mercapto. More preferred are alkyl, alkenyl, or aryl groups having 1 to 8 carbon atoms, and particularly preferred are alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, and propyl, vinyl, or phenyl.

[0161] In a silicone compound containing at least one of the structural units represented by the general formulas

[13] and

[14] , when the compound has a plurality of repeating units of siloxane bonds, the repeating units may be in the form of random copolymerization, block copolymerization, or tapered copolymerization.

[0162] In the present invention, for silicone compounds containing preferred Si-H groups, the Si-H content in the silicone compound is preferably in the range of 0.1 to 1.2 mol / 100 g. A Si-H content in the range of 0.1 to 1.2 mol / 100 g facilitates the formation of a silicone structure during combustion. More preferably, the Si-H content is in the range of 0.1 to 1.0 mol / 100 g, and most preferably in the range of 0.2 to 0.6 mol / 100 g. A low Si-H content makes it difficult to form a silicone structure, while a high Si-H content reduces the thermal stability of the composition. Here, the term "silicone structure" refers to a network structure formed by the reaction between silicone compounds or the reaction between a resin and a silicone.

[0163] The amount of Si-H groups referred to here refers to the number of moles of Si-H structure contained in 100g of silicone compound, which can be determined by measuring the volume of hydrogen gas generated per unit weight of silicone compound using alkaline decomposition method.For example, if 122ml of hydrogen gas is generated per 1g of silicone compound at 25℃, the amount of Si-H is calculated as 0.5mol / 100g using the following formula: 122×273 / (273+25)÷22400×100≒0.5

[0164] The silicone compound of the present invention preferably has an aromatic group content of 10 to 70% by weight. More preferably, the aromatic group content is in the range of 15 to 60% by weight, and most preferably in the range of 25 to 55% by weight. If the aromatic group content in the silicone compound is less than 10% by weight, the silicone compound may be unevenly distributed, resulting in poor dispersion and poor appearance. If the aromatic group content is more than 70% by weight, the molecular rigidity of the silicone compound itself increases, resulting in uneven distribution and poor dispersion, which may also result in poor appearance.

[0165] The amount of aromatic groups herein refers to the proportion of aromatic groups represented by the general formula

[12] in the silicone compound, and can be calculated using the following formula: Aromatic group amount = [A / M] × 100 (weight%) Here, A and M in the above formula respectively represent the following values. A = the total molecular weight of all aromatic groups represented by the general formula

[12] contained in one molecule of the silicone compound M = molecular weight of silicone compound

[0166] Furthermore, the silicone compound used in the present invention preferably has a refractive index at 25° C. in the range of 1.40 to 1.60. More preferably, the refractive index is in the range of 1.42 to 1.59, and most preferably in the range of 1.44 to 1.59. When the refractive index is within the above range, the silicone compound is finely dispersed in the aromatic polycarbonate, thereby providing a resin composition with less cloudiness and good dyeability.

[0167] Furthermore, the silicone compound used in the present invention preferably has a volatilization amount of 18% or less as measured by a heat loss method at 105°C for 3 hours. A silicone compound with a volatilization amount of 10% or less is even more preferred. If the volatilization amount is greater than 18%, problems arise in that the amount of volatiles from the resin increases when the resin composition of the present invention is extruded and pelletized, and further problems arise in that many bubbles tend to form in the molded product.

[0168] The silicone compound used may be either linear or branched as long as it satisfies the above conditions, and various compounds having Si-H groups at any one or more positions in the side chain, terminal, or branch point in the molecular structure can be used.

[0169] Generally, the structure of a silicone compound containing Si-H groups in the molecule is composed of any combination of the four types of siloxane units shown below. M units: (CH3)3SiO 1 / 2 , H(CH3)2SiO 1 / 2 , H2(CH3)SiO 1 / 2 , (CH3)2(CH2=CH)SiO 1 / 2 , (CH3)2(C6H5)SiO 1 / 2 , (CH3)(C6H5)(CH2=CH)SiO 1 / 2 Monofunctional siloxane units such as D unit: a bifunctional siloxane unit such as (CH3)2SiO, H(CH3)SiO, H2SiO, H(C6H5)SiO, (CH3)(CH2=CH)SiO, or (C6H5)2SiO T units: (CH3)SiO3 / 2 , (C3H7)SiO 3 / 2 , HSiO 3 / 2 , (CH2=CH)SiO 3 / 2 , (C6H5)SiO 3 / 2 Trifunctional siloxane units such as Q unit: tetrafunctional siloxane unit represented by SiO2

[0170] The structure of the silicone compound containing Si-H groups used in the present invention is specifically represented by the rational formula D n , T p , M m D n , M m T p , M m Q q , M m D n T p , M m D n Q q , M m T p Q q , M m D n T p Q q , D n T p , D n Q q , D n T p Q q Among these, the preferred structure of the silicone compound is M m D n , M m T p , M m D n T p , M m D n Q q and a more preferred structure is M m D n or M m D n T p is. (The coefficients m, n, p, and q in the above rational formula are integers that represent the degree of polymerization of each siloxane unit. Furthermore, when any of m, n, p, and q is a value of 2 or greater, the siloxane unit with that coefficient can be two or more types of siloxane units that differ in the hydrocarbon groups having 1 to 20 carbon atoms that may have a bonded hydrogen atom or a heteroatom-containing functional group.)

[0171] Here, the sum of the coefficients in each rational formula is the average degree of polymerization of the silicone compound. In the present invention, this average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 4 to 80, and even more preferably in the range of 5 to 60. If the degree of polymerization is less than 3, the volatility of the silicone compound itself becomes high, which poses a problem that a large amount of volatile matter is likely to be released from the resin during processing of a resin composition containing this silicone compound. If the degree of polymerization is more than 150, the flame retardancy and transparency of the resin composition containing this silicone compound are likely to be insufficient. The above silicone compounds may be used alone or in combination of two or more.

[0172] Silicone compounds having such Si-H bonds can be produced by conventional methods. For example, the target silicone compound can be obtained by co-hydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing the by-product hydrochloric acid and low boiling points. In addition, when silicone oils, cyclic siloxanes, or alkoxysilanes having a hydrocarbon group with 1 to 20 carbon atoms, which may have an Si-H bond, an aromatic group represented by the general formula

[10] , or other heteroatom-containing functional groups in the molecule, are used as starting materials, and an acid catalyst such as hydrochloric acid, sulfuric acid, or methanesulfonic acid is used, and water is optionally added for hydrolysis. The polymerization reaction is then carried out, and the acid catalyst and low boiling points used are similarly removed to obtain the target silicone compound.

