JP7670531B2 - Polycarbonate resin composition and molded article - Google Patents

Description

The present invention relates to a polycarbonate resin composition and a molded article. More specifically, the present invention relates to a polycarbonate resin composition that uses a specific polycarbonate-polydiorganosiloxane copolymer and a (meth)acrylic-modified polyorganosiloxane to provide a good molded appearance with reduced black spots and significantly improved low-temperature impact resistance.

Polycarbonate resins are used in many applications, such as machine parts, automobile parts, electrical and electronic parts, and office equipment parts, due to their excellent properties, such as mechanical strength, dimensional stability, and flame retardancy. With their strength in impact resistance, they are sometimes used as housings and exterior parts for various devices, but as their applications expand, the environments in which they are used are also becoming more diverse, and sufficient performance is required even outdoors, at low temperatures such as -30°C, and when exposed to paint or chemicals. For example, they have not been able to provide sufficient performance as a material for outdoor electrical and electronic storage boxes such as information and communication boxes, which require very high impact properties, and junction boxes for solar power generation. A polycarbonate-based material, polycarbonate-polydiorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer"), is known as a resin material with 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, and attempts have been made to improve low-temperature impact resistance by appropriately selecting the polydiorganosiloxane (hereinafter sometimes abbreviated as "POS") skeleton and manufacturing method used and controlling the domain state of POS aggregation (Patent Documents 2 and 3). Methods of 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 is still insufficient. On the other hand, as a method of improving low-temperature impact resistance, a polycarbonate-polydiorganosiloxane copolymer using a long-chain POS with a large POS repeat number has been disclosed (Patent Document 2), but this often causes poor molded appearance such as black spots and the associated blackening, leading to a decrease in aesthetics and uneven coloring in the design, making it difficult to use as an exterior material.

Japanese Patent Application Publication No. 5-247195 Special Publication No. 2006-523243 WO91/00885 Japanese Patent Application Publication No. 4-225060 WO2016/088861

The object of the present invention is to provide a polycarbonate resin composition and molded article that has a good molded appearance with reduced foreign matter and dramatically improved low-temperature impact resistance.

As a result of intensive research into solving the above problems, the inventors discovered that the above problems can be solved by the following configuration, and arrived at the present invention.

(Configuration 1)
(A) A polycarbonate resin composition comprising (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) 100 parts by weight of a resin component (A component) consisting of 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 (meth)acrylic-modified polyorganosiloxane (B component).

[(In the above general formula [1], R ¹ and R ² each independently represent 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 a plurality 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].)

(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 represent 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, and when there are a plurality of such 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.

(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; 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; and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

(Configuration 2)
The polycarbonate resin composition according to the above-mentioned constitution 1, characterized in that p+q in the above-mentioned formula [3] is 50 to 70.
(Configuration 3)
3. The polycarbonate resin composition according to claim 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.
(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.
(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 the A-1 component is 11,000 to 30,000.

(Configuration 6)
5. The polycarbonate resin composition according to claim 4, which satisfies (i) to (iii).
(i) In a cross-sectional image of component A observed using an electron beam microscope, there are 1 to 20 domains with a maximum major axis of 80 nm or more in an area of 850 nm square (722,500 nm ² ).
(ii) the average domain size is between 30 and 100 nm;
(iii) In cross-sectional images of component A observed using an electron beam microscope, no domains with a maximum major axis of 400 nm or more exist within an area of 850 nm square (722,500 nm ² ) in any of the five sample slices.
(Configuration 7)
The polycarbonate resin composition according to any one of the above structures 1 to 6, characterized in that the polydiorganosiloxane block represented by the above formula [3] is a polydiorganosiloxane block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane.
(Configuration 8)
The polycarbonate resin composition according to any one of the above configurations 1 to 7, characterized in that R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the above formula [3] are methyl groups. (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.
(Configuration 10)
The polycarbonate resin composition according to any one of the above structures 1 to 9, characterized in that the B component is an acrylic-modified polyorganosiloxane obtained by graft copolymerizing a (meth)acrylic acid ester (B2 component) with a polyorganosiloxane (B1 component) represented by the following general formula [4]:

[In the above general formula [4], R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y represents an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group. ^X1 and ^X2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group ^{represented by SiR4R5R6} ( ^R4 and ^R5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and ^R6 represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group), m is an integer of 1 to 10,000, n is an integer of 1 or more, and the siloxane chain may be branched.]

(Configuration 11)
11. The polycarbonate resin composition according to claim 10, wherein R ¹ , R ² and R ³ in the formula [4] are methyl groups.
(Configuration 12)
12. The polycarbonate resin composition according to claim 10 or 11, wherein component B2 is methyl methacrylate and/or 2-hydroxyethyl methacrylate.
(Configuration 13)
13. The polycarbonate resin composition according to any one of claims 1 to 12, characterized in that a ^{molded product obtained by continuous molding at a molding temperature of 280°C for 25 shots has a maximum color difference ΔL* value} of 3 or less as measured in accordance with JIS Z 8781-4.
(Configuration 14)
The polycarbonate resin composition according to any one of the above constitutions 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. (Constitution 15)
15. The polycarbonate resin composition according to any one of the above structures 1 to 14, characterized in that it contains 0.01 to 5 parts by weight of a fluorinated drip-preventing agent (D) (Component D) per 100 parts by weight of Component A.
(Configuration 16)
A molded article formed from the polycarbonate resin composition according to any one of Configurations 1 to 15.

The polycarbonate resin composition of the present invention has good low-temperature impact resistance and a molded appearance free of blackening due to black spots, and is therefore suitable for use as a material for outdoor structural members for cold regions, various housing members, and automobile-related parts. It is also useful for various applications such as various electronic and electrical device parts, camera parts, office automation device parts, precision machine parts, machine parts, vehicle parts, agricultural materials, transport containers, play equipment, and miscellaneous goods, and the industrial effects it provides are exceptional.

(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).

(A-1 Component: 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].

In the above formula [1], R ¹ and R ² each independently represent 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 a plurality of each, they may be the same or different.

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. An alkyl group having 1 to 6 carbon atoms is preferable. Examples of alkoxy groups having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, and octoxy groups. An alkoxy group having 1 to 6 carbon atoms is preferable. Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. An cycloalkyl group having 6 to 12 carbon atoms is preferable. Examples of cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyloxy groups. An cycloalkyl group having 6 to 12 carbon atoms is preferable. 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 are each independently an integer from 1 to 4.

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

In the above formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent 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.

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.

R ¹⁹ and R ²⁰ each independently represent 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.

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. An alkyl group having 1 to 6 carbon atoms is preferred. Examples of alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups. An alkoxy group having 1 to 6 carbon atoms is preferred. Examples of cycloalkyl groups having 6 to 20 carbon atoms include cyclohexyl and cyclooctyl groups. A cycloalkyl group having 6 to 12 carbon atoms is preferred. Examples of cycloalkoxy groups having 6 to 20 carbon atoms include cyclohexyloxy and cyclooctyl groups. A cycloalkyl group having 6 to 12 carbon atoms is preferred. 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.

g is an integer from 1 to 10, preferably an integer from 1 to 6. h is an integer from 4 to 7, preferably an integer from 4 to 5.

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

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

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.

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

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.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. An alkyl group having 1 to 6 carbon atoms is preferable. Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group and a naphthyl group. Examples of the substituent include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. It is preferable that R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are a methyl group.

R ⁹ and R ¹⁰ each independently represent 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.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group,
Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, and the like. An alkoxy group having 1 to 6 carbon atoms is preferred.

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

The polydiorganosiloxane block represented by the above formula [3] is preferably a polydiorganosiloxane block derived from a (2-allylphenol)-terminated polydiorganosiloxane or a (2-methoxy-4-allylphenol)-terminated polydiorganosiloxane, i.e., in formula [3], it is preferred that X is a trimethylene group and R ⁹ and R ¹⁰ are hydrogen atoms, or that X is a trimethylene group and R ⁹ and R ¹⁰ are methoxy groups.

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, the formation of maximum domains may be insufficient and low-temperature impact resistance may not be achieved, while if the content is more than the upper limit, there may be major problems in terms of production, such as poor polymerization reaction due to deterioration of the emulsion state or difficulty in granulation due to an excessively low glass transition temperature.

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 kneadability may deteriorate due to the large difference in melt viscosity with the polycarbonate resin (component A-2) to be mixed. If it exceeds the upper limit, the melt viscosity is high and generally high molding processing temperatures are required, which may lead to problems such as thermal deterioration of the resin and reduced productivity due to poor separation in the water washing step during production.

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. 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 even more 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 more than 120, poor marbled appearance and surface peeling occur.

(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 [5].

(In the above general formula [5], R ¹ , R ² , e, f and W are the same as those in formula [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-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxy 2,2-bis(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)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)diphenylmethane, 4,4'-Dihydroxydiphenyl)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'-dihydro Examples of such compounds include 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, 1,4-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.

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, which has excellent strength and good durability, is the most suitable. These may be used alone or in combination of two or more.

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 the component A-1 and 10 to 90 parts by weight of the component A-2, and more preferably 50 to 20 parts by weight of the component A-1 and 50 to 80 parts by weight of the component A-2. If the component A-1 is less than 1 part by weight, sufficient low-temperature impact resistance is not exhibited.

