JP7106434B2 - Polycarbonate resin composition and molded article thereof - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition containing a specific amount of metallic aluminum particles and a molded article thereof.

Polycarbonate-based resin molded products are excellent in transparency, heat resistance, and mechanical properties, so they are used as industrial transparent materials in the electrical/electronics, mechanical, and automotive fields, as well as optical materials such as lenses and optical discs. etc. is widely used.
Furthermore, attempts have been made to greatly improve the product image by adding glossy particles or the like in order to impart decorativeness to the resin molding. Addition of glossy particles or the like makes it possible to obtain a highly designed appearance such as a metallic appearance or a glimmering galaxy appearance that looks like the stars are scattered in the night sky. Patent Document 1 discloses a polyacetal resin composition obtained by adding a metallic pigment as glossy particles to a polyacetal resin composition, and Patent Document 2 discloses a polycarbonate resin composition obtained by adding glossy particles to a polycarbonate resin.

JP 2017-218563 A JP 2009-120674 A

The polyacetal resin composition used in Patent Document 1 is inferior in transparency, further improvement in appearance is desired, and it is also inferior in impact resistance. In the polycarbonate-based resin composition of Patent Document 2, in the vicinity of the confluence of the resin compositions melted during the production of the molded body, the glossy particles contained in the resin composition stand up (orientated) without falling down. Become. As a result, the reflection of light by the glossy particles is disturbed, resulting in appearance problems such as black lines that make the molded product appear dark (dark).

The present inventors have studied to obtain a polycarbonate-based resin composition and a molded article thereof that can suppress appearance defects such as black lines as described above and have excellent impact resistance. As a result, they have found that a polycarbonate resin composition containing a polycarbonate resin containing a specific copolymer unit, a specific amount of metallic aluminum particles, and a specific amount of an ultraviolet absorber can solve the above problems. The present invention relates to the following [1] to [3].

［式中、Ｒ¹及びＲ²はそれぞれ独立に、ハロゲン原子、炭素数１～６のアルキル基又は炭素数１～６のアルコキシ基を示す。Ｘは、単結合、炭素数１～８のアルキレン基、炭素数２～８のアルキリデン基、炭素数５～１５のシクロアルキレン基、炭素数５～１５のシクロアルキリデン基、フルオレンジイル基、炭素数７～１５のアリールアルキレン基、炭素数７～１５のアリールアルキリデン基、－Ｓ－、－ＳＯ－、－ＳＯ₂－、－Ｏ－又は－ＣＯ－を示す。Ｒ³及びＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基又は炭素数６～１２のアリール基を示す。ａ及びｂは、それぞれ独立に０～４の整数を示す。］

［式中、Ｒ³⁰及びＲ³¹は、それぞれ独立に、ハロゲン原子、炭素数１～６のアルキル基又は炭素数１～６のアルコキシ基を示す。Ｘ’は単結合、炭素数１～８のアルキレン基、炭素数２～８のアルキリデン基、炭素数５～１５のシクロアルキレン基、炭素数５～１５のシクロアルキリデン基、－Ｓ－、－ＳＯ－、－ＳＯ₂－、－Ｏ－又は－ＣＯ－を示す。ｄ及びｅは、それぞれ独立に０～４の整数を示す。］
［２］上記［１］に記載のポリカーボネート系樹脂組成物からなる成形体。
［３］自動車内装部品である、上記［２］に記載の成形体。 [1] A polycarbonate block (A-1) comprising a repeating unit represented by the following general formula (I), and a repeating unit represented by the following general formula (II) and having an average repeating number of 85 or more and 95 or less. A polycarbonate system consisting of a polycarbonate-polyorganosiloxane copolymer (A) containing a polyorganosiloxane block (A-2) containing Resin (S), and 0.01 parts by mass or more and 0.05 parts by mass or less of metal aluminum particles (B) and 0.1 parts by mass or more and 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin (S) including the following ultraviolet absorber (C),
The polycarbonate-polyorganosiloxane copolymer (A) contains 5% by mass or more and 7% by mass or less of the polyorganosiloxane block (A-2) and has a viscosity average molecular weight of 16,000 or more and 18,000 or less. death,
The polycarbonate-based resin (S) contains 55% by mass or more and 70% by mass or less of the polycarbonate-polyorganosiloxane copolymer (A), and the polyorganosiloxane block (A-2) is 3% by mass or more and 4% by mass. and having a viscosity average molecular weight of 15,000 or more and 17,000 or less.

[In the formula, 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, a fluorenediyl group, carbon represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-. R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. a and b each independently represents an integer of 0 to 4; ]

[In the formula, R ³⁰ and R ³¹ 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-. d and e each independently represent an integer of 0 to 4; ]
[2] A molded article made of the polycarbonate-based resin composition described in [1] above.
[3] The molded article according to [2] above, which is an automobile interior part.

According to the present invention, a polycarbonate resin composition containing a polycarbonate resin containing a specific copolymerization unit, a specific amount of aluminum particles, and a specific amount of an ultraviolet absorber, when the aluminum particles are blended It is possible to obtain a polycarbonate-based resin composition and a molded article thereof that can suppress appearance defects such as black lines that may occur and that is also excellent in impact resistance.

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate-based resin composition and the molded article thereof of the present invention are described in detail below. In this specification, any definition that is considered preferable can be adopted arbitrarily, and it can be said that a combination of preferable items is more preferable. In this specification, the description of "XX to YY" means "XX or more and YY or less".

The polycarbonate-based resin composition of the present invention is represented by a polycarbonate block (A-1) consisting of a repeating unit represented by general formula (I) described below, and general formula (II) described below, and having an average repeating number of A polycarbonate comprising a polyorganosiloxane block (A-2) containing a repeating unit of 85 or more and 95 or less and a polyorganosiloxane copolymer (A), and a repeating unit represented by the general formula (III) described later. 0.01 parts by mass or more and 0.05 parts by mass or less of metal aluminum particles (B) and 0 .1 parts by mass or more and 0.5 parts by mass or less of an ultraviolet absorber (C), and the polycarbonate-polyorganosiloxane copolymer (A) contains the polyorganosiloxane block (A-2) in an amount of 5% by mass or more. It contains 7% by mass or less and has a viscosity average molecular weight of 16,000 or more and 18,000 or less, and the polycarbonate resin (S) contains the polycarbonate-polyorganosiloxane copolymer (A) in an amount of 55% by mass or more and 70% by mass. 3% by mass or more and 4% by mass or less of the polyorganosiloxane block (A-2), and has a viscosity average molecular weight of 15,000 or more and 17,000 or less.
First, the details of the polycarbonate-based resin (S) contained in the polycarbonate-based resin composition of the present invention will be described below.