[0173] Furthermore, the silicone compound containing Si-H groups has siloxane units M and M represented by the following structural formula: H , D, D H , D φ2, T, T φ (where M is (CH3)3SiO 1 / 2 M H :H(CH3)2SiO 1 / 2 D:(CH3)2SiOD H :H(CH3)SiOD φ2 :(C6H5)2SiT:(CH3)SiO 3 / 2 T φ :(C6H5)SiO 3 / 2 ), and the average number of each siloxane unit per molecule is m and m h , d, d h , d p2 , t, t p In this case, it is preferable that all of the following relations are satisfied. 2 ≦ m+m h <= 40 0.35 ≦ d+d h +d p2 <= 148 0 ≦ t+t p <= 38 0.35 ≦ m h +d h ≦ 110 If the content is outside this range, it will be difficult to simultaneously achieve good flame retardancy and excellent transparency in the resin composition of the present invention, and in some cases it will be difficult to produce the silicone compound containing Si-H groups.

[0174] The content of the silicone compound used in the present invention is preferably 0.1 to 7 parts by weight, more preferably 0.1 to 4 parts by weight, even more preferably 0.1 to 2 parts by weight, and particularly preferably 0.1 to 1 part by weight, per 100 parts by weight of Component A. If the content is too high, the heat resistance of the resin may decrease and gas may be more likely to be generated during processing, while if the content is too low, flame retardancy may not be exhibited.

[0175] (Component D: Fluorine-containing anti-drip agent) The resin composition of the present invention may contain a fluorine-containing anti-dripping agent other than component B. By containing this fluorine-containing anti-dripping agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

[0176] Examples of the fluorinated anti-dripping agent include fluorine-containing polymers capable of forming fibrils, such as polytetrafluoroethylene, tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers such as those disclosed in U.S. Patent No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

[0177] Fibril-forming PTFE has an extremely high molecular weight and tends to bond PTFE molecules together to form fibers under external influences such as shear force. Its molecular weight, calculated from the standard specific gravity, is 1 million to 10 million, more preferably 2 million to 9 million, in number average molecular weight. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Furthermore, such fibril-forming PTFE can be used in a PTFE mixture with other resins to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties.

[0178] Commercially available PTFE products having such fibril-forming ability include, for example, Teflon® 6J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L manufactured by Daikin Industries, Ltd. Representative examples of commercially available aqueous PTFE dispersions include Fluon AD-1 and AD-936 manufactured by Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., and Teflon® 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

[0179] The mixed form of PTFE can be obtained by (1) mixing an aqueous dispersion of PTFE with an aqueous dispersion or solution of an organic polymer and co-precipitation to obtain a co-aggregated mixture (methods described in Japanese Patent Application Laid-Open Nos. 60-258263 and 63-154744, etc.), (2) mixing an aqueous dispersion of PTFE with dried organic polymer particles (method described in Japanese Patent Application Laid-Open No. 4-272957), or (3) uniformly mixing an aqueous dispersion of PTFE with an organic polymer particle solution and simultaneously extracting each medium from the mixture. (4) a method of polymerizing a monomer that forms an organic polymer in an aqueous PTFE dispersion (method described in JP-A-06-220210, JP-A-08-188653, etc.), and (5) a method of uniformly mixing an aqueous PTFE dispersion and an organic polymer dispersion, then polymerizing a vinyl monomer in the mixed dispersion, and then obtaining a mixture (method described in JP-A-11-29679, etc.). Commercially available PTFE blends include "Metablen A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

[0180] The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, of 100% by weight of the PTFE mixture. When the proportion of PTFE is within this range, good dispersibility of PTFE can be achieved. Note that the proportion of the above-mentioned D component indicates the net amount of anti-drip agent, and in the case of mixed PTFE, it indicates the net amount of PTFE.

[0181] The content of component D is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 1.5 parts by weight, and even more preferably 0.1 to 1 part by weight, per 100 parts by weight of component A. If the content of component D is less than 0.01 part by weight, the flame retardancy may be insufficient, while if it exceeds 5 parts by weight, PTFE may precipitate on the surface of the molded article, resulting in poor appearance and possibly leading to an increase in the cost of the resin composition.

[0182] (Other additives) The resin composition of the present invention is preferably blended with the additives described below according to the intended use. (i) Phosphorus-based stabilizers Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphines.

[0183] Specific examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl)phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris(diethylphenyl)phosphite, tris(di-isopropylphenyl)phosphite, tris(di-n-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert- butylphenyl)phosphite, distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0184] Other phosphite compounds that can be used include those that react with dihydric phenols to form a cyclic structure, such as 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0185] Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, and diisopropyl phosphate, and preferred are triphenyl phosphate and trimethyl phosphate.

[0186] Examples of phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylene diphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylene diphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl ... Examples include (2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-n-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis(2,6-di-tert-butylphenyl)-3-phenyl-phenylphosphonite. Tetrakis(di-tert-butylphenyl)-biphenylene diphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, with tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with, and are preferred for, the above-mentioned phosphite compounds having an aryl group substituted with two or more alkyl groups.

[0187] Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0188] Examples of tertiary phosphines include triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolylphosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

[0189] The phosphorus-based stabilizers can be used singly or in combination of two or more. Among the phosphorus-based stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula

[16] are preferred.

[0190] [ka]

[0191] (In the above general formula

[16] , R and R′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different.)

[0192] As described above, the phosphonite compound is preferably tetrakis(2,4-di-tert-butylphenyl)-biphenylene diphosphonite, and stabilizers containing this phosphonite as the main component are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), either of which may be used.

[0193] Among the phosphite compounds of the above formula

[16] , more preferred are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

[0194] Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of these can be used. Bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite is commercially available as ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes Chemicals), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademarks, manufactured by CIBA Specialty Chemicals), and any of these can be used. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and is readily available. Bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is commercially available as ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark, manufactured by Dover Chemical Co.), and either can be used.