The content of the polydiorganosiloxane blocks 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 achieved, and if it is more than the upper limit, poor appearance due to blackening caused by black spots or marbled appearance may easily occur, and thermomechanical properties may also be reduced.

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 achieved, and if it is greater than the upper limit, the solution viscosity may increase, resulting in reduced productivity and insufficient molding flowability.

(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.

In the present invention, the polydiorganosiloxane domain refers to a domain that is mainly 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.

The maximum major axis, average domain size, distribution, and dispersion state of the polydiorganosiloxane domain of the A component molded product in the present invention are evaluated in a cross-sectional observation image of the resin composition of 850 nm square (722,500 nm ² ) using an electron microscope (hereinafter sometimes abbreviated as TEM). In the present invention, the terms "maximum major axis of the domain" and "average domain size" refer to measurements taken by cutting a thin slice from a molded piece of 4.0 mm thickness formed by injection molding and observing it with a TEM. The average domain size of the polydiorganosiloxane domain means the number average value of the individual domain sizes.

Specifically, a molded piece 10 mm wide, 80 mm long, and 4.0 mm thick produced by injection molding was used to cut a thin slice at 15 mm from the gate of the molded piece using a microtome at room temperature, and observed with a TEM at a magnification of 20,000 times. The obtained TEM photograph was subjected to particle analysis using image analysis software Win ROOF Ver. 6.6 (Mitani Shoji Co., Ltd.), and the average size and particle size distribution (frequency distribution) of the polydiorganosiloxane domains in the sample slice were obtained. Here, the maximum major axis (the length when any two points on the outer contour of the particle are selected so that the length between them is the maximum) was used as the size of each domain. A similar analysis was performed on five sample slices, and the average value was used as the value for each sample.

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 fully exhibited, and if it exceeds the upper limit of this range, poor appearance due to black discoloration caused by black spots or marbled appearance may easily occur.

In the present invention, in a cross-sectional observation image of component A using a TEM, preferably 1 to 20 polydiorganosiloxane domains having a maximum major axis of 80 nm or more are present in an area of 850 nm square (722,500 nm ² ), more preferably 2 to 20, even more preferably 4 to 20, and particularly preferably 5 to 20. If there is not even one polydiorganosiloxane domain having a maximum major axis of 80 nm or more, sufficient low-temperature impact resistance may not be exhibited, and if there are more than 20, black discoloration due to black spots and marbled appearance may easily occur. Furthermore, in the present invention, it is preferable that no polydiorganosiloxane domains having a maximum major axis of 400 nm or more are present in an area of 850 nm square (722,500 nm ² ) in any of the five sample slices. When one or more polydiorganosiloxane domains having a maximum major axis of 400 nm or more are present, the appearance may be adversely affected by significant black spots, such as black discoloration or marbled appearance.

(Polydiorganosiloxane)
In the present invention, a polydiorganosiloxane having a specific average chain length and represented by the following general formula [6], hydroxyaryl-terminated polydiorganosiloxane (II), is used as a raw material.

(In the above general formula [6], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent 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; R ⁹ and R ¹⁰ each independently represent 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; and X is a divalent aliphatic group having 2 to 8 carbon atoms.)

The average chain length p+q is preferably a natural number between 50 and 100, more preferably between 50 and 70, and particularly preferably between 60 and 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. In order to satisfy such a specific chain length range, two or more different types of hydroxyaryl-terminated polydiorganosiloxane (II) raw materials having average chain lengths p+q may be mixed to prepare the polydiorganosiloxane. In that case, it is preferable to use polydiorganosiloxane (E-1) having an average chain length p+q of 1 or more and less than 60, and polydiorganosiloxane (E-2) having an average chain length p+q of 60 or more and 200 or less as raw materials. The method for mixing and preparing the polydiorganosiloxane raw material may be either a method of mixing appropriate polydiorganosiloxane raw materials whose ends have been hydroxyaryl-modified together, or a method of premixing polydiorganosiloxane precursors having an appropriate average chain length before the ends are hydroxyaryl-modified together, and then modifying the ends with hydroxyaryls. The average chain length p+q is calculated by nuclear magnetic resonance (NMR) measurement.

When polydiorganosiloxane (E-1) and polydiorganosiloxane (E-2) are mixed, it is preferable to use them in a weight ratio of (E-1):(E-2) = 1:99 to 99:1, and more preferably 10:90 to 90:10.

It is more preferable to use polydiorganosiloxane (E) obtained by blending the above polydiorganosiloxanes (E-1) and (E-2) as the polydiorganosiloxane raw material, and 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.

When premixed, 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, and more preferably 100 or less. As the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the general formula [6], for example, the following compounds are preferably used.

Hydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, and is easily produced by subjecting vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol to a hydrosilylation reaction at the end of a polysiloxane chain having a predetermined degree of polymerization. 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.

<Method for Producing Polycarbonate-Polydiorganosiloxane Copolymer>
The polycarbonate-polydiorganosiloxane copolymer of the present invention can be produced by the steps (i) and (ii).

(Step (i))
The step (i) is a step of reacting a dihydric phenol (I) represented by the following formula [5] 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.

(In the formula, R ¹ , R ² , e, f and W are the same as defined above.)

As the dihydric phenol (I) represented by the formula [5], for example, 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.

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, which has excellent strength and good durability, is the most suitable. These may be used alone or in combination of two or more kinds.

The PC-POS copolymer of the present invention can be produced by following the known production methods described in, for example, WO2011/013846 and WO2019/124556, but the following method is suitable when it is particularly desired to improve low-temperature impact resistance. In order to form coarse domains of 80 nm or more that improve low-temperature impact resistance, it is effective to react a high concentration of polydiorganosiloxane with a carbonate oligomer having a terminal chloroformate group, which allows an unprecedented dispersion state to be expressed even in areas with a low content of siloxane blocks. Furthermore, as described above, a polydiorganosiloxane with a specific average chain length is used as a raw material, and only one type of hydroxyaryl-terminated polydiorganosiloxane (II) may be used, or two or more types may be used. Specifically, a raw material is used that is represented by the hydroxyaryl-terminated polydiorganosiloxane (II) represented by the above general formula [6] and has an average chain length p+q of 50 to 120. In order to satisfy such a 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 that case, it is preferable to use polydiorganosiloxane (E-1) having an average chain length p+q of 1 or more and less than 60 and polydiorganosiloxane (E-2) having an average chain length p+q of 60 or more and 200 or less as raw materials to prepare the polydiorganosiloxane, or to use a raw material obtained by previously mixing polydiorganosiloxane precursors having an appropriate average chain length before the terminals are modified with hydroxyaryls and then modifying the terminals with hydroxyaryls. Furthermore, the polydiorganosiloxane (E-1) and the polydiorganosiloxane (E-2) may be mixed in advance before reacting with the carbonate precursor and the dihydric phenol, or they may be added to the reaction solution in parallel without being mixed 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, and then the polydiorganosiloxane (E-2) is added to the reaction solution to react with the carbonate precursor and the dihydric phenol, which is advantageous in terms of efficiency and cost effectiveness due to simplification of the production process equipment, and the formation of domains of 80 nm or more that contribute to improved impact resistance. By adding the polydiorganosiloxane (E-2) alone last, it is believed that the local introduction of polydiorganosiloxane blocks having a large average chain length into the polymer chain is facilitated, which is advantageous for the formation of domains of 80 nm or more. In either case, it is desirable to add the hydroxyaryl-terminated polydiorganosiloxane (II) to the reaction solution as quickly as possible, and it is preferable to add it all at once. By reacting the hydroxyaryl-terminated polydiorganosiloxane (II) in a higher concentration state, it is believed that the local introduction of polydiorganosiloxane blocks having 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.

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 formulas [5] and [6] is preferably 8 moles or more and less than 11 moles, more preferably 8 to 9.5 moles.

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

The amount of the insoluble organic solvent is the total amount used up to the point where the catalyst is added to start the polycondensation reaction, 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.

In the interfacial polycondensation method for obtaining the PC-POS copolymer of the present invention, if the amount of the water-insoluble organic solvent per mole of the total amount of the dihydric phenols represented by formulas [5] and [6] is less than the lower limit, the polymer quality will decrease due to deterioration of the emulsion state during polymerization, and the solution viscosity will be too high, resulting in a decrease in productivity. If the amount exceeds the upper limit, the formation of domains of 80 nm or more will be insufficient, and impact resistance at extremely low temperatures will not be achieved. Furthermore, a water-insoluble organic solvent may be added immediately after the reaction of the carbonate precursor and dihydric phenol with the polydiorganosiloxane proceeds. Specifically, it is desirable to add 2 moles or more of the water-insoluble organic solvent per mole of the total amount of the dihydric phenols represented by formulas [5] and [6] when the ratio of unreacted polydiorganosiloxane in the reaction solution among the polydiorganosiloxanes used becomes 10% or less. This makes it possible to ensure sufficient reaction progress while suppressing the risk of precipitation of polymer components due to high concentration.

In addition, other comonomers than the dihydric phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) may be used in an amount of 10% by weight or less based on the total weight of the copolymer, provided that the use of these comonomers does not interfere with the production process of the present invention.

In the manufacturing 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.

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 it may be added as a post-added monomer as a reaction raw material to the interfacial polycondensation reaction in the latter stage. The post-added monomer is added to quickly advance the polycondensation reaction in the latter stage, and there is no need to add it if it is not necessary.

