KR20140077164A - Polycarbonate resin composition - Google Patents

Abstract

[R¹ 및 R² 는, 할로겐 원자, 알킬기 또는 알콕시기를 나타낸다. X 는 단결합, 알킬렌기 알킬리덴기, 시클로알킬렌기, 시클로알킬리덴기, -S-, -SO-, -SO₂-, -O- 또는 -CO- 를 나타낸다. a 및 b 는 0 ∼ 4 의 정수를 나타낸다. R³ ∼ R⁶ 은 수소 원자, 할로겐 원자 또는 알킬기, 알콕시기 또는 아릴기를 나타낸다. Y 는 단결합, 지방족 또는 방향족을 포함하는 유기 잔기를 나타낸다. n 은 평균 반복수.]A polycarbonate resin composition having excellent color appearance while maintaining excellent properties of a polyorganosiloxane-polycarbonate copolymer is provided.
Specifically, a polycarbonate-polyorganosiloxane copolymer (A) having a main chain of a repeating unit represented by the general formula (I) and a structural unit represented by the general formula (II) Is 5 to 100% by mass, the content of the structural unit represented by the general formula (II) is 25 to 65, the content of the structural unit represented by the general formula (II) is 2 to 20% by mass, (II) is a polycarbonate-polyorganosiloxane copolymer having a repeating unit represented by the general formula (I) and a structural unit represented by the general formula (II), wherein n in the general formula (II) 0 to 95% by mass of a polycarbonate-polyorganosiloxane copolymer (A-2) having a content of constituent units representing 2 to 20% by mass and an aromatic polycarbonate other than the above (A-1) (A-3) 0 to 95% by mass of a polycarbonate 99.9 to 96 parts by mass of a resin (B) and 0.1 to 4 parts by mass of titanium oxide (provided that the total amount of the component (A) and the component (B) is 100 parts by mass) do.

[R ¹ and R ² represent a halogen atom, an alkyl group or an alkoxy group. X represents a single bond, an alkylene group, an alkylidene group, a cycloalkylene group, a cycloalkylidene group, -S-, -SO-, -SO ₂ -, -O- or -CO-. a and b represent an integer of 0 to 4; R ³ to R ⁶ represent a hydrogen atom, a halogen atom or an alkyl group, an alkoxy group or an aryl group. Y represents an organic residue including a single bond, aliphatic or aromatic. n is the average number of iterations.]

Description

[0001] POLYCARBONATE RESIN COMPOSITION [0002]

The present invention relates to a polycarbonate resin composition.

Polycarbonate resins are excellent in mechanical strength, electrical properties and transparency, and are widely used in various fields such as electric and electronic devices, automobiles, and the like as engineering plastics. Polycarbonate resins are also used in cases such as mobile phones, mobile PCs, digital cameras, video cameras, power tools, etc. In these applications, impact resistance is important in terms of dropping during handling, (Especially color) are also important factors.

However, resin materials are relatively easy to color, and colored resin materials are used in many places. Particularly, white or gray are widely used. On the other hand, a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes referred to as PC-PDMS) obtained by copolymerizing a polyorganosiloxane is known. PC-PDMS is expected to be applied to the above applications because of its excellent properties such as impact resistance. In addition, the use of titanium oxide as a pigment is preferable in view of the importance of impact resistance in the above-mentioned applications and also in designability.

In the past, it has been known that the combination of PC-PDMS and titanium oxide has a white appearance and a good impact strength. For example, there has been known a polycarbonate resin composition (see Patent Document 1) which is excellent in mechanical properties such as impact resistance and rigidity, optical properties and the like, and also has excellent reflectance characteristics. According to Patent Document 1, the composition containing PC-PDMS in which the content of titanium oxide is 5 to 10% shows good reflectance and mechanical strength. In another example, there is known a polycarbonate resin composition which does not contain a phosphorus-based flame retardant or a halogen-based flame retardant, exhibits excellent flame retardancy, and has high reflectivity, high-order lightness and excellent thermal stability (see Patent Document 2). According to Patent Document 2, the PC-PDMS-containing composition in which the content of titanium oxide is 5 to 50% exhibits good reflectance and Izod impact strength and flame retardancy.

Although the compositions described in these documents exhibit high light reflecting properties, the strength of the original PC-PDMS is lower than that of the original PC-PDMS because of the high content of titanium oxide. On the other hand, , It has been desired to develop a PC-PDMS-containing composition having a good reflectance, mechanical strength and the like and having a smaller titanium oxide content.

On the other hand, a composition containing a relatively small amount (for example, 1 to 2.5% by weight) of titanium oxide and PC-PDMS is also known (see Patent Document 3).

Japanese Unexamined Patent Publication No. 5-320519 Japanese Laid-Open Patent Publication No. 2004-91567 Japanese Patent Publication No. 2007-509208

In the PC-PDMS-containing composition described in Patent Document 3, titanium oxide is used in small quantities as a means for improving flame retardancy, but there is no description about color appearance.

It is therefore an object of the present invention to provide a polycarbonate resin composition having excellent color appearance while maintaining excellent properties of a polycarbonate-polyorganosiloxane copolymer.

As a result of intensive studies, the inventors of the present invention have found that when a polysiloxane chain length in a polycarbonate-polyorganosiloxane copolymer is short, it is difficult to exhibit strength, so that a length of a polysiloxane chain length of at least a certain value is required for exhibiting impact resistance, , When the polysiloxane chain length is long, it is possible to find that the appearance of black stripes on the surface of the molded article is poor, although it exhibits good strength. I found that I could have an appearance.

That is, the present invention relates to the following [1] to [10].

(1) A polycarbonate-polyorganosiloxane copolymer having a main chain represented by the general formula (I) and a structural unit represented by the general formula (II), wherein n in the general formula (II) 5 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1) having a constitutional unit represented by the general formula (II) in an amount of 2 to 20% by mass,

A polycarbonate-polyorganosiloxane copolymer having a main chain of a repeating unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), wherein n in the general formula (II) is 70 to 350, 0 to 95% by mass of a polycarbonate-polyorganosiloxane copolymer (A-2) having a constituent unit represented by the formula (II) in an amount of 2 to 20% by mass,

99.9 to 96 parts by mass of a polycarbonate resin composed of 0 to 95% by mass of an aromatic polycarbonate (A-3) other than the above-mentioned (A-1) and (A-2)

(B): 0.1 to 4 parts by mass of titanium oxide (provided that the sum of the components (A) and (B) is 100 parts by mass).

[Chemical Formula 1]

[Wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, SO ₂ -, -O- or -CO-. a and b each independently represent an integer of 0 to 4;

R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y represents an organic residue including a single bond, aliphatic or aromatic. n is the average number of iterations.]

[2] The polycarbonate resin composition according to the above [1], wherein in the constituent unit represented by the general formula (II), Y is an organic residue derived from allylphenol or augenol.

[3] The polycarbonate resin composition according to [1] or [2], wherein in the repeating unit represented by the general formula (I), X is an isopropylidene group and a = b =

[4] The polycarbonate resin composition according to any one of [1] to [3], wherein in the constituent unit represented by the general formula (II), R ³ to R ⁶ are all methyl groups.

[5] The polycarbonate resin composition according to [1] or [2], wherein the content of the structural unit (II) derived from the component (A-2) The polycarbonate resin composition according to any one of the above [1] to [4], wherein the content of the polycarbonate resin composition is 2.5% by mass or less.

[6] The polymer composition according to any one of [1] to [5] above, which further comprises 0.1 to 1 part by mass of a polytetrafluoroethylene-containing mixed powder (C) relative to 100 parts by mass in total of the components (A) A polycarbonate resin composition according to any one of the preceding claims.