［式中、Ｒ¹及びＲ²はそれぞれ独立に、ハロゲン原子、炭素数１～６のアルキル基又は炭素数１～６のアルコキシ基を示す。Ｘは、単結合、炭素数１～８のアルキレン基、炭素数２～８のアルキリデン基、炭素数５～１５のシクロアルキレン基、炭素数５～１５のシクロアルキリデン基、フルオレンジイル基、炭素数７～１５のアリールアルキレン基、炭素数７～１５のアリールアルキリデン基、－Ｓ－、－ＳＯ－、－ＳＯ₂－、－Ｏ－又は－ＣＯ－を示す。Ｒ³及びＲ⁴はそれぞれ独立に、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基又は炭素数６～１２のアリール基を示す。ａ及びｂは、それぞれ独立に０～４の整数を示す。］ <Polycarbonate-polyorganosiloxane copolymer (A)>
The polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes abbreviated as "PC-POS copolymer") (A) contained in the polycarbonate-based resin (S) is represented by the following general formula (I). and a polyorganosiloxane block (A-2) containing a repeating unit represented by the following general formula (II) and having an average repeating number of 85 or more and 95 or less .

[In the formula, 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, a fluorenediyl group, carbon represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-. R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. a and b each independently represents an integer of 0 to 4; ]

In general formula (I) above, the halogen atoms independently represented by R ¹ and R ² include fluorine, chlorine, bromine and iodine atoms.
The alkyl groups independently represented by R ¹ and R ² include methyl group, ethyl group, n-propyl group, isopropyl group, and various butyl groups ("various" means linear and branched groups). The same applies hereinafter in the specification.), various pentyl groups, and various hexyl groups. Examples of the alkoxy groups independently represented by R ¹ and R ² include those having the above alkyl group as the alkyl group moiety.

Examples of the alkylene group represented by X include methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like, and an alkylene group having 1 to 5 carbon atoms is preferred. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. The cycloalkylene group represented by X includes a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group and the like, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. The cycloalkylidene group represented by X includes, for example, a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferred. , a cycloalkylidene group having 5 to 8 carbon atoms is more preferable. The aryl moiety of the arylalkylene group represented by X includes aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, naphthyl group, biphenyl group and anthryl group, and the alkylene group includes the above-mentioned alkylene. The aryl moiety of the arylalkylidene group represented by X includes aryl groups having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group and an anthryl group, and examples of the alkylidene group include the alkylidene groups described above. can be done.

a and b each independently represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1;
Among them, a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or a and b are 0 and X is an alkylene group having 3 carbon atoms, particularly an isopropylidene group. Some are preferred.

In general formula (II) above, the halogen atom represented by R ³ or R ⁴ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group represented by R ³ or R ⁴ includes methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups. Examples of the alkoxy group represented by R ³ or R ⁴ include cases where the alkyl group portion is the aforementioned alkyl group. The aryl group represented by R ³ or R ⁴ includes phenyl group, naphthyl group and the like.
Both R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, and both are methyl groups. It is more preferable to have

More specifically, the polyorganosiloxane block (A-2) containing a repeating unit represented by the general formula (II) is a unit represented by the following general formulas (II-I) to (II-III) It is preferred to have

［式中、Ｒ³～Ｒ⁶は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基または炭素数６～１２のアリール基を示し、複数のＲ³～Ｒ⁶は、互いに同一であっても異なっていてもよい。Ｙは－Ｒ⁷Ｏ－、－Ｒ⁷ＣＯＯ－、－Ｒ⁷ＮＨ－、－Ｒ⁷ＮＲ⁸－、－ＣＯＯ－、－Ｓ－、－Ｒ⁷ＣＯＯ－Ｒ⁹－Ｏ－、または－Ｒ⁷Ｏ－Ｒ¹⁰－Ｏ－を示し、複数のＹは、互いに同一であっても異なっていてもよい。前記Ｒ⁷は、単結合、直鎖、分岐鎖若しくは環状アルキレン基、アリール置換アルキレン基、置換または無置換のアリーレン基、またはジアリーレン基を示す。Ｒ⁸は、アルキル基、アルケニル基、アリール基、またはアラルキル基を示す。Ｒ⁹は、ジアリーレン基を示す。Ｒ¹⁰は、直鎖、分岐鎖もしくは環状アルキレン基、またはジアリーレン基を示す。βは、ジイソシアネート化合物由来の２価の基、またはジカルボン酸若しくはジカルボン酸のハロゲン化物由来の２価の基を示す。ｎはポリオルガノシロキサンの平均鎖長を示す。ｎ－１、及びｐとｑはそれぞれポリオルガノシロキサン単位の平均繰り返し数を示し、１以上の整数であり、ｐとｑの和はｎ－２である。］

[wherein R ³ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms, A plurality of R ³ to R ⁶ may be the same or different. Y is -R ⁷ O-, -R ^{7 COO-, -R 7 NH-, -R 7 NR 8 -, -COO-, -S-, -R 7 COO - R 9 -O-} , or -R ⁷ represents OR ¹⁰ -O-, and plural Y's may be the same or different. R ⁷ above represents a single bond, a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, a substituted or unsubstituted arylene group, or a diarylene group. ^R8 represents an alkyl group, alkenyl group, aryl group or aralkyl group. R ⁹ represents a diarylene group. R ¹⁰ represents a linear, branched or cyclic alkylene group, or a diarylene group. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. n indicates the average chain length of polyorganosiloxane. Each of n-1, p and q represents the average number of repeating polyorganosiloxane units and is an integer of 1 or more, and the sum of p and q is n-2. ]

Halogen atoms independently represented by R ³ to R ⁶ include fluorine, chlorine, bromine and iodine atoms. Examples of the alkyl group independently represented by R ³ to R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups. Examples of the alkoxy groups independently represented by R ³ to R ⁶ include cases where the alkyl group portion is the aforementioned alkyl group. Examples of the aryl group independently represented by R ³ to R ⁶ include a phenyl group and a naphthyl group.
Each of R ³ to R ⁶ is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.
All of R ³ to R ⁶ in general formulas (II-I), (II-II) and/or (II-III) are preferably methyl groups.