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.

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

As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, an organic base such as pyridine, or a mixture of these can be used.

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

As the solvent, a solvent inert to various reactions, such as those used in the production of known polycarbonates, may be used alone or as a mixture of solvents. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, halogenated hydrocarbon solvents such as methylene chloride are preferably used.

There are no particular restrictions on the reaction pressure for oligomer production, and it may be normal pressure, elevated pressure, 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 generated during polymerization in many cases, it is desirable to cool the reaction with water or ice. The reaction time depends on other conditions and cannot be specified in general, but it is usually carried out for 0.2 to 10 hours.

The pH range for the oligomer formation reaction is similar to known interfacial reaction conditions, and the pH is always adjusted to 10 or higher.

In this way, the present invention obtains a mixed solution containing an oligomer of dihydric phenol (I) having a terminal chloroformate group, and then adds the hydroxyaryl-terminated polydiorganosiloxane (II) to the dihydric phenol (I) while stirring the mixed solution, and obtains a polycarbonate-polydiorganosiloxane copolymer by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

In carrying out the interfacial polycondensation reaction, an acid binder may be appropriately added in consideration of the stoichiometric ratio (equivalents) of the reaction. Examples of acid binders 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 an excess amount 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).

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

In such polymerization reactions, a terminal terminator or a molecular weight regulator 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, and the like, 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 of the agent used is in the range of 100 to 0.5 moles, preferably 50 to 2 moles, per 100 moles of all dihydric phenol compounds used, and it is of course possible to use two or more compounds in combination.

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

The reaction time of such a polymerization reaction needs to be relatively long in order to reduce the amount of unreacted polydiorganosiloxane components. It is preferably 30 minutes or more, and 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, it is preferably 180 minutes or less, and more preferably 90 minutes or less.

If desired, small amounts of antioxidants such as sodium sulfite or hydrosulfide may be added.

In addition, 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 phloroglucine, phloroglucide, 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 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 which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, with 1,1,1-tris(4-hydroxyphenyl)ethane being particularly preferred.

The reaction pressure can be reduced, normal, or increased, but is usually suitable for carrying out the reaction at normal pressure or at the reaction system's own pressure. The reaction temperature is selected from the range of -20 to 50°C, and since the polymerization often generates heat, it is desirable to cool the reaction with water or ice. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general, but is usually carried out for 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer can be appropriately subjected to a physical treatment (mixing, fractionation, etc.) and/or a chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a polycarbonate copolymer having a desired reduced viscosity [η _SP /c].

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).

(Component B: (meth)acrylic modified polyorganosiloxane)
The resin composition of the present invention contains a (meth)acrylic-modified polyorganosiloxane as component B. The (meth)acrylic-modified polyorganosiloxane is also called a silicone-modified (meth)acrylic polymer. The present inventors conducted a detailed analysis of the black discoloration and poor appearance caused by black bumps in a specific PC-POS copolymer, and found that the components contained in the PC-POS copolymer exhibit adhesion when melted in a molding machine, and scrape out the carbonized layer and corroded metal attached to the inner wall and screw of the molding machine. As a result of intensive research to solve this problem, it was found for the first time that the (meth)acrylic-modified polyorganosiloxane has the effect of weakening the adhesion of the PC-POS copolymer or forming a lubricant layer on the inner wall and cylinder of the molding machine, and has the effect of suppressing the black discoloration and poor appearance caused by black bumps. Note that when a polyorganosiloxane or a (meth)acrylic resin that is not (meth)acrylic-modified is used as component B, there is no effect of suppressing the black discoloration and poor appearance caused by black bumps.

The (meth)acrylic-modified polyorganosiloxane in the present invention is preferably a (meth)acrylic-modified polyorganosiloxane obtained by graft copolymerizing a (meth)acrylic acid ester (component B2) with a polyorganosiloxane (component B1) represented by the following general formula [4].

[In the above general formula [4], R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y represents an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group. ^X1 and ^X2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group ^{represented by SiR4R5R6} ( ^R4 and ^R5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and ^R6 represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group), m is an integer of 1 to 10,000, n is an integer of 1 or more, and the siloxane chain may be branched.]

In the above general formula [4], R ¹ , R ² and R ³ are preferably each independently a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a methyl group.

Such (meth)acrylic modified polyorganosiloxanes can be produced by known methods. For example, they can be produced by combining hydrolysis, polymerization, and equilibration means using linear or cyclic low molecular weight polyorganosiloxanes or alkoxysilanes having the above groups. Hydrolysis, polymerization, and equilibration can be carried out by known techniques even in a state dispersed in water.

Component B2 is an alkyl ester, hydroxyalkyl ester, or alkoxyalkyl ester of acrylic acid or methacrylic acid, and specific examples thereof include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, n-octyl acrylate, 2-hydroxyethyl acrylate, and 2-methoxyethyl acrylate, and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate. These may be used alone or in combination of two or more, and methyl methacrylate and 2-hydroxyethyl methacrylate are particularly preferred.

It may also contain other monomers copolymerizable with (meth)acrylic acid esters. Representative examples of such monomers include styrene-based compounds such as styrene, vinyl toluene, and α-methylstyrene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, halogenated olefins such as vinyl chloride and vinylidene chloride, vinyl esters such as vinyl acetate and vinyl propionate, unsaturated amides such as acrylamide, methacrylamide, and N-methylolacrylamide, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and maleic anhydride, and other monomers having one double bond. Representative examples of such monomers include polyunsaturated monomers such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate. Two or more of these can be used.

The content of these other copolymerizable monomers is preferably 30% by weight or less, more preferably 25% by weight or less, and even more preferably 20% by weight or less, based on 100% by weight of the total amount with the (meth)acrylic acid ester.

Graft copolymerization can be carried out by known techniques. For example, polyorganosiloxane and (meth)acrylic acid ester or a mixture of polyorganosiloxane and other monomers are emulsified and dispersed in water, and polymerized in the presence of a radical polymerization initiator to carry out graft copolymerization. The emulsifier and radical polymerization initiator used in this method may be any known one for emulsion polymerization. After the polymerization is completed, the graft copolymer can be obtained by salting out, filtering, washing with water, and drying. In this emulsion graft copolymerization, if the polyorganosiloxane is produced in a dispersed state in water as described above, the resulting emulsion of polyorganosiloxane can be used as it is as a raw material for graft copolymerization.

The (meth)acrylic modified polyorganosiloxane of the present invention is a graft copolymer of polyorganosiloxane (B1 component) and (meth)acrylic acid ester (B2 component) at a weight ratio of B1 component/B2 component of preferably 95/5 to 5/95, more preferably 90/10 to 20/80, even more preferably 85/15 to 30/70, and particularly preferably 80/20 to 40/60. In this weight ratio, if the polyorganosiloxane exceeds 95 parts by weight, compatibility with polycarbonate may be insufficient, resulting in poor mechanical strength, whereas if it is less than 5 parts by weight, it may not be possible to prevent the occurrence of black discoloration and poor appearance due to black spots.

Examples of the acrylic-modified polyorganosiloxane in the present invention include "Chaline (trade name) manufactured by Nissin Chemical Industry Co., Ltd.", "Simac (trade name) manufactured by Toa Gosei Co., Ltd.", "KP-578, KP-561P, KP-562P, etc. manufactured by Shin-Etsu Chemical Co., Ltd.", "8BS manufactured by Taisei Fine Chemical Co., Ltd.", and "Zemlac (trade name) and Silyl (trade name), etc. manufactured by Kaneka Corporation." are used.

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 spots cannot be prevented, and if it exceeds 2.5 parts by weight, poor marbled appearance and surface peeling will occur.

(Component C: flame retardant)
The resin composition of the present invention can contain a flame retardant. As the flame retardant, various compounds known as flame retardants for thermoplastic resins, particularly aromatic polycarbonate resins, can be used, but more preferably, (i) organic metal salt-based flame retardants (e.g., organic sulfonic acid alkali (earth) metal salt, boric acid metal salt-based flame retardants, and stannic acid metal salt-based flame retardants, etc., (ii) organic phosphorus-based flame retardants (e.g., monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds, etc.), and (iii) silicone-based flame retardants made of silicone compounds. The incorporation of compounds used as flame retardants not only improves flame retardancy, but also improves, for example, antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

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.

(Organometallic salt flame retardants)
The organic metal salt flame retardant is advantageous in that the heat resistance is almost maintained. The organic metal salt flame retardant most advantageously used in the present invention is an alkali (earth) metal salt of sulfonate. 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.

The metals constituting the metal ions of the fluorine-substituted organic sulfonic acid alkali (earth) metal salts are alkali metals or alkaline earth metals. Examples of alkali metals include lithium, sodium, potassium, rubidium, and cesium. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium. Alkaline metals are more preferred. Therefore, the preferred organic metal salt-based flame retardant is an alkali metal salt of perfluoroalkylsulfonic acid. Among such alkali metals, rubidium and cesium are preferred when a higher transparency is required, but they are not versatile and are difficult to purify, which can result in a disadvantage in terms of cost. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they can conversely be disadvantageous in terms of transparency. Taking these into consideration, the alkali metals in the alkali metal salts of perfluoroalkylsulfonic acid can be used differently, but potassium salts of perfluoroalkylsulfonic acid, which have an excellent balance of properties in all respects, are the most preferred. Such potassium salts can also be used in combination with alkali metal salts of perfluoroalkylsulfonic acid made of other alkali metals.