[7] The positive resist composition according to any one of [1] to [5], further comprising (D) 0.01 to 0.15 parts by mass of at least one member selected from the group consisting of an alkali metal salt of an organic sulfonic acid and an alkaline earth metal salt of an organic sulfonic acid based on 100 parts by mass of the total of 100% , The polycarbonate resin composition according to any one of [1] to [6] above.

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

[9] A component for an electric or electronic device comprising the polycarbonate resin composition according to any one of [1] to [7].

[10] An automotive part comprising the polycarbonate resin composition according to any one of [1] to [7].

According to the present invention, it is possible to provide a polycarbonate resin composition having excellent color appearance while maintaining excellent properties of the polyorganosiloxane-polycarbonate copolymer. The polycarbonate resin composition of the present invention is also excellent in flame retardancy.

[Polycarbonate-based resin composition]

The present invention relates to a polycarbonate-polyorganosiloxane copolymer (A) having a main chain having a repeating unit represented by the general formula (I) and a constitutional unit represented by the general formula (II) , 5 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1) having a content of structural units represented by the general formula (II) of 2 to 20% by mass,

A polycarbonate-polyorganosiloxane copolymer having a main chain of a repeating unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), wherein n in the general formula (II) is 70 to 350, 0 to 95% by mass of a polycarbonate-polyorganosiloxane copolymer (A-2) having a constituent unit represented by the formula (II) in an amount of 2 to 20% by mass,

99.9 to 96 parts by mass of a polycarbonate resin composed of 0 to 95% by mass of an aromatic polycarbonate (A-3) other than the above-mentioned (A-1) and (A-2)

(B): 0.1 to 4 parts by mass of titanium oxide (provided that the total amount of the component (A) and the component (B) is 100 parts by mass).

(2)

[Wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, SO ₂ -, -O- or -CO-. a and b each independently represent an integer of 0 to 4;

R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y represents an organic residue including a single bond, aliphatic or aromatic. n is the average number of iterations.]

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

Examples of the alkyl group represented by R ¹ and R ² each independently include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups (the term "various groups" , The same applies hereinafter), various pentyl groups, and various hexyl groups. Examples of the alkoxy group represented by R ¹ and R ² each independently include the case where the alkyl group is the above alkyl group.

The alkylene group represented by X includes, for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. As the cycloalkylidene group represented by X, for example, a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group and the like can be given, and a cycloalkylidene group having 5 to 10 carbon atoms Group is preferable, and a cycloalkylidene group having 5 to 8 carbon atoms is more preferable.

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

In the general formula (II), examples of the halogen atom represented by R ³ to R ⁶ each independently include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group and the alkoxy group represented by R ³ to R ⁶ each independently include the same groups as those for R ¹ and R ² . Examples of the aryl group represented by R ³ to R ⁶ each independently include a phenyl group and a naphthyl group.

The organic residue containing an aliphatic group represented by Y is, for example, an alkylene group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms). Examples of the organic residue containing an aromatic group represented by Y include an arylene group having 6 to 12 ring-forming carbon atoms such as a phenylene group, a naphthylene group and a biphenyldiyl group.

((A) polycarbonate resin)

- (A-1) -

First, the "polycarbonate-polyorganosiloxane copolymer (A-1)" which is one of the components (A) and is an essential component will be described.

The polycarbonate-polyorganosiloxane copolymer (A-1) preferably contains 2 to 20% by mass, preferably 2 to 15% by mass, more preferably 2 to 20% by mass, of the constituent unit represented by the formula (II) To 10% by mass, more preferably 3 to 8% by mass, still more preferably 4 to 7% by mass, and particularly preferably 4 to 6% by mass. If it is less than 2% by mass, the effect of improving the impact resistance is insufficient, and if it exceeds 20% by mass, the heat resistance deteriorates greatly.

In the structural unit (A-1), the average repeating number n in the structural unit represented by the general formula (II) is 25 to 65, preferably 30 to 60, more preferably 30 to 50, And preferably 30 to 45. In the case of (A-1), when n is less than 25, the effect of improving the impact resistance is not sufficient, and when it exceeds 65, it is difficult to obtain a good color appearance.

The viscosity average molecular weight (Mv) of the polymer (A-1) is preferably 16,000 to 30,000, more preferably 16,000 to 25,000, and still more preferably 17,000 to 23,000. When the viscosity average molecular weight of the component (A-1) is within this range, the strength of the molded product becomes sufficient, the viscosity of the copolymer is not excessively increased, the productivity during production becomes stable, and the molding with a small thickness becomes easy.

The polycarbonate-polyorganosiloxane copolymer (A-1) is obtained by reacting a divalent phenol represented by the following formula (1), a polyorganosiloxane represented by the following formula (2), phosgene, a carbonate ester or a chloroform / RTI > acid, or a mixture thereof. The polycarbonate-polyorganosiloxane copolymer (A-1) can also be prepared by reacting a polycarbonate oligomer (for example, a polycarbonate oligomer having a chloroformate group at the terminal) with a polyorganosiloxane .

In the production of the polycarbonate-polyorganosiloxane copolymer (A-1), the reaction rate of the polyorganosiloxane represented by the following general formula (2) is preferably 95% or more, more preferably 97% , More preferably not less than 99%.

(3)

[In the general formula (1), X, R ¹ to R ² , a and b are the same as those in the general formula (I). In the general formula (2), R ³ to R ⁶ , Y and n are the same as those in the general formula (II), and when producing (A-1), n is 25 to 65 . Z is a halogen ^{atom, -R 7 OH, -R 7 -Z'} -R 8 -OH, -R 7 COOH, -R 7 NH 2, represents an -SH or -COOH, wherein R ⁷ is a substituted or beach A substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, or a substituted or unsubstituted arylene group. Wherein R ⁸ is and represents an arylene ring forming carbon number of 6 to 12, wherein Z 'is a cycloalkylene group, a C 1 -C 8 alkylene group, having a carbon number of 2-8 alkylidene group, a carbon number of 5 to 10 of a carbon number of 5 to 10 < / RTI > cycloalkylidene group. and m represents 0 or 1.]

Examples of the halogen atom represented by Z include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among them, a chlorine atom is preferable.

Examples of the alkylene group represented by R ⁷ in -R ⁷ OH, -R ⁷ -Z'-R ⁸ -OH, -R ⁷ COOH and -R ⁷ NH ₂ represented by Z include methylene, And an alkylene group having 1 to 10 (preferably 1 to 5) carbon atoms such as a propylene group, a trimethylene group and a pentamethylene group. Examples of the cycloalkylene group represented by R ^{7 include} a cycloalkylene group having 3 to 10 ring-forming carbon atoms (preferably 4 to 8 carbon atoms) such as a cyclopentylene group and a cyclohexylene group. The arylene group represented by R ⁷ includes, for example, an arylene group having 6 to 12 ring-forming carbon atoms such as a phenylene group, a naphthylene group and a biphenyldiyl group.

R ⁷ may be substituted by an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 ring-forming carbon atoms, or the like. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and various butyl groups. As the alkoxy group, the alkyl group may be the above-mentioned alkyl group. Examples of the aryl group include a phenyl group and the like.

The alkylene group, alkylidene group, cycloalkylene group and cycloalkylidene group represented by Z 'may be the same as those in the case of X. As Z ', an alkylidene group having 2 to 8 carbon atoms is preferable, and an isopropylidene group is more preferable.

- (A-2) -

Next, the "polycarbonate-polyorganosiloxane copolymer (A-2)" which is one of the components (A) and which is an optional component will be described.

The content of the structural unit represented by the general formula (II) is 2 to 20% by mass, preferably 2 to 15% by mass, and more preferably 2% by mass, in the polycarbonate-polyorganosiloxane copolymer (A- To 10% by mass, more preferably 3 to 8% by mass, and particularly preferably 3 to 7% by mass. If it is less than 2% by mass, the effect of improving the impact resistance is insufficient, and if it exceeds 20% by mass, the heat resistance deteriorates greatly.