-R ⁷ O-, -R ^{7 COO-, -R 7 NH-, -R 7 NR 8 -, -R 7 COO - R 9 -O-} , or -R ⁷ OR ¹⁰ -O- represented by Y The linear or branched alkylene group represented by R ⁷ in above includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Cyclic alkylene groups represented by R ⁷ include cycloalkylene groups having 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms.

（式中ｃは正の整数を示し、通常１～６の整数である） The aryl-substituted alkylene group represented by ^R7 may have a substituent such as an alkoxy group or an alkyl group on the aromatic ring. Specific structures thereof include, for example, the following general formula (i) or ( ii) structure can be shown. Here, when R ⁷ represents an aryl-substituted alkylene group, the alkylene group is attached to Si.

(In the formula, c represents a positive integer, usually an integer of 1 to 6)

The diarylene group represented by R ⁷ , R ⁹ and R ¹⁰ is a group in which two arylene groups are linked directly or via a divalent organic group, specifically -Ar ¹ -W- It is a group having a structure represented by Ar ² —. Ar ¹ and Ar ² each represent an arylene group, and W represents a single bond or a divalent organic group. The divalent organic group represented by W is, for example, an isopropylidene group, a methylene group, a dimethylene group and a trimethylene group.
Arylene groups represented by R ⁷ , Ar ¹ and Ar ² include arylene groups having 6 to 14 ring carbon atoms such as phenylene group, naphthylene group, biphenylene group and anthrylene group. These arylene groups may have arbitrary substituents such as alkoxy groups and alkyl groups.

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

Y is preferably -R ⁷ O-, where R ⁷ is an aryl-substituted alkylene group, particularly a residue of a phenolic compound having an alkyl group, such as an organic residue derived from allylphenol or eugenol More preferred are organic residues derived from
For p and q in formula (II-II), it is preferred that p=q.
Further, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid, for example, a divalent group represented by the following general formulas (iii) to (vii) group.

The average number of repetitions of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) (the number represented by n-1 and p and q in the above formula) should be 85 or more and 95 or less. requires. If the average number of repetitions is less than 85, the impact resistance cannot be sufficiently improved, which is not preferable. On the other hand, if the average repetition number exceeds 95, the transparency is lowered, which is not preferable. From the viewpoint of obtaining higher impact resistance, the average repetition number is preferably 86 or more, more preferably 87 or more, and preferably 90 or less, more preferably 89 or less. The average repetition number is calculated by nuclear magnetic resonance (NMR) measurement.

The PC-POS copolymer (A) should contain 5% by mass or more and 7% by mass or less of the polyorganosiloxane block (A-2). If the amount of polyorganosiloxane in the PC-POS copolymer (A) is outside the above range, it becomes difficult to achieve both excellent impact resistance and transparency, which is not preferred.
The content of the polyorganosiloxane block (A-2) in the PC-POS copolymer (A) is preferably 5.5% by mass or more from the viewpoint of obtaining higher impact resistance, and higher transparency. is preferably less than 7% by mass, more preferably 6.5% by mass or less. The content is calculated by nuclear magnetic resonance (NMR) measurement.

The PC-POS copolymer (A) has a viscosity average molecular weight (Mv) of 16,000 or more and 18,000 or less. If the viscosity-average molecular weight of the PC-POS copolymer (A) is outside the above range, the strength of the molded product will be reduced, or adverse effects such as thermal deterioration during injection molding or extrusion molding will be likely to occur. I don't like it because By using a molecular weight modifier (terminal terminator) or the like, the viscosity average molecular weight can be adjusted within the above range.

The viscosity-average molecular weight of the PC-POS copolymer (A) is preferably 16,500 or more from the viewpoint of obtaining a molded article having higher strength, and from the viewpoint of further suppressing thermal deterioration during molding, preferably less than 18,000.
The viscosity-average molecular weight (Mv) is a value calculated from the following Schnell's formula by measuring the intrinsic viscosity [η] of a methylene chloride solution at 20°C.

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

Specifically, a pre-produced polycarbonate oligomer and polyorganosiloxane, which will be described later, are dissolved in a water-insoluble organic solvent (methylene chloride, etc.), and an alkaline compound aqueous solution (bisphenol A, etc.) of a dihydric phenol compound (bisphenol A, etc.) sodium hydroxide aqueous solution, etc.), using a tertiary amine (triethylamine, etc.) or a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.) as a polymerization catalyst, and a terminal terminator (monohydric phenol such as p-tert-butylphenol ), it can be produced by an interfacial polycondensation reaction. The PC-POS copolymer (A) can also be produced by copolymerizing polyorganosiloxane, dihydric phenol, phosgene, carbonate or chloroformate.

As polyorganosiloxane as a raw material, those represented by the following general formulas (1), (2) and/or (3) can be used.

In the above formula, R ³ to R ⁶ , Y, β, n−1, p and q are as described above, and specific examples and preferred ones are also the same.
Z represents a hydrogen atom or a halogen atom, and multiple Z's may be the same or different.

For example, polyorganosiloxane represented by general formula (1) includes compounds represented by general formulas (1-1) to (1-11) below.

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

In addition, one having the following general formula (4) may be used as the polyorganosiloxane raw material.

In the formula above, R ³ and R ⁴ are the same as described above. The average chain length of the polyorganosiloxane block represented by the general formula (4) is (r×m), and the range of (r×m) is the same as n above.
When the above (4) is used as the polyorganosiloxane raw material, the polyorganosiloxane block (A-2) preferably has units represented by the following general formula (II-IV).