Examples of such perfluoroalkylsulfonic acid alkali metal salt 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 the like, and these can be used alone or in combination of two or more.Among these, potassium perfluorobutanesulfonate is particularly preferred.

The above-mentioned organometallic salt flame retardants preferably have a fluoride ion content of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less, as measured by ion chromatography. 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 substantially 0, but in terms of the balance between the refining process and the effect, a practical value of about 0.2 ppm is preferable. Perfluoroalkylsulfonic acid alkali metal salts having such a fluoride ion content are purified, for example, as follows. Perfluoroalkylsulfonic acid alkali metal salts are 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 salt of perfluoroalkylsulfonic acid is produced by neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or by neutralizing perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide (preferably the latter method). The ion-exchanged water is particularly preferably water having an electrical resistance of 18 MΩ·cm or more. The liquid in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably for 0.5 to 2.5 hours. The liquid is then cooled to a range of 0 to 40°C, more preferably 10 to 35°C. Crystals are precipitated by cooling. The precipitated crystals are removed by filtration. In this way, a suitable purified alkali metal salt of perfluoroalkylsulfonic acid is produced.

When a fluorine-substituted organic sulfonic acid alkali (earth) metal salt is used as the flame retardant, the content is preferably 0.01 to 1.0 parts 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. If 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 and antistatic properties) may be exhibited.

As an 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 (none of which contain a fluorine atom).

Preferred examples of aliphatic sulfonic acid metal salts include alkylsulfonic acid alkali (earth) metal salts, which can be used alone or in combination of two or more (herein, 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 alkylsulfonic acid alkali (earth) metal salts include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, etc., which can be used alone or in combination of two or more.

The aromatic sulfonic acid used in the aromatic sulfonate alkali (earth) metal salt may be at least one acid selected from the group consisting of monomeric or polymeric aromatic sulfide sulfonic acids, aromatic carboxylic acid and ester sulfonic acids, monomeric or polymeric aromatic ether sulfonic acids, aromatic sulfonate sulfonic acids, monomeric or polymeric aromatic sulfonic acids, monomeric or polymeric aromatic sulfone sulfonic acids, aromatic ketone sulfonic acids, heterocyclic sulfonic acids, aromatic sulfoxide sulfonic acids, and aromatic sulfonic acid condensates with methylene bonds, and these may be used alone or in combination of two or more.

Specific examples of aromatic sulfonic acid alkali (earth) metal salts include, for example, 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, benzenesulfonic acid Examples of such compounds 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.

Among the metal salts of organic sulfonic acids that do not contain fluorine atoms, aromatic sulfonic acid alkali (earth) metal salts are preferred, and potassium salts are particularly suitable. When such aromatic sulfonic acid alkali (earth) metal salts are blended as flame retardants, the content 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.

(Organophosphorus flame retardant)
As the organic phosphorus flame retardant of the present invention, a phosphate compound, particularly an aryl phosphate compound, is suitable. Such a phosphate compound is effective in improving flame retardancy, and has a plasticizing effect, so that although the heat resistance is reduced, it is advantageous in that the molding processability of the resin composition of the present invention can be improved. As such a phosphate compound, various phosphate compounds known as flame retardants can be used, but more preferably, one or more phosphate compounds represented by the following general formula [7] can be mentioned.

[In the above general formula [7], 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 having different n numbers, represents the average value thereof; R ²¹ , R ²² , R ²³ , and R Each of ²⁴ is independently a monohydric phenol residue derived from an aryl group selected from the group consisting of phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol.

The phosphate compound of the above formula [7] 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.

Specific examples of suitable dihydric phenols from which Y in the above formula [7] is derived include resorcinol, bisphenol A, and dihydroxydiphenyl, with resorcinol and bisphenol A being particularly preferred.

Preferred specific examples of the monohydric phenol from which R ²¹ , R ²² , R ²³ , and R ²⁴ in the above formula [7] are phenol, cresol, xylenol, and 2,6-dimethylphenol, and among these, phenol and 2,6-dimethylphenol are preferred.

Specific examples of the phosphate compound of the above formula [7] 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.

Another organic phosphorus-based flame retardant is phosphazene. Phosphazene contains phosphorus and nitrogen atoms in the molecule, which can impart flame retardancy to the resin composition. There are no particular limitations on the phosphazene, so long as it does not contain halogen atoms and has a phosphazene structure in the molecule. The phosphazene structure here refers to a structure represented by the formula: -P(R)=N- [wherein R is an organic group]. Phosphazene compounds are represented by the general formulas [8] and [9].

(In the above general formulas [8] and [9], R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ represent hydrogen, a hydroxyl group, an amino group, or an organic group not containing a halogen atom, and n represents an integer of 3 to 10.)

In the above formulas [8] and [9], 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 these, a cyclic phenoxyphosphazene represented by the following general formula [10] is preferred.

[In the above general formula [10], n represents an integer from 3 to 10.]

When an organic phosphorus flame retardant is used as the flame retardant, its content 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. If the content is within this preferred range, the effects expected from the inclusion of the organic phosphorus flame retardant (e.g., flame retardancy) may be exhibited.

(Silicone Compound)
The silicone compound of the present invention is not particularly limited as long as it can obtain the flame retardancy and transparency that are the object of the present invention, but it is preferable that the silicone compound has an aromatic group, and more preferably has a viscosity of 300 cSt or less at 25°C. If the viscosity is high, the transparency of the molded product may decrease. Furthermore, in order for the silicone compound to efficiently exert the flame retardant effect, the dispersion state during the combustion process is important. Viscosity is an important factor that determines such a dispersion state. This is because, when the silicone compound is too easily volatilized during the combustion process, that is, when the silicone compound has too low viscosity, the silicone remaining in the system during combustion is thin, making it difficult to form a uniform silicone structure during combustion. From this viewpoint, 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.

The aromatic groups in silicone compounds are bonded to silicone atoms, which contribute to improved compatibility with polycarbonate resins and maintaining transparency, and are also advantageous in forming a carbonized film during combustion, which contributes to the expression of flame retardant effects. If the compound does not have an aromatic group, it tends to be difficult to obtain transparency in molded products and a high level of flame retardancy.

The silicone compound of the present invention is preferably a silicone compound containing a Si-H group. In particular, it is a silicone compound containing a 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 [11] contained (aromatic group amount) is 10 to 70% by weight,

(In formula [11], 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 [11], 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.

More preferably, the Si-H group-containing unit is at least one silicone compound selected from among silicone compounds containing at least one of the structural units represented by the following general formulas [12] and [13].

(In formula [12] and formula [13], Z ¹ to Z ³ each independently represent 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 [14]. α1 to α3 each independently represent 0 or 1. m2 represents 0 or an integer of 1 or more. Furthermore, in formula [12], when m2 is 2 or more, the repeating unit can be a plurality of repeating units which are different from each other.)

(In formula [14], ^Z4 to ^Z8 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a heteroatom-containing functional group. α4 to α8 each independently represent 0 or 1. m3 represents an integer of 0 or 1 or more. Furthermore, in formula [14], when m3 is 2 or more, the repeating units can each 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.

Examples of the hydrocarbon group having 1 to 20 carbon atoms, which may have a heteroatom-containing functional group, in Z ¹ to Z ⁸ of the structural units represented by the above general formulae [12], [13] and [14] and in X of the general formula [11] include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and decyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl and allyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups, and these groups may further contain various functional groups such as epoxy groups, carboxy groups, carboxylic anhydride groups, amino groups, and mercapto groups. More preferred are alkyl groups, alkenyl groups 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 groups, vinyl groups, or phenyl groups.

In a silicone compound containing at least one of the structural units represented by the general formulas [12] and [13], when the compound has a plurality of repeating units of siloxane bonds, the repeating units may be in the form of a random copolymer, a block copolymer, or a tapered copolymer.

In the present invention, for silicone compounds containing preferred Si-H groups, it is preferable that the amount of Si-H in the silicone compound is in the range of 0.1 to 1.2 mol/100g. When the amount of Si-H is in the range of 0.1 to 1.2 mol/100g, the formation of a silicone structure during combustion becomes easier. More preferably, the amount of Si-H is in the range of 0.1 to 1.0 mol/100g, and most preferably in the range of 0.2 to 0.6 mol/100g. If the amount of Si-H is small, it becomes difficult to form a silicone structure, and if the amount of Si-H is large, the thermal stability of the composition decreases. Here, the silicone structure refers to a network structure formed by the reaction between silicone compounds or the reaction between a resin and silicone.

The amount of Si-H groups referred to here means the number of moles of Si-H structures contained in 100 g of a silicone compound, which can be determined by measuring the volume of hydrogen gas generated per unit weight of the silicone compound using an alkali decomposition method. For example, when 122 ml of hydrogen gas is generated per 1 g of a silicone compound at 25° C., the amount of Si-H is calculated to be 0.5 mol/100 g according to the following formula:
122×273/(273+25)÷22400×100≒0.5

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 and poorly dispersed, resulting in poor appearance. If the aromatic group content is more than 70% by weight, the molecular rigidity of the silicone compound itself becomes high, so that it may also be unevenly distributed and poorly dispersed, resulting in poor appearance.