In the structural unit (A-2), the average repeating number n in the structural unit represented by the general formula (II) is 70 to 350, preferably 80 to 200, more preferably 80 to 110, And preferably 80 to 100. [ When n is less than 70, the effect of improving the impact resistance is not sufficient, and when it exceeds 350, viscosity becomes high and handling becomes poor.

The viscosity average molecular weight (Mv) of the polymer (A-2) is preferably 16,000 to 30,000, more preferably 16,000 to 25,000, and still more preferably 17,000 to 23,000. When the viscosity average molecular weight of the copolymer (A-2) is within this range, the strength of the molded product becomes sufficient and the viscosity of the copolymer is not excessively increased, so that the productivity during production becomes stable and thin molding becomes easy.

The structural unit represented by the general formula (II) in (A-2) is preferably a structural unit represented by the general formula (II) from the viewpoint of suppressing appearance of black streaks and improving the impact resistance, By mass, more preferably 2.5% by mass or less, and more preferably 2.0% by mass or less.

The polycarbonate-polyorganosiloxane copolymer (A-2) is obtained by reacting a divalent phenol represented by the above general formula (1) with a polyorganosiloxane represented by the general formula (2) (where n is 70 to 350) And phosgene, carbonic ester or chloroformate. The polycarbonate-polyorganosiloxane copolymer (A-2) can also be prepared by reacting a polycarbonate oligomer (for example, a polycarbonate oligomer having a chloroformate group at the terminal) with a polyorganosiloxane .

In the production of the polycarbonate-polyorganosiloxane copolymer (A-2), the reaction rate of the polyorganosiloxane represented by the general formula (2) is preferably 90% or more, more preferably 95% , More preferably 97% or more, and particularly preferably 99% or more.

In the polycarbonate resin composition of the present invention, there are various dihydric phenols represented by the general formula (1) used in the raw materials of (A-1) or (A-2) 2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) is preferable. When bisphenol A is used as the dihydric phenol, X is an isopropylidene group in the general formula (I), and (A-1) or (A-2) with a = b = 0.

Examples of bisphenol other than bisphenol A include bisphenols such as bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) naphthylmethane, 1,1- Propane, 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (hydroxyaryl) cycloalkanes such as cyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, and 1,1-bis (4-hydroxyphenyl) cyclododecane; Dihydroxyaryl ethers such as 4,4'-dihydroxyphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; Dihydroxydiaryl sulfide such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; Dihydroxydialyl sulfoxide such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; Dihydroxydiarylsulfone such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone; Dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl; Dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; Bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2- 4-hydroxyphenyl) -5,7-dimethyladamantane, and other dihydroxydiarylamantan derivatives; Bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenyl) Hydroxyphenylthio) -2,3-dioxapentaene, and the like.

These divalent phenols may be used singly or in combination of two or more kinds.

The polyorganosiloxane represented by the general formula (2) is obtained by reacting phenols having an olefinic unsaturated carbon-carbon bond (preferably vinylphenol, allylphenol, oganol, isopropenylphenol, etc.) Can be easily produced by subjecting the end of the polyorganosiloxane chain having hydrolyzation reaction to a hydro-silanation reaction. More preferably, the phenol is allylphenol or ogenol. In this case, Y in the general formula (II) of (A-1) or (A-2) is an organic residue derived from allylphenol or augenol.

The polyorganosiloxane represented by the general formula (2) includes, for example, the followings.

[Chemical Formula 4]

In the above general formula (3) ~ (11), R 3 ~ R 6 is the same as R ³ ~ R ⁶ in the general formula (1). n is the average number of repeating units of the organosiloxane structural unit, and represents 25 to 65 in the case of (A-1) and 70 to 350 in the case of (A-2). Further, c represents a positive integer, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 3.

Among them, the phenol-modified polyorganosiloxane represented by the general formula (3) (preferably c = 3) is preferable from the viewpoint of polymerization easiness. Further, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is one kind of compound represented by the general formula (4) Bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane is preferable from the viewpoint of availability.

The phenol-modified polyorganosiloxane can be prepared by a known method. Known manufacturing methods include, for example, the following.

The?,? - dihydrogen organopolysiloxane is synthesized by reacting cyclotrisiloxane and disiloxane in the presence of an acidic catalyst. At this time, the?,? - dihydrogen organopolysiloxane having a desired repeating unit can be synthesized by changing the injection ratio of cyclotrisiloxane and disiloxane. Subsequently, a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or augenol is added to the?,? - dihydrogen organopolysiloxane in the presence of a catalyst for hydrosilylation reaction to obtain phenol having a desired repeating unit A modified polyorganosiloxane can be produced.

In this step, since the cyclic polyorganosiloxane having a low molecular weight and the phenol compound in an excessive amount remain as impurities, they are heated under reduced pressure to remove these low molecular compounds.

- (A-3) -

Next, the "aromatic polycarbonate (A-3)" which is one of the components (A) will be described.

(A-3) corresponds to both aromatic polycarbonates other than (A-1) and (A-2). Among them, an aromatic polycarbonate comprising only the structural unit represented by the above general formula (I) is preferable as the (A-3).

In the polycarbonate resin composition of the present invention, (A-3) is obtained by reacting a divalent phenol compound and phosgene in the presence of an organic solvent or an aqueous alkali solution inert to the reaction, A method in which an aromatic polycarbonate such as a pyridine method in which a divalent phenol compound is dissolved in a mixed solution of pyridine or pyridine and an inert solvent and directly prepared by introducing phosgene, Is used.

At the time of the reaction, an end terminator, a molecular weight regulator, a branching agent and the like are used, if necessary.

(4-hydroxyphenyl) propane [= bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, Propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy- , 5-dibromophenyl) propane, and other bis (hydroxyaryl) alkanes; (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (hydroxyaryl) cycloalkanes such as cyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, and 1,1-bis (4-hydroxyphenyl) cyclododecane; Dihydroxyaryl ethers such as 4,4'-dihydroxyphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether; Dihydroxydiaryl sulfide such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; Dihydroxydialyl sulfoxide such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxide; Dihydroxydiarylsulfone such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone; Dihydroxydiphenyls such as 4,4'-dihydroxydiphenyl; Dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; Bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane, 2,2- 4-hydroxyphenyl) -5,7-dimethyladamantane, and other dihydroxydiarylamantan derivatives; Bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenyl) Hydroxyphenylthio) -2,3-dioxapentaene, and the like. These divalent phenols may be used alone or in combination of two or more.

(A-3), an end terminator or a molecular weight regulator is usually used.

As the molecular weight regulator, various ones can be used as long as they are usually used for polymerization of a polycarbonate resin.

Specific examples of the monovalent phenol include phenol, on-butyl phenol, m-butyl phenol, pn-butyl phenol, o-isobutyl phenol, m-isobutyl phenol, Pentylphenol, m-hexylphenol, pn-hexylphenol, pt-octylphenol, o-butylphenol, pt-butylphenol, Cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, m-nonylphenol, pn-nonylphenol, o-cumylphenol , m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di- , 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, Or a monoalkylphenol having a branched alkyl group in an ortho, meta or para position, 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene, 4- (1-adamantyl) phenol, and the like can be used. .

Among these monohydric phenols, p-t-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used. It is of course possible to use two or more compounds in combination.

Further, the branched polycarbonate can be used in combination with the dihydric phenol compound in the range of 0.01 to 3 mol%, particularly 0.1 to 1 mol%. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- (4-hydroxyphenyl) Ethylidene] bisphenol, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, 1- [ 3 or more functional groups such as ethyl] -4- [α ', α'-bis (4 "-hydroxyphenyl) ethyl] benzene, fluoroglycine, trimellitic acid, and isastin bis May be used.

