WO2019054194A1

WO2019054194A1 - Polycarbonate resin composition and molded article of same

Info

Publication number: WO2019054194A1
Application number: PCT/JP2018/032204
Authority: WO
Inventors: 智子阿部; 義生岡本; 靖浩茂木
Original assignee: 出光興産株式会社
Priority date: 2017-09-13
Filing date: 2018-08-30
Publication date: 2019-03-21
Also published as: JP2021028351A; TW201915085A

Abstract

A polycarbonate resin composition that includes: a polycarbonate resin composition (S) that includes 1–50 mass% of a styrene resin (B) and 50–99 mass% of a polycarbonate resin (A) that contains a specific polycarbonate-polyorganosiloxane copolymer (A1); and a white pigment (C). The polycarbonate resin composition includes 0.1–40 parts by mass of the white pigment (C) per 100 parts by mass of the polycarbonate resin composition (S).

Description

Polycarbonate resin composition and molded article thereof

The present invention relates to a polycarbonate resin composition and a molded article thereof. More specifically, the present invention relates to a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer, a styrene resin, and a white pigment, and suppressing appearance defects such as black streaks during molding, and a molded article thereof.

Polycarbonate resins are excellent in mechanical strength, electrical properties, transparency and the like, and are widely used as engineering plastics in various fields such as the fields of electric and electronic devices and automobiles. Polycarbonate resin is also used for housings such as mobile phones, mobile personal computers, digital cameras, video cameras, and power tools. In these applications, impact resistance is important because there is a possibility of dropping during handling. , Design (especially color) is also an important factor.
Resin materials including polycarbonate resins can be relatively easily provided with a desired color by blending a colorant such as a pigment. Among polycarbonate resins, a polycarbonate-polyorganosiloxane copolymer (hereinafter sometimes referred to as a PC-POS copolymer) obtained by copolymerizing a polyorganosiloxane is excellent in impact resistance, and thus, it can be used for the above-mentioned applications. Application is expected.

The PC-POS copolymer has high impact resistance and excellent moldability, in addition to the heat resistance and hydrolysis resistance of general homopolycarbonate resins, so it has a thin wall with severe usage conditions and environment. Application to molded articles and high strength members is in progress. However, a resin composition in which a white pigment such as titanium oxide is mixed with a polycarbonate resin containing a PC-POS copolymer as a main component has a problem that a black streak pattern (black streak) is generated at the time of molding. . Therefore, in the white colored polycarbonate resin material, it is necessary to shorten the average chain length of the polyorganosiloxane moiety in the PC-POS copolymer, or to reduce the blending amount of the PC-POS copolymer, and thus the impact resistance Further improvement was difficult.

Patent Document 1 discloses a polycarbonate resin composition containing a PC-POS copolymer and a titanium oxide, wherein the PC-POS copolymer having a short average chain length of the polyorganosiloxane portion and the PC having a long average chain length. It is described that the occurrence of black streaks at the time of molding is suppressed by using in combination with-POS copolymer, and a polycarbonate resin composition excellent in impact resistance is obtained. However, the resin composition disclosed in Patent Document 1 requires the use of a PC-POS copolymer in which the average chain length of the polyorganosiloxane moiety is short.

In addition, white pigments such as titanium oxide, zinc sulfide, and zinc oxide used in white colored polycarbonate resin compositions such as white reflectors attached to backlight units of liquid crystal displays (LCDs) are usually before polycarbonate molding Even after sufficient dehumidification and drying at 100 to 120 ° C., which is the preliminary drying conditions to be carried out in the above, there is still remaining water which can not be completely removed. It is known that when the resin composition containing this water is injection-molded, the water is evaporated by the molding heat to generate a silver streak. In order to overcome this problem, silver is obtained using a polycarbonate resin composition containing a combination of a polycarbonate-based polymer and titanium oxide in which the difference in water concentration by Karl Fischer at 100 ° C. and 300 ° C. is reduced to 2700 mass ppm or less A technique for suppressing the occurrence of streaks is known (for example, Patent Document 2). However, Patent Document 2 does not disclose any technique for suppressing the generation of black streaks during molding, which is a unique phenomenon in polycarbonate resin compositions containing a PC-POS copolymer and a white pigment.