The amount of aromatic groups herein refers to the proportion of aromatic groups represented by the above-mentioned general formula [11] contained in the silicone compound, and can be calculated by the following formula.
Aromatic group amount = [A/M] x 100 (weight%)
Here, A and M in the above formula respectively represent the following values.
A = the total molecular weight of all aromatic group moieties represented by the general formula [11] contained in one molecule of the silicone compound; M = the molecular weight of the silicone compound

Furthermore, the silicone compound used in the present invention desirably 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, it is a silicone compound 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, providing a resin composition with less cloudiness and good dyeability.

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. More preferably, the silicone compound has a volatilization amount of 10% or less. If the volatilization amount is more than 18%, there is a problem that the amount of volatile matter from the resin increases when the resin composition of the present invention is extruded and pelletized, and there is also a problem that the amount of air bubbles generated in the molded product is likely to increase.

The silicone compound used may be linear or branched as long as it satisfies the above conditions, and various compounds having Si-H groups at any one of a side chain, a terminal, a branch point, or at multiple sites in the molecular structure can be used.

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: monofunctional siloxane units such as ( _CH3 ) _{3SiO1/2 ,} H( _CH3 ) _{2SiO1/ 2} , _H2 ( _CH3 )SiO1 _/2 , ( _CH3 ) ₂ ( _CH2 =CH) _{SiO1 / 2} , ( _CH3 ) ₂ ( _C6H5 )SiO1 _{/ 2} , (CH3)( _C6H5 )( _CH2 =CH)SiO1 _/2, etc. D units: bifunctional siloxane units such as ( _CH3 ) _2SiO , H( _CH3 )SiO, _H2SiO , H( _C6H5 )SiO, ( _CH3 )( _CH2 = _CH )SiO, ( _C6H5 ) _2SiO , _etc. T units: ( _CH3 )SiO _{Q unit : a tetrafunctional siloxane} unit _{represented by SiO 2 .}

Specific examples of the structure of the silicone compound containing a Si _{- H group used} in the present invention include rational formulas Dn _{, Tp} , _MmDn , _MmTp , _MmQq , MmDnTp _{, MmDnQq , MmTpQq} , _MmDnTpQq , _DnTp , _DnQq , _{and DnTpQq . Of these , preferred} structures of _the silicone compound _{are MmDn , MmTp , MmDnTp , and MmDnQq , and more preferred structures are MmDn or MmDnTp .}
(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 more, the siloxane unit with that coefficient can be two or more types of siloxane units having different hydrocarbon groups having 1 to 20 carbon atoms that may have a bonded hydrogen atom or a heteroatom-containing functional group.)

Here, the sum of the coefficients in each rational formula is the average degree of polymerization of the silicone compound. In the present invention, the 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, and there is a problem that the resin composition containing this silicone compound is likely to have a large amount of volatile matter when processed. 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 kinds.

Such silicone compounds having Si-H bonds can be produced by conventional methods. For example, the target compound can be obtained by co-hydrolyzing the corresponding organochlorosilanes according to the structure of the target silicone compound and removing the by-products such as hydrochloric acid and low boiling points. In addition, when silicone oils having a hydrocarbon group with 1 to 20 carbon atoms, which may have Si-H bonds, aromatic groups represented by the general formula [10], or other heteroatom-containing functional groups in the molecule, cyclic siloxanes, or alkoxysilanes are used as starting materials, the target silicone compound can be obtained by using an acid catalyst such as hydrochloric acid, sulfuric acid, or methanesulfonic acid, optionally adding water for hydrolysis, proceeding with the polymerization reaction, and then similarly removing the acid catalyst and low boiling points used.

Furthermore, the silicone compound containing Si-H groups has siloxane units represented by the following structural formulas: M, M ^H , D, D ^H , D ^φ2 , T, T ^φ (where M: (CH ₃ ) ₃ SiO _1/2 M ^H : H(CH ₃ ) ₂ SiO _1/2 D: (CH ₃ ) ₂ SiOD ^H : H(CH ₃ )SiO ^φ2 : (C ₆ H ₅ ) ₂ SiT: (CH ₃ )SiO _3/2 T ^φ : (C ₆ H ₅ )SiO _3/2
When the average numbers of siloxane units per molecule are m, _mh , d, _dh , _dp2 , t, and _tp, respectively, it is preferable that all of the following relational expressions 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
Outside this range, it becomes difficult to simultaneously achieve good flame retardancy and excellent transparency in the resin composition of the present invention, and in some cases, it becomes difficult to produce the silicone compound containing Si--H groups.

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 easily generated during processing, and if the content is too low, flame retardancy may not be achieved.

(Component D: Fluorine-containing drip prevention agent)
The resin composition of the present invention may contain a fluorine-containing drip-preventing agent. By containing this fluorine-containing drip-preventing agent, good flame retardancy can be achieved without impairing the physical properties of the molded article.

Fluorine-containing anti-dripping agents include fluorine-containing polymers that have fibril-forming ability, such as polytetrafluoroethylene, tetrafluoroethylene-based copolymers (e.g., tetrafluoroethylene/hexafluoropropylene copolymers, etc.), partially fluorinated polymers such as those shown in U.S. Pat. No. 4,379,910, and polycarbonate resins produced from fluorinated diphenols. Of these, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferred.

PTFE with fibril-forming ability has an extremely high molecular weight, and shows a tendency to bond PTFE together and become fibrous due to external action such as shear force. Its molecular weight is 1 to 10 million, more preferably 2 to 9 million, in number average molecular weight calculated from the standard specific gravity. Such PTFE can be used in solid form or in the form of an aqueous dispersion. Furthermore, such PTFE with fibril-forming ability can be used in a mixed form with other resins to improve dispersibility in resins and to obtain even better flame retardancy and mechanical properties.

Commercially available PTFE products having such fibril-forming ability include, for example, Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemicals Co., Ltd. and Polyflon MPA from Daikin Industries, Ltd.
Representative examples of commercially available aqueous dispersions of PTFE 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 (registered trademark) 30J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.

Examples of mixed PTFE include: (1) a method in which an aqueous dispersion of PTFE is mixed with an aqueous dispersion or solution of an organic polymer and co-precipitated to obtain a co-aggregated mixture (methods described in JP-A-60-258263, JP-A-63-154744, etc.); (2) a method in which an aqueous dispersion of PTFE is mixed with dried organic polymer particles (method described in JP-A-4-272957); and (3) a method in which an aqueous dispersion of PTFE is uniformly mixed with an organic polymer particle solution and the respective media are simultaneously extracted from the mixture. (4) a method of removing the PTFE in an aqueous dispersion (method described in JP-A-06-220210, JP-A-08-188653, etc.), (5) a method of polymerizing a monomer that forms an organic polymer in an aqueous dispersion of PTFE (method described in JP-A-09-95583), and (6) a method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion to obtain a mixture (method described in JP-A-11-29679, etc.). Commercially available products of these mixed forms of PTFE include "Metablen A3800" (trade name) manufactured by Mitsubishi Rayon Co., Ltd., and "BLENDEX B449" (trade name) manufactured by GE Specialty Chemicals.

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 D component indicates the net amount of drip prevention agent, and in the case of mixed PTFE, indicates the net amount of PTFE.

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 parts by weight, the flame retardancy may be insufficient, and if it exceeds 5 parts by weight, PTFE may precipitate on the surface of the molded article, resulting in a poor appearance, as well as increasing the cost of the resin composition.

(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, as well as tertiary phosphines.

Specific examples of phosphite compounds 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-iso-propylphenyl)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.

Further, other phosphite compounds that react with dihydric phenols to form a cyclic structure can also be used, 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.

Examples of phosphate compounds 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, diisopropyl phosphate, etc., and preferably triphenyl phosphate and trimethyl phosphate.

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

Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

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.

The phosphorus-based stabilizers may be used alone or in combination of two or more. Among the phosphorus-based stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula [15] are preferred.

(In the above general formula [15], 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.)

As mentioned 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 can be used.

Among the above formula [15], more suitable phosphite compounds 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.

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 either 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 Corporation), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical Company), and Irgaofos 126 and 126FF (trademarks, manufactured by CIBA SPECIALTY CHEMICALS), and any of these may be used. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as Adekastab PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is commercially available as Adekastab PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark, manufactured by Dover Chemical Co., Ltd.), and either can be used.

(ii) Hindered phenol-based antioxidants As the hindered phenol compound, various compounds that are usually blended in resins can be used. Examples of such hindered phenol compounds include α-tocopherol, butyl hydroxytoluene, 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-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphone, and the like. 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'-di-thiobis(2,6-di-tert-butylphenyl) nol), 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'-hexamethylene bis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] pionyl]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, 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-(3-t Examples of the tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)acetyloxy]-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 are mentioned.

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 preferably used in the present invention. In particular, 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 preferred. The above hindered phenol-based antioxidants can be used alone or in combination of two or more.

It is preferable to use either a phosphorus-based stabilizer or a hindered phenol-based antioxidant, and it is even more preferable to use them in combination. The content of the phosphorus-based stabilizer and the hindered phenol-based antioxidant is 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 use 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.