[0195] (ii) Hindered phenolic antioxidants The hindered phenol compound may be any of various compounds that are usually incorporated into resins, such as α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, and 3,5-di-tert-butyl-4-hydroxybenzyl. Phosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylene-bis(6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4 -methyl-6-tert-butylphenol), 4,4'-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl-6-(3-tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9- Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4,4'-dithiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylene bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate nurate, 1,3,5-tris-2[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate, triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetate, 3,9-bis[2-{3- Examples include {(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene, and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)isocyanurate.

[0196] Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane are preferred in the present invention. 3,9-bis[2-{3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is particularly preferred. The above hindered phenol antioxidants can be used alone or in combination of two or more.

[0197] It is preferable to contain either a phosphorus-based stabilizer or a hindered phenol-based antioxidant, and more preferably to use them in combination. The contents of the phosphorus-based stabilizer and hindered phenol-based antioxidant are each preferably 0.001 to 3 parts by weight, more preferably 0.005 to 2 parts by weight, and even more preferably 0.01 to 1 part by weight, per 100 parts by weight of Component A. When used in combination, it is more preferable to contain 0.01 to 0.3 parts by weight of the phosphorus-based stabilizer and 0.01 to 0.3 parts by weight of the hindered phenol-based antioxidant per 100 parts by weight of Component A.

[0198] (iii) Other heat stabilizers The resin composition of the present invention may also contain other heat stabilizers in addition to the phosphorus-based stabilizer and hindered phenol-based antioxidant. Such other heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in JP-A-7-233160). This compound is commercially available under the trade name Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers containing this compound mixed with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the same company is a suitable example. Such premixed stabilizers can also be used in the present invention. The amount of the lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, and more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of the component A.

[0199] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is used in rotational molding. The content of such sulfur-containing stabilizers is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

[0200] (iv) Mold release agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purposes of improving productivity during molding and reducing distortion of molded articles. Known mold release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (polyethylene wax, 1-alkene polymers, etc.; those modified with functional group-containing compounds such as acid-modified waxes can also be used), silicone compounds, fluorine compounds (fluorinated oils typified by polyfluoroalkyl ethers), paraffin wax, and beeswax. Fatty acid esters are particularly preferred mold release agents. Fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohols may be monohydric alcohols or polyhydric alcohols (dihydric or higher). The carbon number of the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerols (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

[0201] On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably has 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, icosanoic acid, and docosanoic acid, as well as unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferred. Among these, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

[0202] The above-mentioned aliphatic carboxylic acids, such as stearic acid and palmitic acid, are usually produced from natural fats and oils, such as animal fats and oils typified by beef tallow and lard, and vegetable fats and oils typified by palm oil and sunflower oil, and therefore these aliphatic carboxylic acids are usually mixtures containing other carboxylic acid components with different numbers of carbon atoms. Therefore, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids, particularly stearic acid and palmitic acid, which are produced from such natural fats and oils and are in the form of a mixture containing other carboxylic acid components are preferably used.

[0203] The fatty acid ester of the present invention may be either a partial ester or a full ester (full ester). However, partial esters usually have a high hydroxyl value, which can easily induce decomposition of the resin at high temperatures, so full esters are more preferred. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. The iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0204] The content of the mold release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of Component A. Within this range, the polycarbonate resin composition may have good mold and roll releasability. In particular, such an amount of fatty acid ester provides a flame-retardant resin composition having good mold and roll releasability without impairing good color.

[0205] (v) ultraviolet absorbers The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber to suppress ultraviolet degradation in outdoor applications. Specific examples of the ultraviolet absorber include benzophenone-based absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.Specific examples of the ultraviolet absorber include benzotriazole-based ones, such as 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dicumylphenyl)phenylbenzotriazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol], 2-(2-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)benzotriazole, Examples of the 2-hydroxyphenyl-2H-benzotriazole skeleton include 2-(2-hydroxy-5-acryloxyethylphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)benzotriazole, 2-(2-hydroxy-4-octoxyphenyl)benzotriazole, 2,2'-methylenebis(4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis(1,3-benzoxazin-4-one), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole, as well as polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomers.Specific examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-methyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-ethyloxyphenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-propyloxyphenol, and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-butyloxyphenol. Further examples include compounds in which the phenyl group of the above-mentioned compounds is replaced with a 2,4-dimethylphenyl group, such as 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hexyloxyphenol. Specific examples of cyclic iminoester-based ultraviolet absorbers include 2,2'-p-phenylenebis(3,1-benzoxazin-4-one), 2,2'-m-phenylenebis(3,1-benzoxazin-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazin-4-one). Specific examples of cyanoacrylate-based ultraviolet absorbers include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene. Furthermore, the ultraviolet absorber may be a polymeric ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and / or a photostable monomer with a monomer such as an alkyl (meth)acrylate by adopting a structure of a radically polymerizable monomer compound. Suitable examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.Among these, benzotriazole-based and hydroxyphenyltriazine-based compounds are preferred in terms of ultraviolet absorption ability, and cyclic iminoester-based and cyanoacrylate-based compounds are preferred in terms of heat resistance and color. Specific examples include "Chemisorb 79" from Chemipro Kasei Co., Ltd. and "Tinuvin 234" from BASF Japan Ltd. The ultraviolet absorbents may be used alone or in combination of two or more.

[0206] The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, still more preferably 0.05 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight, relative to 100 parts by weight of the resin component. If the content is less than 0.01 part by weight, the weather resistance may be insufficient, and if it exceeds 3 parts by weight, the flame retardancy may be insufficient.

[0207] (vi) Dyes and pigments The polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles with diverse design properties. Examples of dyes and pigments that can be used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as Prussian blue, perinone dyes, quinoline dyes, quinacridone dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the polycarbonate resin composition of the present invention can be blended with a metallic pigment to obtain a better metallic color. Aluminum powder is preferred as a metallic pigment. Furthermore, blending with a fluorescent brightener or other fluorescent dye that emits light can provide even better design effects that take advantage of the emitted color.

[0208] (vii) Fluorescent whitening agents The fluorescent brightener used in the resin composition of the present invention is not particularly limited as long as it is used to improve the color tone of the resin or the like to white or bluish white. Examples include stilbene-based, benzimidazole-based, benzoxazole-based, naphthalimide-based, rhodamine-based, coumarin-based, and oxazine-based compounds. Specific examples include CI Fluorescent Brightener 219:1, Eastman Chemical Company's EASTOBRITE OB-1, and Showa Chemical Co.'s Hakkol PSR. The fluorescent brightener absorbs ultraviolet energy from light and radiates it in the visible region. The content of the fluorescent brightener is preferably 0.001 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of Component A. Even if the amount exceeds 0.1 part by weight, the effect of improving the color tone of the composition may be small.