International Publication No. 2013/051557 International Publication No. 2006/030791

The present invention provides a polycarbonate resin composition containing the PC-POS copolymer, a styrenic resin, and a white pigment, and suppressing the occurrence of appearance defects such as black streaks during molding, and a molded article thereof. To aim.

The present inventors have found that a polycarbonate-based resin composition containing a predetermined PC-POS copolymer and a styrene-based resin, and a polycarbonate-based resin composition containing a predetermined amount of a white pigment, achieve the above-mentioned problems. The
That is, the present invention relates to the following 1 to 16.
1. A polycarbonate-polyorganosiloxane copolymer (A1) containing a polycarbonate block consisting of repeating units represented by the following general formula (I) and a polyorganosiloxane block containing repeating units represented by the following general formula (II) And a white pigment (C), and a polycarbonate resin composition (S) containing 50% by mass or more and 92% by mass or less and 8% by mass or more and 50% by mass or less of a styrene resin (B) Including
The polycarbonate-type resin composition which contains the said white pigment (C) 0.1 mass part or more and 40 mass parts or less with respect to 100 mass parts of said polycarbonate-type resin composition (S).

[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 represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon And an aryl alkylene 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 represent an integer of 0 to 4; ]

2. The polycarbonate resin composition according to the above 1, wherein the styrene resin (B) is an acrylonitrile-butadiene-styrene copolymer.
3. The resin composition according to the above 1 or 2, wherein the average chain length of the polyorganosiloxane block is 50 or more.
4. The polycarbonate resin composition according to any one of 1 to 3, wherein the content of the polyorganosiloxane in the polycarbonate resin (A) is 0.1% by mass or more and 25% by mass or less.
5. The polycarbonate resin composition according to any one of 1 to 4, wherein the viscosity average molecular weight of the polycarbonate resin (A) is 12,000 or more and 50,000 or less.
6. The polycarbonate system according to any one of the above 1 to 5, wherein the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer (A1) is 1.0% by mass to 40% by mass. Resin composition.
7. The polycarbonate resin according to any one of the above 1 to 6, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide pigments, zinc sulfide pigments, zinc oxide pigments, and barium sulfate pigments. Composition.
8. 7. The resin composition according to 7 above, wherein the white pigment (C) is a titanium oxide pigment.
9. The polycarbonate-based resin according to the above 8, wherein the titanium oxide pigment has an inorganic oxide layer composed of one or more inorganic oxides selected from the group consisting of silica, zirconia, and alumina on the surface of titanium oxide particles. Composition.
10. The polycarbonate resin composition according to the above 9, wherein the titanium oxide pigment further has an organic layer on the surface of the inorganic oxide layer.
11. 10. The polycarbonate resin composition according to the above 10, wherein the maximum peak temperature of the generated gas analysis curve obtained by the generated gas analysis using the pyrolysis gas chromatograph device and the FID detector of the organic layer is 380 ° C. or higher.
12. A value obtained by subtracting the water concentration measured by the Karl Fischer method at 0 ° C. or more and 120 ° C. or less from the water concentration measured by the Karl Fisher method at 0 ° C. or more and 300 ° C. or less of the white pigment (C) is 8,000. The polycarbonate resin composition according to any one of the above 1 to 11, which has a mass ppm or less.
13. The polycarbonate resin composition according to any one of the above 1 to 12, which has a viscosity average molecular weight of 12,000 or more and 50,000 or less.
14. The difference between the L value of the measurement target position and the L value of the reference point (ΔL) measured with a colorimeter for the molded article made of the polycarbonate resin composition is 0.18 or less The polycarbonate resin composition according to any one of 1 to 13.
Light source: D65 light source Viewing angle: 10 °
Measurement method: The end along the flow direction of the resin from the gate position of the injection molding machine at the time of molding is on the vertical axis, and the end orthogonal to the vertical axis is on the horizontal axis The position division of 15 × 15 is performed at intervals of 1 cm (longitudinal) × 1 cm (lateral) in order from the point at which the vertical axis and the horizontal axis are orthogonal to each other. Measure the L value of the following reference point after position division and the measurement symmetrical position.
Reference point: 3 horizontal x 8 vertical positions to be measured: 8 horizontal x 3 vertical to 8 horizontal x 14 vertical positions 15. A molded article comprising the polycarbonate resin composition as described in any one of 1 to 14 above.
16. 15. The molded article according to the above 15, wherein the difference (ΔL) between the L value of the measurement target position and the L value of the reference point measured by the colorimeter under the following conditions is 0.18 or less.
Light source: D65 light source Viewing angle: 10 °
Measurement method: The end along the flow direction of the resin from the gate position of the injection molding machine at the time of molding is on the vertical axis, and the end orthogonal to the vertical axis is on the horizontal axis The position division of 15 × 15 is performed at intervals of 1 cm (longitudinal) × 1 cm (lateral) in order from the point at which the vertical axis and the horizontal axis are orthogonal to each other. Measure the L value of the following reference point after position division and the measurement symmetrical position.
Reference point: 3 horizontal × 8 vertical position Measurement symmetrical position: 8 horizontal × 3 vertical × 8 horizontal × 14 position