［式中のＲ³、Ｒ⁴、ｒ及びｍは上述した通りである。］

[R ³ , R ⁴ , r and m in the formula are as described above. ]

［式中、Ｒ¹⁸～Ｒ²¹はそれぞれ独立に水素原子又は炭素数１～１３のアルキル基である。Ｒ²²は炭素数１～６のアルキル基、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１～６のアルコキシ基、又は炭素数６～１４のアリール基である。Ｑ²は炭素数１～１０の２価の脂肪族基である。ｎ－１はポリオルガノシロキサンブロックの繰り返し数を示し、その範囲は上記した通りである。］ The polyorganosiloxane block (A-2) may have a structure represented by the following general formula (II-V).

[In the formula, R ¹⁸ to R ²¹ are each independently a hydrogen atom or an alkyl group having 1 to 13 carbon atoms. R ²² is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Q ² is a divalent aliphatic group having 1 to 10 carbon atoms. n-1 represents the number of repeating polyorganosiloxane blocks, and its range is as described above. ]

In general formula (II-V), the alkyl group having 1 to 13 carbon atoms independently represented by R ¹⁸ to R ²¹ includes methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various Examples include pentyl group, various hexyl groups, various heptyl groups, various octyl groups, 2-ethylhexyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, and various tridecyl groups. Among these, R ¹⁸ to R ²¹ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²² include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups and various hexyl groups. Halogen atoms represented by R ²² include fluorine, chlorine, bromine and iodine atoms. Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ²² include cases where the alkyl group portion is the aforementioned alkyl group. Examples of the aryl group having 6 to 14 carbon atoms represented by R ²² include phenyl group, toluyl group, dimethylphenyl group and naphthyl group.
Among the above, R ²² is preferably a hydrogen atom or an alkoxy group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkoxy group having 1 to 3 carbon atoms, and still more preferably a hydrogen atom.

The divalent aliphatic group having 1 to 10 carbon atoms represented by Q ² is preferably a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms. The saturated aliphatic group preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms. The repetition number n-1 is as described above.

［式中、ｎ－１は前記と同じである。］ Preferred embodiments of the structural unit (II-V) include structures represented by the following formulas (II-VI).

[In the formula, n−1 is the same as described above. ]

［式中、Ｒ¹⁸～Ｒ²²、Ｑ²、及びｎ－１は上記した通りである。］ The polyorganosiloxane block (A-2) represented by the general formula (II-V) or (II-VI) above uses a polyorganosiloxane raw material represented by the following general formula (5) or (6). can be obtained by

[In the formula, R ¹⁸ to R ²² , Q ² and n-1 are as described above. ]

［式中、ｎ－１は上記した通りである。］

[In the formula, n−1 is as described above. ]

The method for producing the polyorganosiloxane is not particularly limited. For example, according to the method described in JP-A-11-217390, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α,ω-dihydrogenorganopentasiloxane, followed by A phenolic compound (eg, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) is added to the α,ω-dihydrogenorganopentasiloxane in the presence of a hydrosilylation reaction catalyst. Thus, a crude polyorganosiloxane can be obtained. Further, according to the method described in Japanese Patent No. 2662310, octamethylcyclotetrasiloxane and tetramethyldisiloxane are reacted in the presence of sulfuric acid (acidic catalyst) to obtain α,ω-dihydrogenorgano A crude polyorganosiloxane can be obtained by subjecting a polysiloxane to an addition reaction with a phenolic compound or the like in the presence of a hydrosilylation reaction catalyst in the same manner as described above. The α,ω-dihydrogenorganopolysiloxane may be used by appropriately adjusting its chain length n depending on the polymerization conditions, or commercially available α,ω-dihydrogenorganopolysiloxane may be used. Specifically, as the hydrosilylation catalyst, those described in JP-A-2016-098292 can be used.

Polycarbonate oligomers can be produced by reacting a dihydric phenol with a carbonate precursor such as phosgene or triphosgene in an organic solvent such as methylene chloride, chlorobenzene or chloroform. When producing a polycarbonate oligomer using a transesterification method, it can also be produced by reacting a dihydric phenol with a carbonate precursor such as diphenyl carbonate.

［式中、Ｒ¹、Ｒ²、ａ、ｂ及びＸは上述した通りである。］ As the dihydric phenol, it is preferable to use a dihydric phenol represented by the following general formula (viii).

[wherein R ¹ , R ² , a, b and X are as defined above. ]

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

Examples of dihydric phenols other than bisphenol A include bis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyaryl ethers, dihydroxydiarylsulfides, dihydroxydiarylsulfoxides, dihydroxydiarylsulfones, dihydroxy diphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantanes, and the like. These dihydric phenols may be used singly or in combination of two or more.

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

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

Examples of dihydroxydiarylsulfides include 4,4'-dihydroxydiphenylsulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide. Examples of dihydroxydiarylsulfoxides include 4,4'-dihydroxydiphenylsulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide. Examples of dihydroxydiarylsulfones include 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone.

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

Examples of dihydric phenols other than the above include 4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol, 10,10-bis(4-hydroxyphenyl)-9-anthrone, 1,5 -bis(4-hydroxyphenylthio)-2,3-dioxapentane and the like.

A terminal terminator (molecular weight modifier) can be used to adjust the molecular weight of the resulting PC-POS copolymer (A). Examples of terminal terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol. Mention may be made of monohydric phenols. These monohydric phenols may be used singly or in combination of two or more.

After the interfacial polycondensation reaction, the aqueous phase and the organic solvent phase are separated by standing appropriately [separation step], and the organic solvent phase is washed (preferably washed with a basic aqueous solution, an acidic aqueous solution, and water in this order) [washing step]. ], and the resulting organic phase is concentrated [concentration step] and dried [drying step] to obtain the PC-POS copolymer (A) contained in the polycarbonate-based resin composition of the present invention. .

<Polycarbonate resin (A')>
The polycarbonate-based resin (S) contained in the polycarbonate-based resin composition of the present invention is the PC-POS copolymer (A) and a polycarbonate resin (A' ).