[0209] (viii) Compounds capable of absorbing heat rays The polycarbonate resin composition of the present invention may contain a compound capable of absorbing heat rays. Suitable examples of such compounds include phthalocyanine-based near-infrared absorbers; metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide, ruthenium oxide, immonium oxide, and titanium oxide; various metal compounds with excellent near-infrared absorption, such as metal boride-based and tungsten oxide-based near-infrared absorbers such as lanthanum boride, cerium boride, and tungsten boride; and carbon fillers. Examples of such phthalocyanine-based near-infrared absorbers include MIR-362 manufactured by Mitsui Chemicals, Inc., and are readily available commercially. Examples of carbon fillers include carbon black, graphite (both natural and synthetic), and fullerenes, with carbon black and graphite being preferred. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, and even more preferably 0.001 to 0.07 parts by weight, based on 100 parts by weight of the resin component. The contents of the metal oxide-based near-infrared absorber, metal boride-based near-infrared absorber, and carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio), more preferably 0.5 to 100 ppm, in the polycarbonate resin composition of the present invention.

[0210] (ix) Light diffusing agent The polycarbonate resin composition of the present invention can contain a light diffusing agent to impart a light diffusing effect. Examples of such light diffusing agents include polymeric fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymeric fine particles are already known as light diffusing agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several micrometers and silicone crosslinked particles such as polyorganosilsesquioxane. Examples of the shape of the light diffusing agent include spherical, discoidal, cylindrical, and irregular shapes. Such spherical shapes do not necessarily need to be perfect spheres and include deformed ones, and such cylindrical shapes include cubes. Preferred light diffusing agents are spherical, and the more uniform their particle size, the better. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and even more preferably 0.01 to 3 parts by weight per 100 parts by weight of Component A. Two or more light diffusing agents can be used in combination.

[0211] (x) Highly reflective white pigment The polycarbonate resin composition of the present invention can contain a highly light-reflecting white pigment to impart a light-reflecting effect. Titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) is particularly preferred as such a white pigment. The content of such highly light-reflecting white pigment is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight, per 100 parts by weight of component A. Two or more types of highly light-reflecting white pigments can be used in combination.

[0212] (xi) Antistatic agents The polycarbonate resin composition of the present invention may require antistatic properties. In such cases, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonate phosphonium salts, such as arylsulfonate phosphonium salts (e.g., dodecylbenzenesulfonate phosphonium salt) and alkylsulfonate phosphonium salts, as well as borate phosphonium salts, such as tetrafluoroborate phosphonium salt. The content of the phosphonium salt is preferably 5 parts by weight or less, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and even more preferably 1.5 to 3 parts by weight, per 100 parts by weight of the resin component. Examples of antistatic agents include (2) organic sulfonate alkali (earth) metal salts, such as lithium organic sulfonate, sodium organic sulfonate, potassium organic sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. As mentioned above, such metal salts are also used as flame retardants. More specifically, examples of such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal organic sulfonate is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight, per 100 parts by weight of component A. In particular, alkali metal salts such as potassium, cesium, and rubidium are suitable.

[0213] Examples of antistatic agents include (3) organic ammonium sulfonates such as ammonium alkylsulfonates and ammonium arylsulfonates. The amount of the ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of antistatic agents include (4) polymers containing a poly(oxyalkylene) glycol component as a constituent component, such as polyetheresteramide. The amount of the polymer is suitably 5 parts by weight or less based on 100 parts by weight of the resin component.

[0214] (xii) Filler The polycarbonate resin composition of the present invention can contain various fillers known as reinforcing fillers. As such fillers, various fibrous fillers, plate-like fillers, and granular fillers can be used. Here, fibrous fillers are fillers with a fibrous shape (including rod-like, needle-like, or shapes with axes extending in multiple directions), and plate-like fillers are fillers with a plate-like shape (including those with an uneven surface or curved plates). Granular fillers are fillers with shapes other than these, including irregular shapes. The fibrous and plate-like shapes are often clear from observation of the shape of the filler, but the difference between them and so-called irregular shapes is that those with an aspect ratio of 3 or more can be considered fibrous or plate-like.

[0215] Preferred examples of plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers obtained by surface-coating these fillers with a different material, such as a metal or metal oxide. The particle size is preferably in the range of 0.1 to 300 μm. This particle size refers to the median diameter (D50) of the particle size distribution measured by X-ray transmission, a type of liquid-phase precipitation method, in the range up to about 10 μm; the median diameter (D50) of the particle size distribution measured by laser diffraction / scattering in the range 10 to 50 μm; and the value measured by vibrating sieving in the range 50 to 300 μm. These particle sizes are those in the resin composition. The plate-like filler may be surface-treated with various coupling agents such as silane-based, titanate-based, aluminate-based, and zirconate-based, or may be in the form of a granule that has been bundled or compressed with various resins such as olefin-based resins, styrene-based resins, acrylic resins, polyester-based resins, epoxy-based resins, and urethane-based resins, or higher fatty acid esters.

[0216] The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm. The upper limit of the fiber diameter is more preferably 13 μm, and even more preferably 10 μm. On the other hand, the lower limit of the fiber diameter is preferably 1 μm. The fiber diameter here refers to the number average fiber diameter. The number average fiber diameter is a value calculated from images obtained by observing with a scanning electron microscope the residue collected after dissolving the molded product in a solvent or decomposing the resin with a basic compound, and the ashing residue collected after ashing in a crucible. Examples of such fibrous fillers include glass fiber, flat cross-section glass fiber, milled glass fiber, carbon fiber, milled carbon fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, titanium oxide whiskers, wollastonite, xonotlite, palygorskite (attapulgite), and sepiolite, and other fibrous inorganic fillers; fibrous heat-resistant organic fillers, such as aramid fiber, polyimide fiber, and polybenzthiazole fiber, are also examples. Examples of fillers coated with a different material include metal-coated glass fiber, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fiber. The method for coating the surface of a different material is not particularly limited, and examples include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD methods (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering. Here, the term "fibrous filler" refers to a fibrous filler having an aspect ratio of 3 or more, preferably 5 or more, and more preferably 10 or more. The upper limit of the aspect ratio is about 10,000, preferably 200. The aspect ratio of such a filler is the value in the resin composition.The flat cross-section glass fiber is a glass fiber having an average major axis of 10 to 50 μm, preferably 15 to 40 μm, and more preferably 20 to 35 μm, and an average major axis to minor axis ratio (major axis / minor axis) of 1.5 to 8, preferably 2 to 6, and even more preferably 2.5 to 5. As with the plate-like filler, the fibrous filler may be surface-treated with various coupling agents, bundled with various resins, or granulated by compression. The content of such a filler is preferably 200 parts by weight or less, more preferably 100 parts by weight or less, even more preferably 50 parts by weight or less, and particularly preferably 30 parts by weight or less, per 100 parts by weight of component A.