The polycarbonate-based resin composition of the present invention can provide a white molded article in which the occurrence of appearance defects such as black streaks at the time of molding is suppressed even if it is a resin composition containing a white pigment.

The schematic diagram which shows the reference point at the time of measuring L value of the molded article which consists of a polycarbonate resin composition of this invention, and a measuring object position. The conceptual diagram which shows the black stripe formed on a molded article.

Hereinafter, the polycarbonate resin composition of the present invention will be described in detail. In the present specification, the preferable definition can be arbitrarily adopted, and a combination of preferable ones can be said to be more preferable. In the present specification, the description of “XX to YY” means “XX or more and YY or less”.

The polycarbonate resin composition of the present invention comprises a polycarbonate block comprising a repeating unit represented by the following general formula (I) and a polycarbonate-poly containing a polyorganosiloxane block comprising a repeating unit represented by the following general formula (II) Polycarbonate resin composition comprising 50% by mass or more and 92% by mass or less of a polycarbonate resin (A) containing an organosiloxane copolymer (A1) and 8% by mass or more and 50% by mass or less of a styrene resin (B) S) and a white pigment (C), wherein the white pigment (C) is contained in an amount of 0.1 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin composition (S) It features.

<Polycarbonate resin (A)>
A polycarbonate resin (A) containing a predetermined polycarbonate-polyorganosiloxane copolymer (A1) is blended in the polycarbonate resin composition of the present invention.

[Polycarbonate-polyorganosiloxane copolymer (A1)]
The polycarbonate-polyorganosiloxane copolymer (A1) contains a polycarbonate block comprising repeating units represented by the following general formula (I) and a polyorganosiloxane block containing repeating units represented by the following general formula (II) .

In the above general formula (I), R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. X represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon And an aryl alkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or -CO-. a and b each independently represent an integer of 0 to 4;
In the above general formula (II), R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms Indicates