［式中、Ｒ³⁰及びＲ³¹は、それぞれ独立に、ハロゲン原子、炭素数１～６のアルキル基又は炭素数１～６のアルコキシ基を示す。Ｘ’は単結合、炭素数１～８のアルキレン基、炭素数２～８のアルキリデン基、炭素数５～１５のシクロアルキレン基、炭素数５～１５のシクロアルキリデン基、－Ｓ－、－ＳＯ－、－ＳＯ₂－、－Ｏ－又は－ＣＯ－を示す。ｄ及びｅは、それぞれ独立に０～４の整数を示す。］ The polycarbonate-based resin (A') is a polycarbonate-based resin other than the PC-POS copolymer (A), and the main chain is composed of repeating units represented by the following general formula (III). As the polycarbonate-based resin, various known polycarbonate-based resins can be used without any particular limitation.

[In the formula, R ³⁰ and R ³¹ 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-. d and e each independently represent an integer of 0 to 4; ]

Specific examples of the groups represented by R ³⁰ and R ³¹ are the same as those for R ¹ and R ² above, and the preferred groups are also the same. R ³⁰ and R ³¹ more preferably represent an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Specific examples of X' are the same as those of X above, and the preferred ones are also the same. d and e are each independently preferably 0 to 2, more preferably 0 or 1;

［式中、Ｒ³⁰、Ｒ³¹、Ｘ’、ｄ及びｅは前記定義の通りであり、好ましいものも同じである。］ Specifically, the polycarbonate-based resin (A′) is prepared by reacting a dihydric phenol-based compound and phosgene in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, followed by a tertiary amine or The interfacial polymerization method, in which a polymerization catalyst such as a quaternary ammonium salt is added for polymerization, or the pyridine method, in which a dihydric phenolic compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent, and phosgene is introduced for direct production. , etc., which can be obtained by a conventional method for producing a polycarbonate can be used.
In the above reaction, if necessary, a molecular weight modifier (terminal terminator), a branching agent and the like are used. Examples of dihydric phenol compounds include those represented by the following general formula (III').

[In the formula, R ³⁰ , R ³¹ , X′, d and e are as defined above, and preferred ones are also the same. ]

Specific examples of the dihydric phenol compound include those described in the method for producing the PC-POS copolymer (A), and the preferred ones are also the same. Among them, bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, and bisphenol A is more preferred.
The polycarbonate-based resin (A') may be used alone or in combination of two or more. Unlike the PC-POS copolymer (A), the polycarbonate resin (A') does not have a polyorganosiloxane block represented by formula (II). Polycarbonate resin may be used.

The polycarbonate resin (S) should contain 55% by mass or more and 70% by mass or less of the PC-POS copolymer (A). If the amount of the PC-POS copolymer (A) in the polycarbonate resin (S) is less than 55% by mass, it is difficult to obtain better impact resistance. If the amount of the PC-POS copolymer (A) in the polycarbonate-based resin (S) exceeds 70% by mass, the resulting resin composition will be inferior in transparency, which is not preferred. From the viewpoint of obtaining better impact resistance and transparency, the content is preferably 58% by mass or more, more preferably 60% by mass or more, preferably less than 70% by mass, and more preferably 65% by mass or less.

The content of the polycarbonate-based resin (A') in the polycarbonate-based resin (S) corresponds to the remainder obtained by removing the PC-POS copolymer (A) from 100% by mass of the polycarbonate-based resin (S).

The polycarbonate resin (S) should contain 3% by mass or more and 4% by mass or less of the polyorganosiloxane block (A-2). If the content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is outside the above range, it will be difficult to achieve both excellent impact resistance and transparency.
The content of the polyorganosiloxane block (A-2) in the polycarbonate resin (S) is preferably 3.3% by mass or more, more preferably 3.5% by mass or more, from the viewpoint of obtaining higher impact resistance. and preferably 3.9% by mass or less from the viewpoint of obtaining more excellent transparency. The content is calculated by nuclear magnetic resonance (NMR) measurement.

The viscosity-average molecular weight (Mv) of the polycarbonate-based resin (S) is 15,000 or more and 17,000 or less. When the viscosity-average molecular weight of the polycarbonate resin (S) is outside the above range, the strength of the molded product is lowered, or adverse effects such as thermal deterioration during injection molding or extrusion molding are likely to occur, which is not preferable. . By using a molecular weight modifier (terminal terminator) or the like, the viscosity average molecular weight can be adjusted within the above range. The viscosity-average molecular weight of the polycarbonate-based resin (S) is preferably 15,000 or more and 16,500 or less. If the viscosity-average molecular weight is within the above range, the strength of the molded product will be more excellent, and thermal deterioration during injection molding or extrusion molding will be more suppressed. The viscosity-average molecular weight of the polycarbonate-based resin (S) is more preferably 15,500 or more from the viewpoint of obtaining a molded product having higher strength, and more preferably 16 from the viewpoint of further suppressing thermal deterioration during molding. , 500. The viscosity-average molecular weight (Mv) is a value measured in the same manner as described for the PC-POS copolymer (A), that is, the intrinsic viscosity [η] of a methylene chloride solution at 20°C is measured, and the following Schnell formula It is a value calculated from

<Metal aluminum particles (B)>
The polycarbonate-based resin composition of the present invention contains 0.01 parts by mass or more and 0.05 parts by mass or less of metal aluminum particles (B) with respect to 100 parts by mass of the polycarbonate-based resin (S).
If the content of the metal aluminum particles (B) is less than 0.01 parts by mass with respect to 100 parts by mass of the polycarbonate resin (S), it is difficult to provide the surface with a design such as a metallic appearance, which is not preferable. . If the content of the metal aluminum particles (B) exceeds 0.05 parts by mass, the impact resistance is lowered, which is not preferable.

The content of the metal aluminum particles (B) is preferably 0.015 parts by mass or more, more preferably 0.02 parts by mass or more, from the viewpoint of imparting design properties such as a metallic appearance to the surface of the molded article, From the viewpoint of obtaining higher impact resistance, it is preferably less than 0.05 parts by mass, more preferably 0.04 parts by mass or less, even more preferably 0.03 parts by mass or less, and even more preferably 0.025 parts by mass or less. is.