[0217] (xiii) Other resins and elastomers In the polycarbonate resin composition of the present invention, a small proportion of other resins or elastomers can be used in place of part of the resin component of Component A, as long as the effects of the present invention are achieved. The amount of other resins or elastomers blended is preferably 20% by weight or less, more preferably 10% by weight or less, and even more preferably 5% by weight or less, based on 100% by weight of the total including Component A. Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, and epoxy resins. Examples of elastomers include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and core-shell elastomers such as MBS (methyl methacrylate / styrene / butadiene) rubber, MB (methyl methacrylate / butadiene) rubber, and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

[0218] (xiv) Other additives The polycarbonate resin composition of the present invention may also contain other flow modifiers, antibacterial agents, dispersants such as liquid paraffin, photocatalytic antifouling agents, photochromic agents, and the like.

[0219] <Production of Resin Composition> Any method can be used to produce the resin composition of the present invention, for example, by thoroughly mixing component A, component B, and optionally other components using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, followed by granulation using an extrusion granulator or a briquetting machine as needed, followed by melt-kneading using a melt kneader such as a vented twin-screw extruder, and pelletizing using equipment such as a pelletizer.

[0220] <Molded product manufacturing> The resin composition of the present invention can be injection-molded from such pellets to obtain molded articles. Injection molding can be performed using not only conventional cold runner molding methods, but also hot runners, which enable runnerless production. Injection molding can also be performed using conventional molding methods, such as gas-assisted injection molding, injection compression molding, ultra-high-speed injection molding, injection press molding, two-color molding, sandwich molding, in-mold coating molding, insert molding, foam molding (including those using supercritical fluids), rapid heating and cooling mold molding, insulated mold molding, and in-mold remelt molding, as well as combinations of these molding methods. Furthermore, molded articles formed from the resin composition can be subjected to various surface treatments, including decorative painting, hard coating, water- and oil-repellent coating, hydrophilic coating, UV-absorbing coating, infrared-absorbing coating, electromagnetic wave-absorbing coating, heat-generating coating, antistatic coating, antistatic coating, conductive coating, and metallization (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.).

[0221] (Low temperature impact strength) The polycarbonate resin composition of the present invention preferably has a notched Charpy impact strength of 30 kJ / m or less when a test piece cooled to -30°C is measured in accordance with ISO 179. 2 More preferably, 40 kJ / m 2 More preferably, it is 50 kJ / m or more. 2 The notched Charpy impact strength is 30 kJ / m or more. 2 If it is less than this, it is difficult to apply it to outdoor structural members for cold regions, various housing members, and automobile-related parts.

[0222] (Appearance and color stability) The appearance of a three-tiered plate made using the polycarbonate resin composition of the present invention is characterized by only slight defects such as black discoloration due to black particles, marbled appearance, surface peeling, color unevenness, and transmission unevenness, and it is more preferable that the above-mentioned appearance defects are not observed. If the above conditions are not met, costs will increase due to the occurrence of products with defective appearances, and productivity will be significantly reduced due to the need to disassemble and clean the molding machine as a countermeasure, making the plate unsuitable for use as an exterior material. In addition, the black discoloration due to black particles is a problem that occurs when the color L during continuous molding is increased. * Fluctuation of ΔL * It can also be evaluated by the value, where L * is the CIE 1976 L standardized in JIS Z 8781-4. * a * b * The polycarbonate resin composition of the present invention was molded by 25 continuous shots at a molding temperature of 280°C, and the L value was measured in accordance with JIS Z 8781-4. * Maximum color difference ΔL of the value * The value is preferably 3 or less, more preferably 2 or less, more preferably 1 or less, and even more preferably 0.5 or less. * If the value exceeds the above range, it may result in increased costs due to the occurrence of products with defective appearance, and may also result in a significant decrease in productivity due to the need to disassemble and clean the molding machine as a countermeasure, making it unsuitable for use as an exterior material. [Example]

[0223] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. Unless otherwise specified, parts in the examples are parts by weight and % is % by weight. Evaluations were made according to the following methods.

[0224] (1) Viscosity average molecular weight (Mv) The specific viscosity (η SP ) was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin pellets or polycarbonate-polydiorganosiloxane copolymer in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP )=(t-t0) / t0 [t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls] The calculated specific viscosity (η SP ) and the viscosity average molecular weight Mv was calculated using the following formula: η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 Mv 0.83 c=0.7

[0225] (2) Polydiorganosiloxane component content and average polydiorganosiloxane repeat number (p + q) Using NMR JNM-AL400 manufactured by JEOL Ltd., polycarbonate-polydiorganosiloxane copolymer 1 The average chain length (p+q) was calculated by measuring the H-NMR spectrum and comparing the integral ratio of the peak derived from the dihydric phenol (I) with the integral ratio of the peak derived from the hydroxyaryl-terminated polydiorganosiloxane (II). Similarly, the average chain length (p+q) was calculated by comparing the integral ratio of the peak derived from the hydroxyaryl-terminated polydiorganosiloxane with the integral ratio of the peak derived from the polydiorganosiloxane.