As a halogen atom which R < ¹ > and R < ² > respectively independently show in said general formula (I), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
As the alkyl group represented by R ¹ and R ² are each independently a methyl group, an ethyl group, n- propyl group, and isopropyl group, various butyl groups ( "Various", a straight chain and any branched And the same applies hereinafter), various pentyl groups, and various hexyl groups. As an alkoxy group which R < ¹ > and R < ² > respectively independently show, the case where an alkyl group site | part is the said alkyl group is mentioned.
Examples of the alkylene group represented by X include a methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group, an isopropylidene group and the like. Examples of the cycloalkylene group represented by X include a cyclopentadiyl group, a cyclohexanediyl group, a cyclooctanediyl group and the like, and a cycloalkylene group having a carbon number of 5 to 10 is preferable. As a cycloalkylidene group which X represents, a cyclohexylidene group, 3, 5, 5- trimethylcyclohexylidene group, 2-adamantylidene group etc. are mentioned, for example, A C5-C10 cycloalkylidene group is preferable. And a cycloalkylidene group having 5 to 8 carbon atoms is more preferable. Examples of the aryl moiety of the aryl alkylene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl group, naphthyl group, biphenyl group and anthryl group. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring carbon atoms, such as phenyl group, naphthyl group, biphenyl group and anthryl group.
a and b each independently represent an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.
Among them, those in which a and b are 0 and X is a single bond or an alkylene group having 1 to 8 carbon atoms, or those in which a and b are 0 and X is an alkylidene group, particularly isopropylidene group are preferable. It is.

In the general formula (II), the halogen atom shown by R ³ or R ⁴ are each independently a fluorine atom, a chlorine atom, a bromine atom, and iodine atom. Examples of the alkyl group independently represented by R ³ or R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. The alkoxy group shown R ³ or R ⁴ each independently include the alkyl group moiety is a said alkyl group. The aryl group represented by R ³ or R ⁴ are each independently a phenyl group, a naphthyl group, and the like.
Each of R ³ and R ⁴ 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, both of which are methyl It is more preferable that

The polyorganosiloxane block containing a repeating unit represented by the above general formula (II) preferably has a unit represented by the following general formulas (II-I) to (II-III).

[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, The plurality of R ³ to R ⁶ may be identical to or different from one another. Y is ^{^{-R 7 O -, - R 7}} COO -, - R 7 NH -, - R 7 NR 8 -, - COO -, - S -, - R 7 COO-R 9 -O-, or -R ⁷ O—R ¹⁰ —O— is shown, and a plurality of Y may be the same as or different from each other. R ⁷ represents a single bond, a linear, branched or cyclic alkylene group, a divalent organic residue containing an aliphatic group and an aromatic group, a substituted or unsubstituted arylene group, or a diarylene group. R ⁸ represents an alkyl group, an alkenyl group, an aryl group or an aralkyl group. R ⁹ represents a diarylene group. R ¹⁰ represents a linear, branched or cyclic alkylene group or a diarylene group. β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. n shows the average chain length of polyorganosiloxane. p and q are each an integer of 1 or more, and the sum of p and q is n-2. ]

The halogen atom represented by R ³ to R ⁶ independently includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group independently represented by R ³ to R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, and various hexyl groups. Examples of the alkoxy group represented by R ³ to R ⁶ independently include the case where the alkyl group moiety is the above-mentioned alkyl group. The aryl group represented by R ³ to R ⁶ independently includes a phenyl group, a naphthyl group and the like.
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.
It is preferable that all of R ³ to R ^{6 in the} general formulas (II-I), (II-II) and / or (II-III) are methyl groups.

Y is -R ⁷ shows ^{O -, - R 7 COO -} , - R 7 NH -, - R 7 NR 8 -, - R 7 COO-R 9 -O-, or -R ⁷ O-R ¹⁰ -O- The linear or branched alkylene group represented by R ⁷ in the above includes an alkylene group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and the cyclic alkylene group includes 5 to 15 carbon atoms, preferably carbon Several 5-10 cycloalkylene groups can be mentioned.

The divalent organic residue containing an aliphatic group and an aromatic group represented by R ⁷ may further have a substituent such as an alkoxy group or an alkyl group in the aromatic ring, and the specific structure thereof is For example, the structure of the following general formula (x) or (xi) can be shown. In the following general formula, an alkylene group is bonded to Si.