(iii) Other Heat Stabilizers The resin composition of the present invention may contain other heat stabilizers other than the phosphorus-based stabilizer and the hindered phenol-based antioxidant. Such other heat stabilizers are preferably used in combination with either one of these stabilizers and antioxidants, and particularly preferably used in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers typified by 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). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and this compound can be used. Furthermore, stabilizers in which this compound is mixed with various phosphite compounds and hindered phenol compounds are commercially available. Suitable examples include Irganox HP-2921 manufactured by the above company. In the present invention, such premixed stabilizers can also be used. The amount of the lactone stabilizer to be added is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of component A.

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 applied to 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.

(iv) Mold release agent The polycarbonate resin composition of the present invention preferably further contains a mold release agent for the purpose of improving the productivity during molding and reducing distortion of the molded product. As such a mold release agent, a known one can be used. For example, 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 modification can also be used), silicone compounds, fluorine compounds (fluorine oils represented by polyfluoroalkyl ethers, etc.), paraffin wax, beeswax, etc. can be mentioned. Among them, fatty acid esters can be mentioned as a preferred mold release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such aliphatic alcohols may be monohydric alcohols or polyhydric alcohols having dihydric or higher valences. The carbon number of the alcohol is in the range of 3 to 32, more preferably in the range of 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, mannitol, etc. Polyhydric alcohols are more preferred in the fatty acid ester of the present invention.

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, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetoleic acid. Among the above, the aliphatic carboxylic acid is preferably one having 14 to 20 carbon atoms. Among them, saturated aliphatic carboxylic acids are preferred. Stearic acid and palmitic acid are particularly preferred.

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 such as beef tallow and lard, and vegetable fats and oils such as 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 produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used.

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 and are prone to inducing decomposition of the resin at high temperatures, so full esters are more preferable. 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.

The content of the 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. In 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 with good mold and roll releasability without impairing the good hue.

(v) Ultraviolet Absorber The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber in order to suppress ultraviolet degradation in outdoor applications. Specific examples of the ultraviolet absorber include benzophenone-based ultraviolet 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 absorbent include benzotriazole-based ultraviolet absorbents 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) Examples of the copolymer include 2-hydroxyphenyl-2H-benzotriazole skeleton-containing polymers such as 2-(2-hydroxy-5-acryloxyethylphenyl)-2H-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 copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole and vinyl monomers copolymerizable with the monomer. Specific examples of the ultraviolet absorber include hydroxyphenyltriazine-based compounds such as 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 the ultraviolet absorber include cyclic iminoesters such as 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazine-4-one). Specific examples of the ultraviolet absorber include cyanoacrylates such as 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 polymer type ultraviolet absorber obtained by copolymerizing such an ultraviolet absorbing monomer and/or a light stable monomer with a monomer such as an alkyl (meth)acrylate by adopting a structure of a monomer compound capable of radical polymerization. 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 the above, benzotriazole and hydroxyphenyl triazine are preferred in terms of ultraviolet absorbing ability, and cyclic imino ester and cyanoacrylate are preferred in terms of heat resistance and color. Specific examples include "Chemisorb 79" from Chemipro Chemical Co., Ltd. and "Tinuvin 234" from BASF Japan Co., Ltd. The ultraviolet absorber may be used alone or in a mixture of two or more kinds.

The content of the ultraviolet absorber is preferably 0.01 to 3 parts by weight, more preferably 0.01 to 1 part by weight, even more preferably 0.05 to 1 part by weight, and particularly preferably 0.05 to 0.5 parts by weight, per 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.

(vi) Dyes and Pigments The polycarbonate resin composition of the present invention further contains various dyes and pigments, and can provide molded products that exhibit a variety of designs. Examples of dyes and pigments 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 suitable as the metallic pigment. In addition, by blending a fluorescent brightener or other fluorescent dye that emits light, a better design effect that makes use of the luminous color can be imparted.

(vii) Fluorescent brightener In the resin composition of the present invention, the fluorescent brightener 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, and examples thereof 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 Company's "HAKKOL PSR." Here, the fluorescent brightener has the effect of absorbing ultraviolet energy of light and radiating this energy 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, relative to 100 parts by weight of component A. Even if the content exceeds 0.1 parts by weight, the effect of improving the color tone of the composition may be small.

(viii) Compounds having heat ray absorption ability The polycarbonate resin composition of the present invention may contain a compound having heat ray absorption ability. Suitable examples of such compounds include phthalocyanine-based near infrared absorbing agents, metal oxide-based near infrared absorbing agents such as ATO, ITO, iridium oxide, ruthenium oxide, immonium oxide, and titanium oxide, various metal compounds having excellent near infrared absorbing ability such as metal boride-based and tungsten oxide-based near infrared absorbing agents such as lanthanum boride, cerium boride, and tungsten boride, and carbon fillers. As such phthalocyanine-based near infrared absorbing agents, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (both natural and artificial), and fullerene, and preferably carbon black and graphite. These can be used alone or in combination of two or more kinds. 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), and more preferably in the range of 0.5 to 100 ppm, in the polycarbonate resin composition of the present invention.

(ix) Light Diffusion Agent The polycarbonate resin composition of the present invention can contain a light diffusion agent to impart a light diffusion effect. Examples of such light diffusion agents include polymer fine particles, inorganic fine particles with a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles already known as light diffusion agents for polycarbonate resins. More preferred examples include acrylic crosslinked particles with a particle size of several μm and silicone crosslinked particles represented by polyorganosilsesquioxane. Examples of the shape of the light diffusion agent include spherical, discoid, columnar, and indefinite shapes. Such spheres do not need to be perfect spheres and include deformed ones, and such columnar shapes include cubes. A preferred light diffusion agent is spherical, and the more uniform the particle size, the more preferred it is. The content of the light diffusion 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, relative to 100 parts by weight of component A. Two or more types of light diffusion agents can be used in combination.

(x) Highly light-reflective white pigment The polycarbonate resin composition of the present invention can contain a highly light-reflective white pigment to impart a light-reflecting effect. Titanium dioxide pigment (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-reflective 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-reflective white pigments can be used in combination.

(xi) Antistatic Agent The polycarbonate resin composition of the present invention may require antistatic performance, and in such a case, it is preferable to include an antistatic agent. Examples of such antistatic agents include (1) organic sulfonate phosphonium salts such as arylsulfonate phosphonium salts, such as dodecylbenzenesulfonate phosphonium salts, and alkylsulfonate phosphonium salts, as well as borate phosphonium salts such as tetrafluoroborate phosphonium salts. The content of the phosphonium salt is appropriately 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, relative to 100 parts by weight of the resin component. Examples of the antistatic agent 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, such metal salts include metal salts of dodecylbenzenesulfonic acid and metal salts of perfluoroalkanesulfonic acid. The content of the alkali (earth) metal salt of 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.

Examples of antistatic agents include (3) organic ammonium sulfonate salts such as ammonium alkylsulfonate salts and ammonium arylsulfonate salts. The amount of the ammonium salts is preferably 0.05 parts by weight or less based on 100 parts by weight of the resin component. Examples of antistatic agents include (4) polymers that contain a poly(oxyalkylene) glycol component as a constituent component, such as polyether ester amide. The amount of the polymer is preferably 5 parts by weight or less based on 100 parts by weight of the resin component.

(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, the fibrous filler is a filler having a fibrous shape (including rod-like, needle-like, or a shape in which the axis extends in multiple directions), and the plate-like filler is a filler having a plate-like shape (including a filler having an uneven surface or a filler having a curved plate). The granular filler is a filler having a shape other than these, including an indefinite shape. The above-mentioned fibrous or plate-like shape is often clear from the observation of the shape of the filler, but, for example, as a difference from the so-called indefinite shape, a filler having an aspect ratio of 3 or more can be said to be fibrous or plate-like.

Preferred examples of plate-like fillers include glass flakes, talc, mica, kaolin, metal flakes, carbon flakes, and graphite, as well as plate-like fillers in which the surface of these fillers is coated 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. In the range up to about 10 μm, the particle size refers to the value based on the median diameter (D50) of the particle size distribution measured by the X-ray transmission method, which is one of the liquid phase precipitation methods, in the range of 10 to 50 μm, the value based on the median diameter (D50) of the particle size distribution measured by the laser diffraction/scattering method, and in the range of 50 to 300 μm, the value based on the vibration sieving method. The particle size is the particle size 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 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.

The fiber diameter of the fibrous filler is preferably in the range of 0.1 to 20 μm.
The fiber diameter is preferably 3 μm, 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 an image 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 fibers, flat cross-section glass fibers, milled glass fibers, carbon fibers, milled carbon fibers, metal fibers, asbestos, rock wool, ceramic fibers, slag fibers, 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, typified by heat-resistant organic fibers such as aramid fibers, polyimide fibers, and polybenzothiazole fibers, as well as fibrous fillers obtained by surface-coating these fillers with a different material such as a metal or metal oxide. Examples of fillers surface-coated with a different material include metal-coated glass fibers, metal-coated glass flakes, titanium oxide-coated glass flakes, and metal-coated carbon fibers. The method of surface coating of different materials is not particularly limited, and examples thereof include various known plating methods (e.g., electrolytic plating, electroless plating, hot-dip plating, etc.), vacuum deposition, ion plating, CVD (e.g., thermal CVD, MOCVD, plasma CVD, etc.), PVD, and sputtering. Here, the 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, and preferably 200. The aspect ratio of such a filler is a value in a resin composition. The flat cross-section glass fiber is a glass fiber having an average major axis value of 10 to 50 μm, preferably 15 to 40 μm, and more preferably 20 to 35 μm, and an average major axis/minor axis ratio (major axis/minor axis) of 1.5 to 8, preferably 2 to 6, and more preferably 2.5 to 5. The fibrous filler may be surface-treated with various coupling agents, bundled with various resins, and granulated by compression, in the same manner as the plate-like filler. 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.