[0226] (3) Average size of polydiorganosiloxane domains After drying component A with hot air at 120°C for 5 hours, a molded piece measuring 10 mm wide, 80 mm long, and 4.0 mm thick was molded using an injection molding machine (Japan Steel Works, Ltd., JSW J-75EIII) at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 50 seconds. A 2 mm deep section of the resulting molded piece, located 15 mm from the gate and 5 mm from the side edge, was cut perpendicular to the resin flow direction using a microtome (Leica Microsystems EM UC6). Ultrathin sections were then prepared by attaching them to a grid (JEOL Ltd., EM FINE GRID No. 2632 F-200-CU 100PC / CA) and observing them using a JEOL Ltd., TEM JEM-2100, at an accelerating voltage of 200 kV. The observation magnification was 20,000x. The obtained micrographs were subjected to particle analysis using image analysis software WinROOF Ver. 6.6 (Mitani Corporation), and the average size of the polydiorganosiloxane domains in the sample slices was determined. The maximum major axis (the length between any two points on the particle's outer contour chosen so that the distance between them is the maximum) was used as the size of each domain. The same analysis was performed on five sample slices, and the average value was used as the value for each sample.

[0227] (4) Visual appearance of molded specimen and ΔL * The resin composition pellets were dried with hot air at 120°C for 5 hours, and then 25 rectangular plates measuring 50 mm wide, 100 mm long, and 2 mm thick were continuously molded using an injection molding machine (NEX50-5E, manufactured by Nissei Plastic Industrial Co., Ltd.) at a molding temperature of 280°C, a mold temperature of 70°C, and a molding cycle of 40 seconds. The appearance was evaluated visually. Poor appearance included black discoloration due to black spots, marbled appearance, and surface peeling on the bent surface when the rectangular plate was bent 90°. The evaluation was based on the presence and severity of each defect. [Black stuff] ◎: No blackening due to black spots is observed. ○: Blackening caused by black spots is slight, gradually subsides, or occurs at a frequency of 20% or less. ×: There is noticeable black discoloration due to black spots. [Marble look] ⊚: No defects in marble-like appearance. ◯: There is some defect in the marbled appearance, but it is minor. ×: Significantly poor marble appearance accompanied by glare. [Surface peeling] ⊚: No surface peeling is observed. ○: There is some surface peeling, but it is minor. ×: Significant surface peeling is observed.

[0228] The obtained molded pieces were measured in accordance with JIS Z 8781-4 using a spectrophotometer CE-7000A (manufactured by Greta Macbeth) under a D65 light source, a 10-degree visual field, and a reflection method according to CIE 1976 L * a * b * Lightness L * The L value of the 25 pieces obtained was measured. * The highest L value * value and lowest L * The difference in values ​​is the maximum color difference ΔL * The value was set as

[0229] (5) Low-temperature impact strength evaluation (notched Charpy impact strength) The resin composition pellets were dried with hot air at 120°C for 5 hours and then injection-molded (FANUC Corporation, ROBOSHOT α-S100iA) to produce molded specimens measuring 10 mm in width, 80 mm in length, and 4.0 mm in thickness at a molding temperature of 290°C, a mold temperature of 80°C, and a molding cycle of 40 seconds. The notched Charpy impact strength of the specimens cooled to -30°C was measured in accordance with ISO 179.

[0230] [Both-end phenol-modified polydiorganosiloxane] In the examples and comparative examples, a polydiorganosiloxane compound having the following structure was used as the dihydric phenol (II) having a polydiorganosiloxane structure. (II)-1: p + q = 40 (KF-2201 manufactured by Shin-Etsu Chemical Co., Ltd.) (II)-2: p + q = 90 (KF-2102 manufactured by Shin-Etsu Chemical Co., Ltd.) (II)-3: 2-allylphenol-terminated polydimethylsiloxane with p+q=130, synthesized in accordance with the method for producing 2-allylphenol-terminated polydiorganosiloxane described in Japanese Patent Publication No. 2662310.

[0231] [Production of polycarbonate-polydiorganosiloxane copolymer] PC-POS-1 to PC-POS-6 were produced by the following method. The properties of each copolymer are shown in Table 1.