<Ultraviolet absorber (C)>
The polycarbonate-based resin composition of the present invention contains 0.1 parts by mass or more and 0.5 parts by mass or less of the ultraviolet absorber (C) with respect to 100 parts by mass of the polycarbonate-based resin (S). If the content of the ultraviolet absorber (C) in the composition is less than 0.1 part by mass, the weather resistance will be insufficient, which is not preferred. If the content of the ultraviolet absorber (C) exceeds 0.5 parts by mass, it will lead to contamination of the mold, which is not preferred. The amount of the ultraviolet absorber (C) is preferably 0.2 parts by mass or more and preferably 0.4 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin (S).

Examples of the ultraviolet absorber (C) contained in the polycarbonate-based resin composition of the present invention include benzotriazole-based, benzoxazinone-based, salicylate-based, malonic acid ester-based, oxalyl alanide-based, triazine-based, benzophenone-based, and cyanoacrylates. various compounds such as These can be used individually by 1 type or in combination of 2 or more types. As the ultraviolet absorber (C), a benzotriazole-based ultraviolet absorber is preferable from the viewpoint of weather resistance.

Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-butylphenyl)benzotriazole, 2-( 2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3' ,5′-diamylphenyl)benzotriazole, 2-(2′-hydroxy-3′-dodecyl-5′-methylphenyl)benzotriazole, 2-(2′-hydroxy-3′,5′-dicumylphenyl ) benzotriazole, 2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] and the like.

<Other additives>
The polycarbonate-based resin composition of the present invention comprises a PC-POS copolymer (A), a polycarbonate-based resin (S) consisting of a polycarbonate resin (A'), metal aluminum particles (B), and an ultraviolet absorber (C ), other components described below may be included as long as they do not impair the effects of the present invention. Other additives include antioxidants, release agents, reinforcing materials, fillers, elastomers for improving impact resistance, colorants, antistatic agents, resins other than polycarbonate resins, and the like. Some additives are more specifically described below.

<Colorant>
As the coloring agent, those having no hiding property are preferable, and dyes and pigments can be used. Examples of dyes include methine dyes, pyrazolone dyes, perinone dyes, azo dyes, quinophthalone dyes, and anthraquinone dyes. Examples of pigments include inorganic pigments, organic pigments, mixtures of organic pigments having complementary colors, mixtures of organic pigments of three primary colors, and mixtures of organic pigments having complementary colors. Examples of inorganic pigments include black pigments such as carbon black (grades MT, FT, SRF, GPF, FET, HAF, ISAF, SAF, MPC, etc.), chromium (Cr), nickel (Ni), copper (Cu), praseodymium ( Pr), platinum, ruthenium, titanium and other metals, and their oxides. Examples of white pigments include titanium oxide, zinc oxide, lithopone, zinc sulfide, white lead, and the like.

Mixture of organic pigments of primary colors Examples of organic pigments of three primary colors include red (R) perylene-based pigments, lake pigments, azo-based pigments, quinacridone-based pigments, anthraquinone-based pigments, anthracene-based pigments, azo-based pigments, and isoindoline-based pigments. , isoindolinone-based pigments, etc. alone or as a mixture of at least two of them. For green (G), single or at least two types of multi-halogen phthalocyanine pigments, multi-halogen copper phthalocyanine pigments, triphenylmethane basic dyes, azo pigments, isoindoline pigments, isoindolinone pigments, etc. Mixtures of the above may be mentioned. Blue (B) includes copper phthalocyanine-based pigments, indanthrone-based pigments, indophenol-based pigments, cyanine-based pigments, and dioxazine-based pigments, either singly or as a mixture of at least two of them. Mixtures of these three primary colors can be used.

Examples of mutually complementary colors in the mixture of mutually complementary organic pigments include combinations of red and cyanine, blue, green and magenta, purple, and blue and yellow. Specific examples of individual colors include, in addition to the above three primary colors, disazo-based pigments, isoindoline-based pigments, and isoindolinone-based pigments for yellow, and dioxandine-based pigments for purple. A mixture of these organic pigments having a complementary relationship is used.

<Filler>
Examples of fillers include inorganic fillers such as talc, mica, clay, wollastonite, bentonite, glass fiber, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, hydrotalcite, magnesium oxide, calcium oxide, and calcium carbonate and the like can be preferably used.

<Antioxidant>
Phenolic antioxidants and phosphorus antioxidants can be preferably used as antioxidants.
Examples of phenolic antioxidants include triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, N,N -hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris(3,5-di -tert-butyl-4-hydroxybenzyl)isocyanurate, 3,9-bis[1,1-dimethyl-2-[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl ]-2,4,8,10-tetraoxaspiro(5,5)undecane and the like.

Examples of phosphorus antioxidants include triphenylphosphite, trisnonylphenylphosphite, tris(2,4-di-tert-butylphenyl)phosphite, tridecylphosphite, trioctylphosphite, and trioctadecylphosphite. , didecylmonophenylphosphite, dioctylmonophenylphosphite, diisopropylmonophenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, bis(2,6-di-tert-butyl- 4-methylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di -tert-butylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite and the like.
These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more types. The amount of the antioxidant to be added is preferably about 0.05 to 1.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin (S). If the antioxidant is within the above range, higher flame retardancy can be obtained. From this point of view, the amount of antioxidant added is more preferably 0.08 parts by mass or more, more preferably 0.5 parts by mass or less, still more preferably 0.3 parts by mass or less, and particularly preferably 0.15 parts by mass. Part by mass or less.

The polycarbonate-based resin composition of the present invention is obtained by blending each of the above-described components in the above-mentioned proportions, and further optionally various optional components in appropriate proportions, and kneading the mixture.
In one aspect of the present invention, the total content of the polycarbonate resin (S), the metal aluminum particles (B) and the ultraviolet absorber (C) is based on the total amount (100% by mass) of the polycarbonate resin composition, preferably 80 to 100% by mass, more preferably 95 to 100% by mass, even more preferably 97 to 100% by mass, particularly preferably 98 to 100% by mass, most preferably 99 to 100% by mass.

Blending and kneading are premixed with commonly used equipment such as ribbon blenders, drum tumblers, etc., Henschel mixers, Banbury mixers, single screw extruders, twin screw extruders, multi-screw extruders and It can be carried out by a method using a co-kneader or the like. The heating temperature during kneading is usually appropriately selected within the range of 240° C. or higher and 320° C. or lower. For this melt-kneading, it is preferable to use an extruder, particularly a vent-type extruder.