(Mixing ratio of each component (A)

The content of (A-1) to (A-3) in the polycarbonate resin (A) is from 5 to 100% by mass of (A-1), from 0 to 95% by mass of (A- -3) 0 to 95% by mass.

When the content of (A-1) in the component (A) is less than 5 mass%, the content of the polyorganosiloxane block portion containing the constituent unit represented by the general formula (II) %. In this case, the uniformity of the reaction may be lowered in the step (A-1) during the production of the polymer (A-1), and the separability between the polymer and the washing water deteriorates in the step of washing the polymer , The productivity of (A-1) is significantly lowered. On the other hand, when the content of (A-2) or (A-3) exceeds 95 mass%, the ratio of (A- The content of the polyorganosiloxane block portion containing the constitutional unit represented by the formula (II) is required to be large, which is not preferable for the same reason as described above.

The content of (A-1) in the component (A) is preferably 20 to 100 mass%, more preferably 30 to 100 mass%, further preferably 40 to 100 mass% , The content of (A-2) is preferably 0 to 80 mass%, more preferably 0 to 70 mass%, still more preferably 0 to 60 mass%, and particularly preferably 0 to 40 mass% , The content of (A-3) is preferably 0 to 80 mass%, more preferably 0 to 70 mass%, still more preferably 0 to 60 mass%, and particularly preferably 0 to 40 mass%.

The component (A) is preferably composed of (A-1) and (A-2), (A-1) and (A- It is also preferable that all of them are formed. When the component (A) contains only (A-1) and (A-2), the content ratio of both components is preferably from 20 to 95% by mass of (A-1) and from 80 to 5% by mass of (A-1), preferably 20 to 90 mass%, and (A-2) 80 to 10 mass%, more preferably 40 to 80 mass% and (A- (A-1) is 50 to 70% by mass and (A-2) is 50 to 30% by mass.

(A-1) and (A-3), the content ratio of both is preferably from 20 to 95 mass% of (A-1) and from 80 to 5 mass% of (A- Is 20 to 90% by mass of (A-1) and 80 to 10% by mass of (A-3), more preferably 50 to 90% by mass of (A-1) and 50 to 10% by mass of (A-3).

When the component (A) contains all of (A-1) to (A-3), the content of the component (A-1) is preferably 20 to 80% by mass, (A-1), 10 to 60 mass% and (A-3) 10 to 50 mass%, more preferably 25 to 60 mass% ) Is 25 to 60% by mass.

((B) titanium oxide)

In the polycarbonate resin composition of the present invention, the content of (B) titanium oxide (titanium dioxide: TiO ₂ ) is 0.1-4 parts by mass with respect to 99.9-96 parts by mass of (A) from the viewpoint of impact resistance, (A) and (B) is preferably 0.5 to 3 parts by mass, more preferably 0.5 to 2 parts by mass with respect to 99.5 to 98 parts by mass of the component (A), relative to 99.5 to 97 parts by mass of the component (A) The total amount of the components is 100 parts by mass).

The primary average particle diameter of the titanium oxide is preferably 0.05 to 0.5 占 퐉, more preferably 0.1 to 0.4 占 퐉, and still more preferably 0.15 to 0.3 占 퐉.

The titanium oxide may be coated with its surface. The surface of the titanium oxide may be covered with a hydrous oxide and / or an oxide of at least one element including elements such as aluminum, silicon, magnesium, zirconia titanium, and tin. The titanium oxide may be further subjected to surface treatment by a polyol not containing a nitrogen atom, an organic silicon compound, alkanolamines, higher fatty acids, or the like. As the titanium oxide, it is preferable that the titanium oxide is coated with a hydrous oxide and / or an oxide of aluminum or silicon. Titanium oxide surface-treated with a polyol not containing a nitrogen atom is also preferable.

Examples of the polyol that does not contain a nitrogen atom covering the titanium oxide include trimethylol propane, trimethylol ethane, ditrimethylol propane, trimethylol propane ethoxylate, and pentaerythritol. Of these, From the viewpoint of preventing degradation, trimethylolpropane and trimethylolethane are preferred. These polyols may be used singly or in combination of two or more kinds.

A method of covering the surface with a polyol not containing a nitrogen atom may be either a wet method or a dry method. The wet method is a method in which titanium oxide is added to a mixture of a polyol not containing a nitrogen atom and a low boiling point solvent, followed by stirring, and then a low boiling point solvent is removed. In the dry method, a mixed solution obtained by mixing a polyol not containing a nitrogen atom and titanium oxide in a mixer such as a Henschel mixer or a tumbler, or a polyol containing no nitrogen atom in a solvent, or dispersing the mixed solution is sprayed onto titanium oxide .

The titanium oxide may be produced by a chlorine method or a sulfuric acid method. The crystal structure of titanium oxide can be any of rutile type and anatase type, but rutile type is preferable from the viewpoints of heat stability and light resistance of the polycarbonate resin composition.

((C) polytetrafluoroethylene-containing mixed powder)

The polycarbonate resin composition of the present invention may further contain a polytetrafluoroethylene-containing mixed powder as component (C). The polytetrafluoroethylene-containing mixed powder is composed of polytetrafluoroethylene-based particles having an average particle diameter of 10 m or less and organic polymer particles.

The morphology of the polytetrafluoroethylene-containing mixed powder varies depending on the blending ratio of the polytetrafluoroethylene-based particles and the organic-based polymer particles and the particle diameter, and is not particularly limited. For example, the polytetrafluoroethylene-based particles may be surrounded by the organic polymer particles, or conversely, the polytetrafluoroethylene-based particles may surround the organic polymer particles, And the like.

The polytetrafluoroethylene-containing mixed powder used in the present invention is composed of polytetrafluoroethylene particles having a particle diameter of 10 m or less and an organic polymer, and polytetrafluoroethylene is not formed into an aggregate of 10 m or more in the powder There is a need. Such a polytetrafluoroethylene-containing mixed powder may be obtained by mixing an aqueous dispersion of a polytetrafluoroethylene particle having a particle diameter of 0.05 to 1.0 탆 and an aqueous dispersion of an organic polymer particle and pulverizing the mixture by coagulation or spray drying, A polymer obtained by polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 占 퐉 and then solidifying or pulverizing the polymer by spray drying or a polytetrafluoroethylene having a particle diameter of 0.05 to 1.0 占 퐉 It is preferable to emulsify and polymerize a monomer having an ethylenically unsaturated bond in a dispersion in which an aqueous dispersion of fluoroethylene particles and an aqueous dispersion of organic polymer particles are mixed and then solidify or spray-dry the dispersion.

The aqueous dispersion of polytetrafluoroethylene particles having a particle diameter of 0.05 to 1.0 μm is obtained by polymerizing a tetrafluoroethylene monomer by emulsion polymerization using a fluorinated surfactant. In emulsion polymerization, fluorinated olefins such as hexafluoropropylene, chlorotrifluoroethylene, fluoroalkylethylene and perfluoroalkyl vinyl ether, and perfluoroalkyl (meth) acrylates as copolymerization components in polytetrafluoroethylene, Fluoroalkyl (meth) acrylates such as acrylate can be used. These copolymerization components are preferably 10 mass% or less with respect to tetrafluoroethylene.

As commercial raw materials for the polytetrafluoroethylene-based particle aqueous dispersion, Fluon AD-1 and AD-936 manufactured by Asahi ICI Fluoropolymer Co., Polyflon D-1 and D-2 manufactured by Daikin Industries, And Teflon (registered trademark) 30J manufactured by Fluoro Chemical Co., Ltd. as representative examples.