[0232] (PC-POS-1 manufacturing method) A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 17,590 parts of ion-exchanged water and 6,883 parts of a 25% aqueous sodium hydroxide solution, and 3,748 parts (16.41 moles) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as the dihydric phenol (I) represented by the general formula [6] and 7.5 parts of hydrosulfite were dissolved therein. Then, 11,246 parts of methylene chloride (8 molar equivalents relative to the total amount of dihydric phenol) was added, and 1,900 parts of phosgene was blown in over 70 minutes at 16 to 24°C with stirring. A solution of 1,324 parts of a 25% aqueous solution of sodium hydroxide and 149 parts of p-tert-butylphenol dissolved in 1,342 parts of methylene chloride (0.96 molar equivalents relative to the total amount of dihydric phenols) was added, and while stirring, a solution of 397 parts (0.128 moles) of the above KF-2201 (as the dihydric phenol (II) represented by the general formula [7]) dissolved in 214 parts of methylene chloride (0.15 molar equivalents relative to the total amount of dihydric phenols) was added, and then a solution of 264 parts (0.037 moles) of KF-2102 dissolved in 142 parts of methylene chloride (0.10 molar equivalents relative to the total amount of dihydric phenols) was added to emulsify the mixture, followed by vigorous stirring again. While stirring, 4.2 parts of triethylamine were added to the reaction solution at 26°C. 15 minutes later, 2795 parts of methylene chloride (2 molar equivalents relative to the total amount of dihydric phenols) were added. Stirring was continued for 1 hour after the addition of triethylamine at a temperature of 26-31°C to terminate the reaction. After the reaction was completed, the organic phase was separated, diluted with methylene chloride, washed with water, and then acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase reached nearly the same as that of ion-exchanged water, the mixture was placed in a kneader filled with warm water, and the methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, the mixture was dried for 12 hours at 120°C in a hot air circulating dryer. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeat number (p+q) of 52, a viscosity-average molecular weight of 16,000, a polydiorganosiloxane component content of 12.5 wt %, an average polydiorganosiloxane domain size of 42 nm, 13 polydiorganosiloxane domains with a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0233] (PC-POS-2 manufacturing method) The same procedure as in the production of PC-POS-1 was followed, except that a solution of 198 parts (0.064 moles) of the above KF-2201 as the dihydric phenol (II) represented by the general formula [7] dissolved in 100 parts of methylene chloride (0.07 molar equivalents relative to the total amount of dihydric phenols) was added, and then a solution of 463 parts (0.064 moles) of KF-2102 dissolved in 230 parts of methylene chloride (0.16 molar equivalents relative to the total amount of dihydric phenols) was added. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeat number (p+q) of 67, a viscosity-average molecular weight of 16,100, a polydiorganosiloxane component content of 12.5 wt%, an average polydiorganosiloxane domain size of 59 nm, 17 polydiorganosiloxane domains with a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0234] (PC-POS-3 manufacturing method) The same production method as for PC-POS-1 was used, except that a solution of 661 parts (0.091 mole) of the above KF-2102 dissolved in 356 parts of methylene chloride (0.25 molar equivalents based on the total amount of dihydric phenol) was added as the dihydric phenol (II) represented by general formula [7]. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeat number (p + q) of 90, a viscosity-average molecular weight of 16,000, a polydiorganosiloxane content of 12.6 wt%, an average polydiorganosiloxane domain size of 69 nm, 32 polydiorganosiloxane domains with a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0235] (PC-POS-4 manufacturing method) The same procedure was used to prepare PC-POS-1, except that 661 parts (0.066 moles) of the dihydric phenol (II) represented by general formula [7] (II)-3 (repeating number p + q = 130) dissolved in 356 parts of methylene chloride (0.25 molar equivalents based on the total amount of dihydric phenol) was added. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeating number (p + q) of 130, a viscosity-average molecular weight of 16,100, a polydiorganosiloxane content of 12.7 wt%, an average polydiorganosiloxane domain size of 92 nm, 43 polydiorganosiloxane domains with a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0236] (PC-POS-5 manufacturing method) The same procedure as in the production of PC-POS-1 was followed, except that a solution of 66 parts (0.021 mole) of the above KF-2201 (as the dihydric phenol (II) represented by the general formula [7]) dissolved in 33 parts of methylene chloride (0.021 molar equivalents relative to the total amount of dihydric phenols) was added, followed by a solution of 154 parts (0.021 mole) of KF-2102 dissolved in 77 parts of methylene chloride (0.06 molar equivalents relative to the total amount of dihydric phenols), and a solution of 99 parts of p-tert-butylphenol dissolved in 891 parts of methylene chloride (0.64 molar equivalents relative to the total amount of dihydric phenols) was added. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeat number (p+q) of 67, a viscosity-average molecular weight of 20,000, a polydiorganosiloxane component content of 4.4 wt%, an average polydiorganosiloxane domain size of 31 nm, four polydiorganosiloxane domains with a maximum length of 80 nm or more, and zero polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0237] (PC-POS-6 manufacturing method) This polycarbonate-polydiorganosiloxane copolymer was produced under the conditions described in Example 8 of WO 2011 / 013846. A reactor equipped with a thermometer, stirrer, and reflux condenser was charged with 21,592 parts of ion-exchanged water and 3,675 parts of 48.5% aqueous sodium hydroxide solution. 3,880 parts (17.00 moles) of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) as the dihydric phenol (I) represented by the general formula [6] and 7.6 parts of hydrosulfite were dissolved in the mixture. Then, 14,565 parts of methylene chloride (10 molar equivalents relative to the total amount of dihydric phenol) was added, and 1,900 parts of phosgene was blown in over 60 minutes at 22-30°C with stirring. 7283 parts of methylene chloride (5 molar equivalents relative to the total amount of dihydric phenol) was added, and a solution of 1131 parts of 48.5% aqueous sodium hydroxide and 108 parts of p-tert-butylphenol dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenol) was added. While stirring, a solution of 430 parts (0.139 moles) of the above KF-2201 (as dihydric phenol (II) represented by the general formula [7]) dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenol) was added at a rate of 0.0004 molar equivalents / min relative to the dihydric phenol (I) to emulsify the mixture, and then vigorously stirred again. With stirring, 4.3 parts of triethylamine was added at a temperature of 26-31 ° C. and the mixture was stirred for 1 hour to complete the reaction. After the reaction was complete, the organic phase was separated, diluted with methylene chloride, washed with water, and then acidified with hydrochloric acid and washed again. When the conductivity of the aqueous phase reached nearly the same level as that of ion-exchanged water, the mixture was placed in a kneader filled with warm water and the methylene chloride was evaporated while stirring to yield a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, the mixture was dried in a hot-air circulating dryer at 120°C for 12 hours. The resulting polycarbonate-polydiorganosiloxane copolymer had an average polydiorganosiloxane repeat number (p + q) of 40, a viscosity-average molecular weight of 19,400, a polydiorganosiloxane content of 8.4 wt%, an average polydiorganosiloxane domain size of 10 nm, 0 polydiorganosiloxane domains with a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains with a maximum length of 400 nm or more.

[0238] [Table 1]

[0239] (PC-1) Linear aromatic polycarbonate resin powder (Teijin Ltd., Panlite L-1250WP) with a solution viscosity of 23,900 and a molecular weight of 2,2-bis(4-hydroxyphenyl)propane as a repeating unit.

[0240] (B component) B-1: Tetrafluoroethylene-hexafluoropropylene copolymer (FEP) (manufactured by Daikin Corporation, Neoflon NP-101 (trade name), melting point 265°C) B-2: Ethylene-tetrafluoroethylene copolymer (ETFE) (manufactured by Daikin Corporation, Neoflon EP610 (trade name), melting point 220°C) B-3: Polyvinylidene fluoride (PVDF) (KF Polymer 1000 (trade name), manufactured by Kureha Corporation, melting point 173°C) B-4 (Comparative Example): Polytetrafluoroethylene (PTFE) (Polyflon FA-500H (trade name), manufactured by Daikin Corporation, melting point 327°C)

[0241] (C component) C-1: Cyclic phenoxyphosphazene (Fushimi Pharmaceutical Co., Ltd., Lavitol FP-110T (product name))

[0242] (D component) D-1: A polytetrafluoroethylene-based mixture, a mixture of polytetrafluoroethylene acrylic copolymers produced by emulsion polymerization (polytetrafluoroethylene content: 50% by weight) (Mitsubishi Rayon Co., Ltd., Metablen A3750 (trade name))

[0243] (Other ingredients) E-1: stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (manufactured by BASF Japan Ltd.: Irganox 1076 (trade name)) E-2: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos168 (trade name) manufactured by BASF Japan Ltd.) F-1: UV absorber (ADEKA Corporation, Adekastab LA-31 (product name)) TiO2: Titanium dioxide (Tipake PC-3 (product name) manufactured by Ishihara Sangyo Kaisha, Ltd.)