(xiii) Other resins and elastomers In the polycarbonate resin composition of the present invention, other resins and elastomers can be used in small proportions in place of a part of the resin component of component A, as long as the effects of the present invention are exhibited. The amount of the other resins and elastomers 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 with 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 the elastomer 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.

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

<Production of Resin Composition>
Any method may be adopted for producing the resin composition of the present invention. For example, the A component, the B component, and any other components may be thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then granulated as necessary using an extrusion granulator or a briquetting machine, followed by melt kneading using a melt kneader such as a vented twin-screw extruder, and pelletizing using a device such as a pelletizer.

<Production of Molded Products>
The resin composition of the present invention can be obtained by injection molding such pellets. In such injection molding, not only the usual cold runner type molding method but also hot runners that enable runnerless production can be used. In addition, in injection molding, not only usual molding methods but also 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, heat insulating mold molding, and in-mold remelting molding, as well as molding methods consisting of combinations thereof, can be used. Furthermore, various surface treatments can be performed on molded articles formed from the resin composition. As surface treatments, various surface treatments such as decorative painting, hard coating, water-repellent/oil-repellent coating, hydrophilic coating, ultraviolet absorbing coating, infrared absorbing coating, electromagnetic wave absorbing coating, heat generating coating, antistatic coating, antistatic coating, conductive coating, and metallizing (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying, etc.) can be performed.

(Low temperature impact strength)
The polycarbonate resin composition of the present invention has a notched Charpy impact strength of preferably 30 kJ/m2 or more, more preferably 40 kJ/ ^m2 or more, and even more preferably 50 kJ/ ^m2 or more, as measured on a test piece cooled to -30° ^C in accordance with ISO 179. If the notched Charpy impact strength is less than 30 kJ/ ^m2 , it is difficult to apply the composition to outdoor structural members, various housing members, and automobile-related parts for cold regions.

(Appearance and color stability)
The appearance of the three-stage plate made using the polycarbonate resin composition of the present invention is characterized by only slight defects such as black discoloration due to black spots, 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 is not satisfied, the production of products with defective appearance will lead to increased costs, and the productivity will be significantly reduced by disassembling and cleaning the molding machine as a countermeasure, making it unsuitable for use as an exterior material. In addition, the black discoloration appearance defect due to black spots can also be evaluated by the variation ΔL ^* value of the hue L ^* during continuous molding. Here, L ^* is a value representing the lightness in the CIE 1976 L ^* a ^* b ^* color space standardized in JIS Z 8781-4, and sensitively reflects the effect of black discoloration due to black spots. The polycarbonate resin composition of the present invention has a maximum color difference ΔL ^* value of L ^* value measured in accordance with JIS Z 8781-4 for a molded product obtained by continuous molding for 25 shots at a molding temperature of 280° C., of preferably 3 or less, more preferably 2 or less, more preferably 1 or less, and even more preferably 0.5 or less. If the ΔL ^* value exceeds the above range, it may lead to an increase in costs due to the occurrence of products with defective appearance, and a significant decrease in productivity due to the need to disassemble and clean the molding machine as a countermeasure, and the composition is unsuitable for use as an exterior material.

The present invention will be described in more detail below with reference to examples, but these 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 performed according to the following methods.

(1) Viscosity average molecular weight (Mv)
The specific viscosity (η _SP ) calculated by the following formula 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−t ₀ )/t ₀
[ _t0 is the number of seconds that methylene chloride falls, and t is the number of seconds that the sample solution falls]
The viscosity average molecular weight Mv was calculated from the determined specific viscosity (η _SP ) according to 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

(2) Polydiorganosiloxane Component Content and Average Number of Repeats of Polydiorganosiloxane (p+q)
^{The 1} H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer was measured using an NMR JNM-AL400 manufactured by JEOL Ltd., and the integral ratio of the peak derived from the dihydric phenol (I) was compared with the integral ratio of the peak derived from the hydroxyaryl-terminated polydiorganosiloxane (II) to calculate the average chain length p+q. Similarly, the integral ratio of the peak derived from the hydroxyaryl terminal was compared with the integral ratio of the peak derived from the polydiorganosiloxane to calculate the average chain length p+q.

(3) Average size of polydiorganosiloxane domain Component A was dried with hot air at 120° C. for 5 hours, and then molded in an injection molding machine (manufactured by Japan Steel Works, Ltd., JSW
A molded piece having a width of 10 mm, a length of 80 mm, and a thickness of 4.0 mm was molded using a microtome (EM UC6 manufactured by Leica Microsystems) at a molding temperature of 290° C., a mold temperature of 80° C., and a molding cycle of 50 seconds. A portion of the intersection of the obtained molded piece, 15 mm from the gate and 5 mm from the side end, and 2 mm deep, was cut perpendicular to the flow direction of the resin using a microtome (EM UC6 manufactured by JEOL Ltd.).
The particles were attached to a microscopic microscope (FINE GRID No. 2632 F-200-CU 100PC/CA) and observed at an accelerating voltage of 200 kV using a TEM JEM-2100 manufactured by JEOL Ltd. The observation magnification was 20,000 times. The obtained micrographs were subjected to particle analysis using image analysis software Win ROOF Ver. 6.6 (Mitani Shoji Co., Ltd.) to obtain the average size of the polydiorganosiloxane domains in the sample slices. Here, the maximum major axis (the length when any two points on the outer contour of the particle are selected so that the length 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.

(4) Visual appearance of molded piece and ΔL ^*
After drying the pellets of the resin composition with hot air at 120°C for 5 hours, 25 square plates with a width of 50 mm, a length of 100 mm, and a thickness of 2 mm were continuously molded using an injection molding machine (NEX50-5E, manufactured by Nissei Plastics Co., Ltd.) at a molding temperature of 280°C, a mold temperature of 70°C, and a molding cycle of 40 seconds, and the appearance was evaluated visually. Examples of appearance defects include black discoloration due to black spots, marbled appearance, and surface peeling of the bent surface when the square plate is bent by 90°, and the evaluation was based on the presence or absence and the degree of each.

[Black stuff]
⊚: No blackening due to black spots is observed.
◯: Blackening due to black spots is slight, gradually subsides, or occurs at a frequency of 20% or less.
×: There is noticeable blackening due to black spots.
[Marble pattern]
⊚: No defects in marble-like appearance.
◯: There is some defect in the marbled appearance, but it is minor.
×: There is noticeable glare and poor marbled appearance.
[Surface peeling]
⊚: No surface peeling was observed.
A: There is surface peeling, but it is minor.
×: Significant surface peeling is observed.

The obtained molded pieces were measured for CIE 1976 L ^* a ^* b* lightness L ^* value in accordance with JIS Z 8781-4 using a spectrophotometer CE-7000A (Greta Macbeth) under ^a D65 light source and a 10- ^degree visual field in reflection. The difference between the highest L ^* value and the lowest L ^* value among the obtained 25 pieces was taken as the maximum color difference ΔL ^* value.

(5) Low-temperature impact strength evaluation (notched Charpy impact strength)
The pellets of the resin composition were dried with hot air at 120°C for 5 hours, and then injection molded (FANUC Corporation, ROBOSHOT α-S100iA) to produce molded pieces with a width of 10 mm, a length of 80 mm, and a thickness of 4.0 mm 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 test pieces cooled to -30°C was measured in accordance with ISO179.

[Both Ends 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 end-modified polydimethylsiloxane with p+q=130, synthesized according to the method for producing 2-allylphenol end-modified polydiorganosiloxane described in Japanese Patent No. 2662310.

[Preparation 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.
(Production method of PC-POS-1)
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 [5] and 7.5 parts of hydrosulfite were dissolved therein. Then, 11,246 parts of methylene chloride (8 molar equivalents with respect to the total amount of the 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 sodium hydroxide solution 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 [6] 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 vigorously stirring again. Under such stirring, 4.2 parts of triethylamine were added when the reaction solution was at 26°C, and 15 minutes later, 2795 parts of methylene chloride (2 molar equivalents relative to the total amount of dihydric phenols) were added, and the reaction was terminated by continuing stirring for 1 hour from the addition of triethylamine at a temperature of 26-31°C. After the reaction was completed, the organic phase was separated, diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, it was introduced into a kneader filled with warm water, and the methylene chloride was evaporated while stirring to obtain a powder of a polycarbonate-polydiorganosiloxane copolymer. After dehydration, the mixture was dried for 12 hours at 120°C in a hot air circulation 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.

(Production method of PC-POS-2)
The same production method as in the production of PC-POS-1 was carried out, except that a solution prepared by dissolving 198 parts (0.064 moles) of the above-mentioned KF-2201 as the dihydric phenol (II) represented by the general formula [6] in 100 parts of methylene chloride (0.07 molar equivalents relative to the total amount of dihydric phenols) was added, and then a solution prepared by dissolving 463 parts (0.064 moles) of KF-2102 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 having a maximum length of 80 nm or more, and 0 polydiorganosiloxane domains having a maximum length of 400 nm or more.