The organic polymer particles are not particularly limited and include, for example, polycarbonate (PC), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, 6-nylon, 6,6- Polyether ether ketone, polysulfone, polyether sulfone, polyamideimide, polyetherimide, polypropylene, polyethylene, polystyrene, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyarylate, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, , A high impact polystyrene, a polyalkyl (meth) acrylate, a polyacetal, a copolymer comprising an aromatic alkenyl compound and a vinyl cyanide compound, a phenol resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, Resins, polyurethanes, ethylene-propylene copolymers, styrene-butadiene Block copolymers, random copolymers and block copolymers of polybutadiene, polyisoprene, styrene-butadiene, hydrogenated products of block copolymers thereof, diene rubbers such as acrylonitrile-butadiene copolymer and butadiene-isoprene copolymer, - random copolymers and block copolymers of propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and alpha -olefins, ethylene-unsaturated carboxylates such as ethylene-methacrylate and ethylene- Acrylic ester-butadiene copolymers such as acrylic elastomers such as butyl acrylate-butadiene, copolymers of ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-butadiene copolymers, Ethylene-propylene non-conjugated diene terpolymers such as hexadiene copolymers, butylene-isoprene copolymers (Meth) acrylate, a polyorganosiloxane and a polyalkyl (meth) acrylate, a rubber-like polymer having an aromatic vinyl monomer and a vinyl cyanide monomer , A polyorganosiloxane and a polyalkyl (meth) acrylate grafted with a vinyl monomer, and a component copolymerizable therewith, in an amount of 50 parts by mass By mass or less, and the like. These may be used alone, or two or more of them may be used in combination.

From the viewpoint of dispersibility of polytetrafluoroethylene, those having affinity to a polycarbonate-based resin are preferable, and those comprising a polyalkyl (meth) acrylate as a main component and a rubbery polymer are preferable, (Meth) acrylate having an alkyl group of at least 30 mass%.

Examples of the rubbery polymer include random copolymers of polybutadiene, polyisoprene, styrene-butadiene, block copolymers, water additives of the block copolymers, acrylonitrile-butadiene copolymers, and butadiene-isoprene copolymers Rubber, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and? -Olefins, ethylene-methacrylates such as ethylene- Unsaturated carboxylic acid esters, acrylic ester-butadiene copolymers such as acrylic elastomers such as butyl acrylate-butadiene, copolymers of ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, Ethylene-propylene-non-conjugated diene terpolymers such as ethylene-propylene-hexadiene copolymers, And the like. These may be used alone, or two or more of them may be used in combination.

Of these, ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer diene rubber and acrylic elastomer are preferable, and polybutadiene and styrene-butadiene copolymers are exemplified. Polybutadiene, styrene- , Polyorganosiloxane, polyalkyl (meth) acrylate, polyorganosiloxane, and polyalkyl (meth) acrylate. As the production method of these organic polymers, conventionally known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like are used.

The mixing ratio of the polytetrafluoroethylene-based particles and the organic polymer particles in the polytetrafluoroethylene-containing mixed powder is not particularly limited, but it is preferable that the polytetrafluoroethylene-based particles are contained in an amount of 0.1 to 90% by mass. The polytetrafluoroethylene-containing mixed powder is obtained by mixing an aqueous dispersion obtained by stirring and mixing a polytetrafluoroethylenic particle dispersion and an organic polymer particle dispersion into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, , And the like.

When the component (C) is blended in the polycarbonate resin composition of the present invention, the blending amount thereof is preferably 0.1 to 1 part by mass, more preferably 0.1 to 1 part by mass based on 100 parts by mass of the total of the components (A) and (B) Is from 0.1 to 0.6 parts by mass.

((D) an alkali metal salt of an organic sulfonic acid and / or an alkaline earth metal salt of an organic sulfonic acid)

In the polycarbonate resin composition of the present invention, at least one member selected from an alkali metal salt of an organic sulfonic acid and an alkaline earth metal salt of an organic sulfonic acid may be further blended as the component (D) from the viewpoint of flame retardancy.

Examples of the alkali metal salt or alkaline earth metal salt of the organic sulfonic acid include alkali metal salts and alkaline earth metal salts of organic sulfonic acids having at least one carbon atom,

Examples of the organic acid sulfonic acid include organic sulfonic acid and polystyrene sulfonic acid.

Examples of the alkali metal include sodium, potassium, lithium and cesium.

Examples of the alkaline earth metals include magnesium, calcium, strontium and barium. Among them, an alkali metal salt of sodium, potassium and cesium is preferably used as the organic acid sulfonic acid salt.

Among the various alkali metal salts of organic sulfonic acids and the alkali earth metal salts of organic sulfonic acids, organic sulfonic acids represented by the following general formula (12)

(C _c F _{2c + 1} SO ₃ ) _d M (12)

Wherein m represents an alkali metal such as lithium, sodium, potassium and cesium, or an alkaline earth metal such as magnesium, calcium, strontium and barium, and d represents a valence of M Is preferably an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid.

These metal salts include those described in, for example, Japanese Patent Publication No. 47-40445.

Examples of the perfluoroalkanesulfonic acid in the general formula (12) include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutane Sulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, and perfluorooctanesulfonic acid. In particular, potassium salts thereof are preferably used.

In addition, examples of the alkylsulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, diphenylsulfonic acid, naphthalenesulfonic acid, 2,5-dichlorobenzenesulfonic acid, 2,4,5-trichlorobenzenesulfonic acid, diphenylsulfone- -3,3'-disulfonic acid, naphthalenetrisulfonic acid, fluorine substituents thereof, and alkali metal salts and alkaline earth metal salts of organic sulfonic acids such as polystyrenesulfonic acid.

Particularly, as the organic sulfonic acid, perfluoroalkanesulfonic acid and diphenylsulfonic acid are preferable.

As the alkali metal salt and / or alkaline earth metal salt of polystyrene sulfonic acid,

[Chemical Formula 5]

[In the formula (13), X represents a sulfonic acid group, and m represents an integer of 1 to 5. Y represents a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms. n is a molar fraction, and 0 < n < = 1.).

Examples of the metal include sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, and the like.

Y is a hydrogen atom or a hydrocarbon group of 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.

m is an integer of 1 to 5, and n is 0 <n? 1.

That is, the sulfonic acid group (X) may be completely substituted with respect to the aromatic ring, partially substituted or unsubstituted.

When the component (D) is blended in the polycarbonate resin composition of the present invention, the blending amount thereof is preferably 0.01 to 0.15 parts by mass, more preferably 0.01 to 0.15 parts by mass, per 100 parts by mass of the total of the components (A) Is 0.02 to 0.13 parts by mass, and more preferably 0.03 to 0.1 parts by mass.

(Other components)

In the polycarbonate resin composition of the present invention, various known additives to be added to the polycarbonate resin composition can be formulated as other components, if necessary, conventionally. These other components include, for example, reinforcing materials, fillers, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, lubricants, release agents, dyes, pigments, other flame retardants, and elastomers for improving impact resistance .

When other components are blended in the polycarbonate resin composition of the present invention, the amount thereof is preferably 20 parts by mass or less, more preferably 20 parts by mass or less, per 100 parts by mass in total of the components (A) and (B) Is not more than 10 parts by mass, more preferably not more than 5 parts by mass.

The polycarbonate resin composition of the present invention is preferably blended with a phosphorus stabilizer.

The polycarbonate resin composition of the present invention contains titanium oxide. When titanium oxide is added to a polycarbonate resin, an undesirable effect of decomposing the polycarbonate resin and lowering its molecular weight is exhibited have. The phosphorus stabilizer can inhibit this undesirable effect as much as possible.

Examples of the phosphorus stabilizer used in the present invention include aromatic phosphine compounds and / or phosphoric acid compounds.

Examples of the aromatic phosphine compound include triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, tris- (p-tolyl) phosphine, tris- (p-nonylphenyl) Tris- (naphthyl) phosphine, diphenyl- (hydroxymethyl) -phosphine, diphenyl- (acetoxymethyl) -phosphine, diphenyl- (p-ethylcarboxyethyl) (p-chlorophenyl) phosphine, tris- (p-fluorophenyl) phosphine, diphenylbenzylphosphine, diphenyl -? - cyanoethylphosphine, diphenyl- , Diphenyl-1,4-dihydroxyphenyl-2-phosphine, and phenylnaphthylbenzylphosphine. Of these, triphenylphosphine is particularly preferably used.