<Molded body>
Using the melt-kneaded polycarbonate resin composition of the present invention or the pellets obtained after melt-kneading as raw materials, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, and Various moldings can be produced by a foam molding method or the like. In particular, pellets obtained by melt-kneading can be suitably used for production of injection-molded articles by injection molding and injection compression molding.

The molded article of the present invention may be subjected to texturing or the like in order to further enhance the design. For example, the molding surface of the mold during injection molding is subjected to texture processing that reproduces the grain pattern (unevenness) by chemical corrosion (etching), and the polycarbonate resin composition is injected into this mold to form the surface of the resin molding. The texturing process can be performed by transferring a three-dimensional texturing pattern to the surface. By applying texturing to the molded body of the present invention, the light incident on the top surface of the geometrically textured surface is reflected in various directions by reflection and scattering at the uneven portions, so that the surface of the molded body becomes brighter as a whole. , the black line is also less visible, which is preferable.
The height of the unevenness in texturing is not particularly limited, but can be, for example, 5 μm or more and 700 μm or less. When the unevenness height of the uneven pattern is within the above range, the visibility of the uneven pattern is excellent and it is easy to form a fine pattern rich in design, which is preferable. More specifically, the height of the unevenness is more preferably 10 μm or more and 350 μm or less.

The molded article of the present invention may be two-color molded. In that case, the polycarbonate-based resin composition of the present invention should be injected on at least one of the primary side and the secondary side.
Since the molded article of the present invention suppresses appearance defects such as black lines and has excellent impact resistance, it can be used as housings for parts for electrical and electronic equipment, parts for automobiles and building materials, and particularly as interior parts for automobiles. It can be used preferably.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Characteristic values and evaluation results in each example were determined according to the following procedures.

(1) Polydimethylsiloxane chain length and content It was calculated from the integral value ratio of methyl groups of polydimethylsiloxane by NMR measurement. In this specification, polydimethylsiloxane may be abbreviated as PDMS.
<Method for quantifying chain length of polydimethylsiloxane>
¹ H-NMR measurement conditions NMR equipment: ECA-500 manufactured by JEOL RESONANCE Co., Ltd.
Probe: 50TH5AT/FG2
Observation range: -5 to 15 ppm
Observation center: 5 ppm
Pulse repetition time: 9 seconds Pulse width: 45°
NMR sample tube: 5φ
Sample amount: 30-40mg
Solvent: deuterated chloroform Measurement temperature: room temperature Accumulation times: 256 For allylphenol-terminated polydimethylsiloxane A: Integrated value of methyl group in dimethylsiloxane moiety observed around δ-0.02 to 0.5 B: δ2. Integrated value of methylene group of allylphenol observed around 50 to 2.75 Chain length of polydimethylsiloxane = (A/6)/(B/4)
In the case of eugenol-terminated polydimethylsiloxane A: Integrated value of methyl group of dimethylsiloxane part observed around δ-0.02 to 0.5 B: Methylene group of eugenol observed around δ 2.40 to 2.70 Integral value Chain length of polydimethylsiloxane = (A/6)/(B/4)

<Method for quantifying polydimethylsiloxane content>
Method for quantifying the amount of polydimethylsiloxane copolymerized in PTBP-terminated polycarbonate copolymerized with allylphenol-terminated polydimethylsiloxane NMR equipment: ECA-500 manufactured by JEOL RESONANCE Co., Ltd.
Probe: 50TH5AT/FG2
Observation range: -5 to 15 ppm
Observation center: 5 ppm
Pulse repetition time: 9 seconds Pulse width: 45°
Number of times of integration: 256 times NMR sample tube: 5φ
Sample amount: 30-40mg
Solvent: deuterated chloroform Measurement temperature: room temperature A: Integrated value of the methyl group of the BPA portion observed around δ 1.5 to 1.9 B: dimethylsiloxane portion observed around δ -0.02 to 0.3 Integrated value of methyl group C: Integrated value of butyl group of p-tert-butylphenyl moiety observed around δ1.2 to 1.4 a = A/6
b=B/6
c=C/9
T = a + b + c
f=a/T×100
g=b/T×100
h=c/T×100
TW=f×254+g×74.1+h×149
PDMS (wt%) = g x 74.1/TW x 100

(2) Viscosity-average molecular weight The viscosity-average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution at 20°C using an Ubbelohde viscometer, obtaining the intrinsic viscosity [η] from this, and calculating the following formula (Schnell's formula ).

<Production example: Production of polycarbonate oligomer>
2000 ppm of sodium dithionite relative to bisphenol A (BPA) (later dissolved) was added to a 5.6% by weight aqueous sodium hydroxide solution. BPA was dissolved in this so that the BPA concentration was 13.5% by mass to prepare an aqueous sodium hydroxide solution of BPA.
This sodium hydroxide aqueous solution of BPA was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at flow rates of 40 L/hr, 15 L/hr of methylene chloride and 4.0 kg/hr of phosgene. The tubular reactor had a jacket portion, and cooling water was passed through the jacket to keep the temperature of the reaction solution at 40°C or less. The reaction liquid discharged from the tubular reactor was continuously introduced into a baffled tank reactor having an internal volume of 40 L and equipped with swept-back blades. The reaction was carried out by adding 0.07 L/hr of a sodium hydroxide aqueous solution of 0.07 L/hr by mass, 17 L/hr of water, and 0.64 L/hr of a 1 mass % triethylamine aqueous solution. The reaction liquid overflowing from the tank-type reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
The polycarbonate oligomer thus obtained had a concentration of 341 g/L and a chloroformate group concentration of 0.71 mol/L.