(Production method of PC-POS-3)
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 equivalent based on the total amount of dihydric phenol) was added as the dihydric phenol (II) represented by the general formula [6]. The polycarbonate-polydiorganosiloxane copolymer obtained had an average polydiorganosiloxane repeat number (p+q) of 90, a viscosity average molecular weight of 16,000, a polydiorganosiloxane component content of 12.6% by weight, an average size of polydiorganosiloxane domains 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.

(Production method of PC-POS-4)
The same production method as for PC-POS-1 was used, except that a solution of 661 parts (0.066 moles) of the above (II)-3 (number of repetitions p+q=130) as the dihydric phenol (II) represented by the general formula [6] dissolved in 356 parts of methylene chloride (0.25 molar equivalents relative to the total amount of dihydric phenol) was added. The polycarbonate-polydiorganosiloxane copolymer obtained had an average polydiorganosiloxane repetition number (p+q) of 130, a viscosity average molecular weight of 16,100, a polydiorganosiloxane component content of 12.7% by weight, an average size of polydiorganosiloxane domains 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.

(Production method of PC-POS-5)
The same production method as in the production of PC-POS-1 was carried out, 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 [6] dissolved in 33 parts of methylene chloride (0.021 molar equivalent based on the total amount of dihydric phenols) was added, and then a solution of 154 parts (0.021 mole) of KF-2102 dissolved in 77 parts of methylene chloride (0.06 molar equivalent based on the total amount of dihydric phenols) was added, and a solution of 99 parts of p-tert-butylphenol dissolved in 891 parts of methylene chloride (0.64 molar equivalent based on 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 weight %, an average polydiorganosiloxane domain size of 31 nm, the number of polydiorganosiloxane domains having a maximum length of 80 nm or more was 4, and the number of polydiorganosiloxane domains having a maximum length of 400 nm or more was 0.

(Production method of PC-POS-6)
A polycarbonate-polydiorganosiloxane copolymer produced under the production conditions of Example 8 described in WO2011/013846. A reactor equipped with a thermometer, a stirrer, and a reflux condenser was charged with 21,592 parts of ion-exchanged water and 3,675 parts of a 48.5% aqueous sodium hydroxide solution, and 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 [5] and 7.6 parts of hydrosulfite were dissolved therein. 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 a period of 60 minutes at 22 to 30° C. with stirring. 7283 parts of methylene chloride (5 molar equivalents relative to the total amount of dihydric phenols) was added, 1131 parts of 48.5% aqueous sodium hydroxide solution and a solution of 108 parts of p-tert-butylphenol dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenols) were added, and while stirring, a solution of 430 parts (0.139 moles) of the above KF-2201 as dihydric phenol (II) represented by the general formula [6] dissolved in 800 parts of methylene chloride (0.55 molar equivalents relative to the total amount of dihydric phenols) 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. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26°C, and the reaction was terminated by continuing stirring at a temperature of 26 to 31°C for 1 hour. 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 was almost 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 with stirring to obtain a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, the mixture was dried at 120°C for 12 hours in a hot air circulation dryer. The polycarbonate-polydiorganosiloxane copolymer obtained had an average polydiorganosiloxane repeat number (p+q) of 40, a viscosity average molecular weight of 19,400, a polydiorganosiloxane component content of 8.4% by weight, an average size of polydiorganosiloxane domains 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.

(PC-1)
Linear aromatic polycarbonate resin powder with a solution viscosity of 23,900 and a molecular weight of 23,900, which has a repeating skeleton of 2,2-bis(4-hydroxyphenyl)propane (Panlite L-1250WP, manufactured by Teijin Limited)

(Component B)
B-1: (meth)acrylic modified polyorganosiloxane (product name: Chaline R170, manufactured by Nissin Chemical Co., Ltd., a graft copolymer using polydimethylsiloxane as the B1 component and methyl methacrylate as the B2 component, polydimethylsiloxane content: 70% by weight)
B-2 (Comparative Example): Polydimethyl silicone (KF96-1000cs (product name) manufactured by Shin-Etsu Chemical Co., Ltd.)
B-3 (Comparative Example): Polymethyl methacrylate resin (Acrypet VH001 (product name) manufactured by Mitsubishi Chemical Corporation)

(Component C)
C-1: Cyclic phenoxyphosphazene (Ravitor FP-110T (product name) manufactured by Fushimi Pharmaceutical Co., Ltd.)

(Component D)
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 (product name))

(Other ingredients)
E-1: 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate (manufactured by BASF Japan Ltd.: Irganox 1076 (trade name))
E-2: Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168 (trade name) manufactured by BASF Japan Ltd.)
F-1: UV absorber (ADEKA STAB LA-31 (product name) manufactured by ADEKA CORPORATION) TiO ₂ : Titanium dioxide (Ishihara Sangyo Kaisha, Ltd., Typeque PC-3 (product name))

[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 using a blender, and melt-kneaded using a vented twin-screw extruder to obtain pellets. The various additives used were premixed with polycarbonate resin in advance at a concentration of 10 to 100 times the amount of each additive, and then the entire mixture was mixed using a blender. The vented twin-screw extruder used was a KTX-30 (diameter 30 mmφ) manufactured by Kobe Steel, Ltd. A strand was extruded under the conditions of a cylinder temperature and a die temperature of 280° C., a screw rotation speed of 150 rpm, a discharge rate of 20 kg/h, and a vent suction degree of 3 kPa, and after cooling in a water bath, the strand was cut using a pelletizer and pelletized. The results of the various evaluations are shown in Tables 2 and 3.

[Examples 1 to 10, Comparative Examples 1 to 8]
As is clear from the above table, the compositions of Examples 1 to 10 show good low-temperature impact resistance exceeding 40 kJ/ ^m2 , while suppressing black discoloration due to black spots, marbled appearance, and surface peeling. In contrast, Comparative Examples 1 and 2, which do not contain B component or have a small amount of B component, cause black discoloration due to black spots. On the other hand, Comparative Example 3, which has a large amount of B component, and Comparative Example 7, which uses a PC-POS copolymer with a large POS repeat number, cause strong marbled appearance defects and surface peeling. On the other hand, Comparative Example 6, which uses a PC-POS copolymer with a small POS repeat number, and Comparative Example 8, which does not use a PC-POS copolymer, have poor low-temperature impact resistance. In addition, Comparative Examples 4 and 5, which use a polyorganosiloxane or (meth)acrylic resin that is not (meth)acrylic modified as B component, cause black discoloration due to black spots.

Claims (15)

(A) A polycarbonate resin composition comprising (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) 100 parts by weight of a resin component (A component) consisting of 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 (meth)acrylic-modified polyorganosiloxane (B component).
[(In the above general formula [1], R ¹ and R ² each independently represent 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 a plurality 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].)
(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 represent 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, and when there are a plurality of such 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.
(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; 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; and X is a divalent aliphatic group having 2 to 8 carbon atoms.) The polycarbonate resin composition according to claim 1, characterized in that p+q in the above formula [3] is 50 to 70. The polycarbonate resin composition according to claim 1 or 2, characterized in that the content of the polydiorganosiloxane block represented by the above formula [3] in component A-1 is 4 to 20% by weight. The polycarbonate resin composition according to any one of claims 1 to 3, characterized in that the content of the polydiorganosiloxane block represented by the above formula [3] in component A is 2.5 to 6.5% by weight. The polycarbonate resin composition according to any one of claims 1 to 4, characterized in that the viscosity average molecular weight of component A-1 is 11,000 to 30,000. 6. The polycarbonate resin composition according to any one of claims 1 to 5, 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. 7. The polycarbonate resin composition according to claim 1 , wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula [3] are methyl groups. 8. 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. The polycarbonate resin composition according to any one of claims 1 to 8, characterized in that component B is a (meth)acrylic-modified polyorganosiloxane obtained by graft copolymerizing a (meth)acrylic acid ester (component B2) with a polyorganosiloxane (component B1) represented by the following general formula [ 4] :
[In the above general formula [4], R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and Y represents an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group. ^X1 and ^X2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a group ^{represented by SiR4R5R6} ( ^R4 and ^R5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, and ^R6 represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, or an organic group having at least one group selected from the group consisting of a vinyl group, an allyl group, and a γ-(meth)acryloxypropyl group, and an SH group), m is an integer of 1 to 10,000, n is an integer of 1 or more, and the siloxane chain may be branched.] The polycarbonate resin composition according to claim 9 , wherein R ¹ , R ² and R ³ in the formula [4] are methyl groups. 11. The polycarbonate resin composition according to claim 9 , wherein component B2 is methyl methacrylate and/or 2-hydroxyethyl methacrylate. The polycarbonate resin composition according to any one of claims 1 to 11, characterized in that a molded product ^{obtained by continuous molding for 25 shots at a molding temperature of 280°C has a maximum color difference ΔL*} value ^of 3 or less as measured in accordance with JIS Z 8781-4. 13. The polycarbonate resin composition according to any one of claims 1 to 12 , further comprising 0.001 to 20 parts by weight of a flame retardant (C) (Component C) per 100 parts by weight of Component A. The polycarbonate resin composition according to any one of claims 1 to 13 , further comprising 0.01 to 5 parts by weight of a fluorinated drip-preventing agent (D) (Component D) per 100 parts by weight of Component A. A molded article formed from the polycarbonate resin composition according to any one of claims 1 to 14 .