Examples of the phosphoric acid compound include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and esters thereof. Specific examples include triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, Silane monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, diphenyl isooctyl phosphite, diphenyl-n-octyl phosphite, monobutyl diphenyl phosphite, monodecyldiphenyl phosphite (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert- butylphenyl) octylphosphate (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, Phosphate, triphenyl phosphite , Diphenylmonoctalkenylphosphate, dibutylphosphate, dioctylphosphate, diisopropylphosphate, 4,4'-biphenylene diphosphospin tetrakis (2,4-di-tert-butylphenyl) Dimethylphosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like.

Preferred are diphenyl isooctyl phosphite, diphenyl-n-octyl phosphite, trisnonyl phenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzene phosphonic acid.

When the above phosphorus stabilizer is blended, it is preferably 0.1 to 1 part by mass based on 100 parts by mass of the total of the components (A) and (B).

The polycarbonate resin composition of the present invention can be obtained by blending the above components (A) and (B) and, if necessary, the above additives, and kneading.

The compounding and kneading are carried out by a commonly used method, for example, a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a coneizer, a multiaxial screw extruder, can do.

The heating temperature at the time of kneading is usually selected in the range of 250 to 320 占 폚.

The polycarbonate resin composition of the present invention obtained as described above can be molded by various conventionally known molding methods such as an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method, Can be used.

In this specification, a combination of the preferable ones (inclusive of preferable ranges) is of course preferable, and any desirable one (including preferred ranges) can be combined in all the specifications.

Example

Embodiments of the present invention will be further described. Further, the present invention is not limited at all by these examples. In each example, the viscosity average molecular weight (Mv), the amount of unreacted PDMS, and the reaction rate of PDMS were determined by the following methods.

(1) Method of measuring viscosity average molecular weight (Mv)

The intrinsic viscosity [?] Of the methylene chloride solution at 20 占 폚 was measured with a Ubbelohde type viscometer and calculated from the following relation (Schnell's equation).

[?] = 1.23 10 ^-5 Mv ^0.83

(2. Method for calculating the amount of unreacted PDMS)

(I) 50 ml of acetone and 150 ml of n-hexane were added to a solution prepared by dissolving 6 g of the polycarbonate-polydimethylsiloxane copolymer obtained in each Example in 50 ml of methylene chloride, and the mixture was stirred for 30 minutes.

(Ii) The filtrate was recovered by suction filtration using a filter paper (No. 5A), and the recovered filtrate was concentrated and dried, and the weight of the resulting dry matter was measured. The obtained dry solid was dissolved in deuterated chloroform and subjected to ¹ H-NMR measurement. The integral value x of the proton (? 6.7 ppm) of the ortho position of the hydroxyl group of the unreacted phenol-modified polydimethylsiloxane and the integral value y of the proton (? 0.6 ppm) attributed to the methylene chain, The ratio z (%) of the reaction PDMS was calculated.

z = 2 x x / y x 100

(Iii) On the other hand, a standard sample prepared by adding 150 to 2000 ppm of phenol-modified polydimethylsiloxane to the polycarbonate-polydimethylsiloxane copolymer was separately prepared and the same operation as described above was carried out to obtain an amount of unreacted PDMS (ppm, = Amount of phenol-modified polydimethylsiloxane added) was determined.

(Ppm) of unreacted PDMS was calculated from the relationship between z obtained in (ii) and (iii).

(3. Calculation of Reaction Rate of PDMS)

The reaction rate of PDMS was calculated according to the following formula.

PDMS reaction rate (mass%) = (1 - amount of unreacted PDMS (mass%) / amount of polydimethylsiloxane residue (mass%)) × 100

Synthesis Example 1 Synthesis Example of Polycarbonate Oligomer

2000 ppm by mass sodium dithionite was added to 5.6% by mass aqueous solution of sodium hydroxide to dissolve bisphenol A, bisphenol A was dissolved in the resulting solution so that the bisphenol A concentration was 13.5% by mass, and an aqueous solution of sodium hydroxide of bisphenol A Lt; / RTI &gt;

This phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr at a flow rate of 40 l / hr of an aqueous sodium hydroxide solution of bisphenol A and 15 l / hr of methylene chloride. The tubular reactor had a jacket portion, and cooling water was passed through the jacket to maintain the temperature of the reaction solution at 40 캜 or lower.

The reaction liquid exiting the tubular reactor was continuously introduced into an internal volume 40 L bubble-form molding reactor equipped with a retreating wing, to which 2.8 L / hr of an aqueous solution of sodium hydroxide of bisphenol A and 0.07 L of a 25 mass% aqueous sodium hydroxide solution / hr, water 17 l / hr, and a 1 mass% aqueous triethylamine solution at 0.64 l / hr. The reaction liquid overflowing from the molding reactor was continuously withdrawn, and the water phase was separated and removed by stopping it, and a methylene chloride phase was collected.

The polycarbonate oligomer thus obtained had a concentration of 318 g / l and a chloroformate group concentration of 0.75 mol / l. The weight average molecular weight (Mw) was 1190.

GPC (column: TOSOH TSK-GEL MULTIPORE HXL-M (2) + Shodex KF801 (1), temperature: 40 占 폚) was used as the developing solvent, and THF (tetrahydrofuran) , Flow rate: 1.0 ml / min, detector: RI] as a standard polystyrene reduced molecular weight (weight average molecular weight: Mw).

Production Example 1 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-1]

15 liters of the polycarbonate oligomer solution prepared in Synthesis Example 1, 8.9 liter of methylene chloride, 2-ethylhexyl acrylate having an average repetition number of dimethylsiloxy units of 40, 307 g of allylphenol-terminated polydimethylsiloxane (PDMS-1) and 8.8 ml of triethylamine were introduced, 1389 g of 6.4% by mass aqueous sodium hydroxide solution was added thereto under stirring, 10 minutes of polycarbonate oligomer and 2-allylphenol The reaction of terminally modified polydimethylsiloxane was carried out.

To this polymerization solution was added a methylene chloride solution of pt-butylphenol (PTBP) [obtained by dissolving 129 g of PTBP in 2.0 L of methylene chloride], an aqueous solution of sodium hydroxide of bisphenol A [581 g of sodium hydroxide and 2.3 g of sodium dithionite, 8.5 l of an aqueous solution of bisphenol A dissolved therein] was added, and the polymerization reaction was carried out for 50 minutes. 10 L of methylene chloride was added for dilution, and the mixture was stirred for 10 minutes. Then, the mixture was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was isolated.

A methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was washed successively with a 15% by volume aqueous solution of 0.03 mol / l sodium hydroxide and 0.2 mol / l hydrochloric acid, The cleaning was repeated with pure water until the electric conductivity became 0.01 μS / m or less. The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the resulting flakes were dried at 120 DEG C under reduced pressure.

The polycarbonate-polydimethylsiloxane copolymer (SiPC-1) thus obtained had a polydimethylsiloxane residue amount of 4.8 mass% determined by NMR measurement, a viscosity of 49.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 18,600. The amount of unreacted PDMS-1 was 150 ppm or less, and the reaction rate of PDMS-1 was 99.5% or more.

Production Example 2 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-2]

Butylphenol (PTBP) was used as a methylene chloride solution of PTBP 107 (PTBP) in the same manner as in Production Example 1 except that the amount of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 was 256 g, was dissolved in 2.0 L of methylene chloride to prepare a polycarbonate-polydimethylsiloxane copolymer.