[0244] [Production of polycarbonate resin composition] Components A to D and various additives were weighed according to the compositions shown in Tables 2 and 3, mixed uniformly in a blender, and melt-kneaded in a vented twin-screw extruder to obtain pellets. Each additive was premixed with polycarbonate resin at a concentration of approximately 10 to 100 times the blending amount, and then the entire mixture was mixed in the blender. The vented twin-screw extruder used was a KTX-30 (diameter 30 mm) manufactured by Kobe Steel, Ltd. Strands were extruded under conditions of cylinder and die temperatures of 280°C, screw rotation speed of 150 rpm, discharge rate of 20 kg / h, and vent suction of 3 kPa. After cooling in a water bath, the strands were cut in a pelletizer and pelletized. Various evaluation results are shown in Tables 2 and 3.

[0245] [Table 2]

[0246] [Table 3]

[0247] [Examples 1 to 13, Comparative Examples 1 to 7] As is clear from the above table, the compositions of Examples 1 to 13 have a 40 kJ / m 2It can be seen that the results show good low-temperature impact resistance exceeding 100 kJ / s, while suppressing poor black discoloration due to black particles, a marbled appearance, and surface peeling. In contrast, Comparative Examples 1 and 2, which do not contain component B or contain a small amount of component B, exhibit poor black discoloration due to black particles. On the other hand, Comparative Example 3, which contains a large amount of component B, and Comparative Example 6, which uses a PC-POS copolymer with a large POS repeat number, exhibit severe poor marbled appearance and also cause surface peeling. Conversely, Comparative Example 5, which uses a PC-POS copolymer with a small POS repeat number, and Comparative Example 7, which does not use a PC-POS copolymer, exhibit poor low-temperature impact resistance. Furthermore, Comparative Example 4, which uses PTFE as component B, exhibits poor black discoloration due to black particles.

Claims

1. (A) A polycarbonate resin composition comprising: (A-1) 1 to 100 parts by weight of a polycarbonate-polydiorganosiloxane copolymer comprising a polycarbonate block represented by the following general formula [1] and a polydiorganosiloxane block represented by the following general formula [3]; and (A-2) 0 to 99 parts by weight of an aromatic polycarbonate resin comprising a polycarbonate block represented by the following general formula [1], per 100 parts by weight of a resin component (Component A) comprising: (B) 0.3 to 2.5 parts by weight of a fluororesin (Component B) containing polymerization units represented by the following general formula [4] or polymerization units represented by the following general formula [4] and polymerization units represented by the following general formula [5]; wherein the content of the polydiorganosiloxane block represented by the following formula [3] in Component A-1 is 4 to 20% by weight, and the content of the polydiorganosiloxane block represented by the following formula [3] in Component A is 2.5 to 6.5% by weight. 【Chemistry 1】 [(In the above general formula [1], R １ and R ２ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of each, they may be the same or different; e and f each represent an integer of 1 to 4; and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]: 【Chemistry 2】 (In the above general formula [2], R １１ , R １２ , R １３ , R １４ , R １５ , R １６ , R １７ and R １８ each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R １９ and R ２０ each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxy group; when there are a plurality of groups, they may be the same or different; g is an integer from 1 to 10, and h is an integer from 4 to 7. 【Transformation 3】 (In the above general formula [3], R ３ , R ４ , R ５ , R ６ , R ７ and R ８ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R ９ and R １０ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and the average chain length p+q is a natural number from 50 to 120. X is a divalent aliphatic group having 2 to 8 carbon atoms. 【Chemistry 4】 (In the above general formula [4], R ｆ １ , R ｆ ２ , R ｆ ３ and R ｆ ４ each independently represents a fluorine atom, a hydrogen atom, or a fluoroalkyl group having 1 to 5 carbon atoms, except when all of them are fluorine atoms. 【Transformation 5】

2. 2. The polycarbonate resin composition according to claim 1, wherein p+q in the formula [3] is 50 to 70.

3. 3. The polycarbonate resin composition according to claim 1, wherein the viscosity average molecular weight of component A-1 is 11,000 to 30,000.

4. 4. The polycarbonate resin composition according to claim 1, which satisfies the above (i) to (iii). (i) In a cross-sectional image of component A observed using an electron microscope, an 850 nm square (722,500 nm ２ ) there are 1 to 20 domains with a maximum major axis of 80 nm or more. (ii) The average domain size is 30 to 100 nm. (iii) In the cross-sectional observation image of the A component using an electron microscope, all five sample slices had an 850 nm square (722,500 nm ２ ) there are no domains with a maximum diameter of 400 nm or more.

5. 5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein the polydiorganosiloxane block represented by the formula [3] is a polydiorganosiloxane block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane.

6. R in the above formula [3] ３ , R ４ , R ５ , R ６ , R ７ and R ８ 6. The polycarbonate resin composition according to claim 1, wherein is a methyl group.

7. 7. The polycarbonate resin composition according to claim 1, wherein the polycarbonate block represented by the formula [1] is a polycarbonate block derived from 2,2-bis(4-hydroxyphenyl)propane.

8. 8. The polycarbonate resin composition according to claim 1, wherein the melting point of component B is 170 to 280°C.

9. In the above formula [4], R ｆ １ , R ｆ ２ , R ｆ ３ is a fluorine atom, and R ｆ ４ 9. The polycarbonate resin composition according to claim 1, wherein is a fluoromethyl group.

10. In the above formula [4], R ｆ １ , R ｆ ２ , R ｆ ３ and R ｆ ４ The polycarbonate resin composition according to any one of claims 1 to 8, wherein is a hydrogen atom.

11. The L measured in accordance with JIS Z 8781-4 of the molded product obtained by 25 shots of continuous molding at a molding temperature of 280°C. ＊ Maximum color difference ΔL of the value ＊ 11. The polycarbonate resin composition according to claim 1, wherein the value of [Delta] is 3 or less.

12. 12. The polycarbonate resin composition according to claim 1, further comprising 0.001 to 20 parts by weight of a flame retardant (C) (Component C) per 100 parts by weight of Component A.

13. 13. The polycarbonate resin composition according to claim 1, further comprising 0.01 to 5 parts by weight of a fluorinated anti-dripping agent (Component D) per 100 parts by weight of Component A.

14. A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 13.

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