<Polycarbonate-polyorganosiloxane copolymer (A)>
15 L of the polycarbonate oligomer solution prepared in the above production example, 10.1 L of methylene chloride, and polydimethylsiloxane having an average chain length n of 88 were placed in a 50 L tank-type reactor equipped with a baffle plate, a paddle-type stirring blade, and a cooling jacket. 407 g of o-allylphenol end-modified polydimethylsiloxane (PDMS) and 8.4 mL of triethylamine were charged, and 1065 g of an aqueous sodium hydroxide solution prepared by dissolving 85 g of sodium hydroxide in 980 mL of pure water was added thereto under stirring, and the polycarbonate oligomer and the polycarbonate oligomer were added for 20 minutes. Reaction with allylphenol-terminated PDMS was performed.
In this polymerization solution, a methylene chloride solution of p-tert-butylphenol (PTBP) (70.4 g of PTBP dissolved in 1.0 L of methylene chloride), an aqueous sodium hydroxide solution of bisphenol A (618 g of sodium hydroxide and dithionite An aqueous solution prepared by dissolving 2.1 g of sodium in 9.0 L of pure water and dissolving 1093 g of bisphenol A) was added, and the polymerization reaction was carried out for 40 minutes.
After adding 13 L of methylene chloride for dilution and stirring for 20 minutes, the mixture was separated into an organic phase containing polycarbonate-polydimethylsiloxane copolymer (PC-PDMS copolymer) and an aqueous phase containing excess bisphenol A and sodium hydroxide. , the organic phase was isolated.
The methylene chloride solution of the PC-PDMS copolymer thus obtained was washed with 15% by volume of 0.03 mol/L sodium hydroxide aqueous solution and 0.2 mol/L hydrochloric acid in that order. Washing with pure water was repeated until the electric conductivity in the aqueous phase of the sample became 5 μS/cm or less.
The methylene chloride solution of the PC-PDMS copolymer obtained by washing was concentrated and pulverized, and the resulting flakes were dried at 120° C. under reduced pressure to produce a PC-PDMS copolymer (A).
The PC-PDMS copolymer (A) thus obtained had a PDMS block content of 6.0% by mass and a viscosity-average molecular weight Mv of 17,700 as determined by NMR.

<Polycarbonate resin (A')>
Aromatic homopolycarbonate resin (A') [manufactured by Idemitsu Kosan Co., Ltd., Toughlon FN1500 (trade name), viscosity average molecular weight = 14,200]
<Metal aluminum particles (B)>
M-70 (Raw material code used within Sanyo Kako Co., Ltd., aluminum particles)
<Ultraviolet absorber (C)>
"LA-31RG (trade name)"[2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], Co., Ltd. Made by ADEKA]

<Other ingredients>
Antioxidant: "IRGAFOS 168 (trade name)" [tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Japan Ltd.]

Examples 1-3, Comparative Examples 1-3
The PC-PDMS copolymer (A), the polycarbonate resin (A'), the metal aluminum particles (B), the UV absorber (C) and other components were mixed in the proportions shown in Table 1, and the vent type The mixture was supplied to a twin-screw extruder (TEM35B, manufactured by Toshiba Machine Co., Ltd.) and melt-kneaded at a screw rotation speed of 150 rpm, a discharge rate of 20 kg/hr, and a resin temperature of 295 to 300° C. to obtain a pellet sample for evaluation.

[Evaluation test]
After drying the pellets obtained above at 100° C. for 5 hours, they were injection molded using an injection molding machine at a cylinder temperature of 280° C. and a mold of 80° C. to obtain desired test pieces necessary for the following evaluations. Using this test piece, Y highlight/shade, Charpy impact strength, and black line of the molded product were evaluated. The results are also shown in Table 1.

<Y highlight/shade>
Using a three-dimensional spectrophotometer "DDS3000" (manufactured by Nippon Denshoku Industries Co., Ltd.), the Y value was measured at an incident angle of -45 degrees and a reflection angle of -40 to 70 degrees for the molded test piece having a thickness of 3 mm. The difference between the Y value at a reflection angle of 30 degrees and the reflection angle of -30 degrees was defined as Y highlight/shade. The Y value was calibrated using the value of the standard white plate as 100%. A case where the Y highlight/shade was 2 or more was judged as "A", and a case where it was less than 2 was judged as "B".

<Charpy impact strength>
The obtained pellets were injection molded under the conditions described above to prepare a Charpy test piece (4 mm thick). Measure the Charpy impact strength at 23 ° C. and -30 ° C. in accordance with ISO179-1: 2010 using a test piece in which a notch (r = 0.25 mm ± 0.05 mm) is added to this test piece by post-processing. did.

<Black line evaluation>
Molding was carried out using a tensile test piece mold with a two-point gate, and black lines in the welded portions of the obtained moldings were observed with the naked eye and evaluated as follows.
A: No black line is visible.
B: A black line is clearly visible.

The polycarbonate-based resin composition obtained in the present invention suppresses appearance defects such as black lines and has excellent impact resistance. In particular, it can be suitably used as an automobile interior part.

Claims (3)

Polyorgano containing a polycarbonate block (A-1) consisting of a repeating unit represented by the following general formula (I), and a repeating unit represented by the following general formula (II) and having an average repeating number of 85 or more and 95 or less Polycarbonate resin (S ), and 0.01 parts by mass or more and 0.05 parts by mass or less of metal aluminum particles (B) and 0.1 parts by mass or more and 0.5 parts by mass or less of ultraviolet rays with respect to 100 parts by mass of the polycarbonate resin (S) including an absorbent (C),
The polycarbonate-polyorganosiloxane copolymer (A) contains 5% by mass or more and 7% by mass or less of the polyorganosiloxane block (A-2) and has a viscosity average molecular weight of 16,000 or more and 18,000 or less. death,
The polycarbonate-based resin (S) contains 55% by mass or more and 70% by mass or less of the polycarbonate-polyorganosiloxane copolymer (A), and the polyorganosiloxane block (A-2) is 3% by mass or more and 4% by mass. and having a viscosity average molecular weight of 15,000 or more and 17,000 or less.

[In the formula, 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, a fluorenediyl group, carbon represents an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO ₂ -, -O- or -CO-. R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. a and b each independently represents an integer of 0 to 4; ]

[In the formula, R ³⁰ and R ³¹ 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-. d and e each independently represent an integer of 0 to 4; ] A molded article made of the polycarbonate-based resin composition according to claim 1 . 3. The molded article according to claim 2, which is an automobile interior part.