The polycarbonate-polydimethylsiloxane copolymer (SiPC-2) thus obtained was found to have a polydimethylsiloxane residue amount of 4.0 mass% determined by NMR measurement, a viscosity of 55.9 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 21,400. The amount of unreacted PDMS-1 was 150 ppm or less, and the reaction rate of PDMS-1 was 99.5% or more.

Production Example 3 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-3]

The amount of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 was determined to be 384 g, and a methylene chloride solution of pt-butylphenol (PTBP) polydimethylsiloxane copolymer (SiPC-3) was prepared in the same manner as in the synthesis of polycarbonate-polydimethylsiloxane copolymer (SiPC-3).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-3) thus obtained had a polydimethylsiloxane residue amount of 6.1 mass% determined by NMR measurement, a viscosity of 47.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 17,700. The amount of unreacted PDMS-1 was 150 ppm or less, and the reaction rate of PDMS-1 was 99.5% or more.

Production Example 4 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-4]

Allylphenol-terminated PDMS (PDMS-2) having a repetition number of dimethylsiloxy units of 52 was used instead of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 in Production Example 3 ) Was used in place of the polycarbonate-polydimethylsiloxane copolymer (SiPC-4).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-4) thus obtained was found to have a polydimethylsiloxane residue amount of 6.0 mass% determined by NMR measurement, a viscosity of 47.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 17,700. The amount of unreacted PDMS-2 was 150 ppm or less, and the reaction rate of PDMS-2 was 99.5% or more.

Production Example 5 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-5]

Polycarbonate-polydimethylsiloxane copolymer (SiPC-1) was prepared in the same manner as in Production Example 1, except that the amount of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 was used in an amount of 768 g. 5).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-5) thus obtained had a polydimethylsiloxane residue amount of 12 mass% determined by NMR measurement, a viscosity of 46.8 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 17,400. The amount of unreacted PDMS-1 was 200 ppm, and the reaction rate of PDMS-1 was 99.5% or more.

Production Example 6 Polycarbonate-polydimethylsiloxane copolymer (A-1) [SiPC-6]

A polycarbonate-polydimethylsiloxane copolymer (SiPC-6) was obtained in the same manner as in Production Example 1, except that the amount of Ogenerol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 was changed to 256 g ).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-6) thus obtained had a polydimethylsiloxane residue amount of 4.7 mass% determined by NMR measurement, a viscosity of 49.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 18,600. The amount of unreacted PDMS-1 was 150 ppm or less, and the reaction rate of PDMS-1 was 99.5% or more.

Production Example 7 Polycarbonate-polydimethylsiloxane copolymer (A-2) [SiPC-7]

Allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 150 in place of 256 g of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 in Production Example 2 Polycarbonate-polydimethylsiloxane copolymer (SiPC-7) was prepared in the same manner as in Example 1 except that 256 g of polypropylene-3) was used.

The polycarbonate-polydimethylsiloxane copolymer (SiPC-7) thus obtained had a polydimethylsiloxane residue amount of 3.9 mass% determined by NMR measurement, a viscosity of 55.9 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 21,400. The amount of unreacted PDMS-3 was 150 ppm or less, and the reaction rate of PDMS-3 was 99.5% or more.

Production Example 8 Polycarbonate-polydimethylsiloxane copolymer (A-3) [SiPC-8]

Allylphenol-terminated PDMS (PDMS-4) having a repetition number of dimethylsiloxy units of 20 was used in place of the 2-allylphenol-terminated PDMS-PDMS-3 having a repetition number of dimethylsiloxy units of 150 ) Was used in place of the polycarbonate-polydimethylsiloxane copolymer (SiPC-8).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-8) thus obtained had an amount of polydimethylsiloxane residues determined by NMR measurement of 4.1% by mass, a viscosity of 55.4 measured according to ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 21,200. The amount of unreacted PDMS-4 was 150 ppm or less, and the reaction rate of PDMS-4 was 99.5% or more.

Production Example 9 Synthesis of Polycarbonate-Polydimethylsiloxane Copolymer (A-2) [SiPC-9]

In the same manner as in Production Example 6 except that 2-allylphenol-terminated PDMS (PDMS-4) having a repetition number of dimethylsiloxy units of 90 was used instead of 2-allylphenol-terminated PDMS (PDMS- ) Was used in place of the polycarbonate-polydimethylsiloxane copolymer (SiPC-9).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-9) thus obtained had a polydimethylsiloxane residue amount of 4.0 mass% determined by NMR measurement, a viscosity of 55.9 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 21,400. The amount of unreacted PDMS-4 was 150 ppm or less, and the reaction rate of PDMS-4 was 99.5% or more.

Production Example 10 Polycarbonate-polydimethylsiloxane copolymer (A-2) [SiPC-10]

Allylphenol-terminated PDMS (PDMS-4) having a repetition number of dimethylsiloxy units of 90 was used instead of 2-allylphenol-terminated PDMS (PDMS-1) having a repetition number of dimethylsiloxy units of 40 in Production Example 3 ) Was used in place of the polycarbonate-polydimethylsiloxane copolymer (SiPC-10).

The polycarbonate-polydimethylsiloxane copolymer (SiPC-10) thus obtained was found to have a polydimethylsiloxane residue amount of 6.0 mass% determined by NMR measurement, a viscosity of 47.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 17,700. The amount of unreacted PDMS-4 was 150 ppm or less, and the reaction rate of PDMS-4 was 99.5% or more.

Production Example 11 Synthesis of Polycarbonate-Polydimethylsiloxane Copolymer (A-2) [SiPC-11]

(Synthesis of PDMS-containing polycarbonate oligomer)

2000 ppm by mass of sodium dithionite was added to 5.6% by mass aqueous sodium hydroxide solution to dissolve bisphenol A, and BPA was dissolved therein to give a bisphenol A concentration of 13.5% by mass to prepare an aqueous solution of sodium hydroxide of bisphenol A Respectively.

A tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 40 l / hr of sodium hydroxide aqueous solution of bisphenol A, 9.3 mass% of methylene chloride solution of PDMS-2 at 17 l / hr and phosgene at 4.0 kg / And passed continuously. The tubular reactor had a jacket portion, and cooling water was passed through the jacket to maintain the temperature of the reaction solution at 40 캜 or lower.

The reaction liquid exiting the tubular reactor was continuously introduced into an internal volume 40 L bubble-form molding reactor equipped with a retreating wing, to which 2.8 L / hr of an aqueous solution of sodium hydroxide of bisphenol A and 0.07 L of a 25 mass% aqueous sodium hydroxide solution / hr, water 17 l / hr, and a 1 mass% aqueous triethylamine solution at 0.64 l / hr. The reaction liquid overflowing from the molding reactor was continuously withdrawn, and the water phase was separated and removed by stopping it, and a methylene chloride phase was collected.

The polycarbonate oligomer thus obtained had a concentration of 400 g / l and a chloroformate group concentration of 0.75 mol / l. The weight average molecular weight (Mw) was 2,110.

(Production of SiPC-11)

15 L of the polycarbonate oligomer solution prepared above, 8.9 L of methylene chloride, a methylene chloride solution of pt-butylphenol (PTBP) [PTBP 129 (manufactured by Mitsubishi Chemical Corporation)], and 8.8 ml of triethylamine. To this solution, an aqueous solution of sodium hydroxide of BPA [an aqueous solution prepared by dissolving 675 g of sodium hydroxide and 2.4 g of sodium dithionate in 9.9 L of water And 1231 g of bisphenol A dissolved therein] was added and polymerization reaction was carried out for 60 minutes. 10 L of methylene chloride was added for dilution, and the mixture was stirred for 10 minutes. Then, the mixture was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and sodium hydroxide, and the organic phase was isolated.

A methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was washed successively with a 15% by volume aqueous solution of 0.03 mol / l sodium hydroxide and 0.2 mol / l hydrochloric acid, The cleaning was repeated with pure water until the electric conductivity became 0.01 μS / m or less. The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the resulting flakes were dried at 120 DEG C under reduced pressure.

The polycarbonate-polydimethylsiloxane copolymer (SiPC-11) thus obtained had a polydimethylsiloxane residue amount of 20 mass% determined by NMR measurement, a viscosity of 49.5 measured in accordance with ISO1628-4 (1999) , And the viscosity average molecular weight (Mv) was 18,600. The amount of unreacted PDMS-2 was 150 ppm or less, and the reaction rate of PDMS-2 was 99.5% or more.

&Lt; Examples 1 to 16 and Comparative Examples 1 to 7 &gt;

(Granulation) pellets were obtained at a resin temperature of 280 占 폚 using a single-screw extruder with a vent of 40 mmφ.

The obtained assembled pellets were dried at 120 DEG C for 8 hours and then injection molded at an extrusion molding machine at a molding temperature of 280 DEG C and a mold temperature of 80 DEG C to obtain test pieces. Using the assembled pellets or test pieces obtained by injection molding, the following measurements were carried out. The results are shown in Table 1.

(1) Izod impact strength

In accordance with JIS-K-7110, the notched formation Izod impact strength was measured at -20 占 폚 and 23 占 폚.

(2) appearance of molded article

Preliminary drying was carried out at 120 DEG C for 5 hours in a dryer and then the molded product having a thickness of 1.5 mm, a length of 140 mm and a width of 140 mm was subjected to injection molding under the conditions of injection molding for 10 shots, , And evaluated according to the following evaluation criteria.

?: No brown to black stripe was observed on the surface of the molded article

X: Brown to black stripe was observed on the surface of the molded article

(Injection molding conditions)

Injection molding machine: "IS150E" manufactured by Toshiba Machine Co., Ltd.

Cylinder temperature: 300 ° C

Mold temperature: 80 ℃

(3) Flammability

A vertical combustion test according to the UL94 method equivalent to a thickness of 1.5 mm was carried out.

The annotations in Tables 1 and 2 will be described below.

* 1: Polycarbonate-polydimethylsiloxane copolymer prepared in Production Examples 1 to 11

* 2: Bisphenol A polycarbonate having a viscosity of 46.6 and a viscosity average molecular weight (Mv) of 17,300 (trade name, available from Idemitsu Kosan Co., Ltd., p-t-butylphenol in the terminal group)

* 3: Bisphenol A polycarbonate having a viscosity of 51.1, a viscosity average molecular weight (Mv) of 19,300 (trade name, manufactured by Idemitsu Kosan Co., Ltd., p-t-

* 4: Bisphenol A polycarbonate having a viscosity of 55.6 and a viscosity average molecular weight (Mv) of 21,300 (trade name, manufactured by Idemitsu Kosan Co., Ltd., p-t-

* 5: "CR-63" (manufactured by Ishihara Sangyo Co., Ltd., titanium dioxide treated with 1% of silica and alumina and 0.5% of dimethylsilicone, average particle diameter: 0.21 μm)

* 6: &quot; CR-60-2 &quot; (titanium oxide coated with polyol, manufactured by Ishihara Industries Co., Ltd., average particle diameter: 0.21 mu m)

* 7: &quot; PC3 &quot; (manufactured by Ishihara Industries Co., Ltd., rutile type, surface amount: 10 mu mol / g, surface salt amount: 4 mu mol / g)

* 8: &quot; Metabrene A-3800 &quot; (trade name, manufactured by Mitsubishi Rayon Co., Ltd.)

* 9: "F-top KFBS" (trade name, component: potassium perfluorobutanesulfonate, manufactured by Mitsubishi Materials Electronics Co., Ltd.)

* 10: IRGAFOS168 (trade name, tris (2,4-di-t-butylphenyl) phosphite, manufactured by Chiba Specialty Chemicals Co., Ltd.)

* 11: Polydimethylsiloxane residue

It can be seen from Table 1 that the polycarbonate resin composition of the present invention has excellent color appearance while retaining excellent properties (for example, impact resistance, particularly impact resistance at low temperature) of the polyorganosiloxane-polycarbonate copolymer . In Examples 12 and 14, flame retardancy was also excellent.

On the other hand, in Comparative Examples 1 and 3 in Table 2, it was confirmed that the polycarbonate resin composition containing (A-1) and (A-2) Lt; 0 &gt; C) is remarkably lowered. (A-2) having an average repeating number n of 70 to 350 in the polycarbonate resin composition containing no (A-1) having an average repeating number n of 25 to 65 from the comparative examples 2, 4, It is understood that the color appearance is deteriorated. In the polycarbonate resin composition containing (A-2) and (A-3) as in Comparative Example 5, the impact resistance at 23 캜 was kept high, but the impact resistance at low temperature (-20 캜) Is significantly reduced. Also, as in Comparative Example 7, it was found that when the content of the titanium oxide as the component (B) was excessively large, the impact resistance remarkably decreased at both 23 占 폚 and -20 占 폚.

Industrial availability

The polycarbonate resin composition obtained by the present invention can be widely used in various fields such as electric and electronic devices, automobiles, and the like. In particular, it can be used as a material of a case of a mobile phone, a mobile PC, a digital camera, a video camera, an electric power tool, and the like.

Claims (10)

(A): a polycarbonate-polyorganosiloxane copolymer having a main chain of a repeating unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), wherein n in the general formula (II) , 5 to 100% by mass of a polycarbonate-polyorganosiloxane copolymer (A-1) having a constituent unit represented by the general formula (II) in an amount of 2 to 20% by mass,
A polycarbonate-polyorganosiloxane copolymer having a main chain of a repeating unit represented by the general formula (I) and a constitutional unit represented by the general formula (II), wherein n in the general formula (II) is 70 to 350, 0 to 95% by mass of a polycarbonate-polyorganosiloxane copolymer (A-2) having a constituent unit represented by the formula (II) in an amount of 2 to 20% by mass,
99.9 to 96 parts by mass of a polycarbonate resin composed of 0 to 95% by mass of an aromatic polycarbonate (A-3) other than the above-mentioned (A-1) and (A-2)
(B): 0.1 to 4 parts by mass of titanium oxide (provided that the sum of the components (A) and (B) is 100 parts by mass).
[Chemical Formula 1]

[Wherein R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO-, SO ₂ -, -O- or -CO-. a and b each independently represent an integer of 0 to 4;
R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Y represents an organic residue containing a single bond, aliphatic or aromatic. n is the average number of iterations.] The method according to claim 1,
Wherein the constituent unit represented by the general formula (II) is an organic residue derived from allylphenol or augenol. 3. The method according to claim 1 or 2,
In the polycarbonate-based resin composition, in the repeating unit represented by the general formula (I), X is an isopropylidene group and a = b = 0. 4. The method according to any one of claims 1 to 3,
In the structural unit represented by the general formula (II), R ³ to R ⁶ are all methyl groups. 5. The method according to any one of claims 1 to 4,
(A-1) to (A-3) in the polycarbonate resin as the component (A), the content of the constituent unit derived from the component (A-2) By mass or less, based on the total amount of the polycarbonate resin composition. 6. The method according to any one of claims 1 to 5,
(C) 0.1 to 1 part by mass of a polytetrafluoroethylene-containing mixed powder, based on 100 parts by mass of the total of the component (A) and the component (B). 7. The method according to any one of claims 1 to 6,
(D) 0.01 to 0.15 parts by mass of at least one member selected from the group consisting of an alkali metal salt of an organic sulfonic acid and an alkaline earth metal salt of an organic sulfonic acid, based on 100 parts by mass of a total of 100 parts by mass of the component (A) Resin composition. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 7. A part for electric / electronic devices comprising the polycarbonate resin composition according to any one of claims 1 to 7. An automotive part comprising the polycarbonate resin composition according to any one of claims 1 to 7.