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

The diarylene group represented by R ⁷ , R ⁹ and R ¹⁰ refers to a group in which two arylene groups are directly or via a divalent organic group, and more specifically, -Ar ¹ -W- It is a group having a structure represented by Ar ^2- . Here, 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, isopropylidene, methylene, dimethylene or trimethylene.
Examples of the arylene group 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, anthrylene group and the like. These arylene groups may have any substituent such as an alkoxy group or an alkyl group.
The alkyl group represented by R ⁸ includes a linear or branched alkyl group having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. The alkenyl group includes linear or branched ones having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include phenyl group and naphthyl group. Examples of the aralkyl group include phenylmethyl and phenylethyl.
The linear, branched or cyclic alkylene group represented by R ¹⁰ is the same as R ⁷ .

Y is preferably -R ⁷ O-, and R ⁷ is a divalent organic residue containing an aliphatic group and an aromatic group. In particular, R ⁷ is preferably a divalent residue of a phenolic compound having an alkyl group, and more preferably, for example, a divalent organic residue derived from allylphenol or a divalent organic residue derived from eugenol. Specifically, R ⁷ is preferably a structure represented by the above general formula (x) or (xi).

For p and q in formula (II-II), it is preferred that p = q, ie p = (n-2) / 2, q = (n-2) / 2.

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, and, for example, a divalent group represented by the following general formulas (xiii) to (xvii) Groups are mentioned.

The average chain length n of the polyorganosiloxane block in the PC-POS copolymer (A1) used in the present invention is preferably 50 or more. That is, n in formulas (II-I) and (II-III) is preferably 50 or more, and in the case of (II-II), the number obtained by adding 2 to the sum of p and q is in the above range It is preferable that The average chain length is calculated by nuclear magnetic resonance (NMR) measurement.
When the average chain length n is 50 or more, the low temperature impact resistance of the molded article is good. The average chain length n is more preferably 55 or more, still more preferably 60 or more, still more preferably 80 or more, most preferably 85 or more, more preferably 500 or less, still more preferably 300 or less, still more preferably It is 150 or less, most preferably 120 or less. The average chain length is calculated by nuclear magnetic resonance (NMR) measurement. When the average chain length n exceeds 500, the handling at the time of producing the PC-POS copolymer (A1) becomes difficult and the economy is poor, so 500 or less is preferable.

The content of the polyorganosiloxane block in the PC-POS copolymer (A1) used in the present invention is preferably 1.0% by mass or more and 40% by mass or less from the viewpoint of obtaining better impact characteristics. More preferably, it is 1.0 mass% or more and 30 mass% or less, still more preferably 2.0 mass% or more and 10 mass% or less, and particularly preferably 4.0 mass% or more and 8.0 mass% or less.

The viscosity average molecular weight (Mv) of the PC-POS copolymer (A1) used in the present invention can be appropriately adjusted using a molecular weight modifier or the like so as to achieve the target molecular weight depending on the use and product used. Is preferably 12,000 or more and 50,000 or less, more preferably 15,000 or more and 30,000 or less, still more preferably 16,000 or more and 25,000 or less, and particularly preferably 16,000 or more and 22,000 or less .
When the viscosity average molecular weight is 12,000 or more, a molded article having sufficient impact strength can be obtained. If the viscosity average molecular weight is 50,000 or less, the flowability is not too low, the moldability is good, and injection molding or extrusion molding can be performed at a temperature at which thermal degradation does not occur.
The viscosity average molecular weight (Mv) is a value calculated by measuring the intrinsic viscosity [η] of a methylene chloride solution (concentration: g / L) at 20 ° C. and using the following Schnell's equation.

As the PC-POS copolymer (A1), only one type may be used, or two or more types may be used in combination. When two or more PC-POS copolymers (A1) are used, for example, PC-POS co-polymers having different average chain lengths of the polyorganosiloxane blocks, the content of the polyorganosiloxane blocks, or the viscosity average molecular weights mutually different. The example which combines 2 or more types of polymers can be mentioned. The plurality of PC-POS copolymers (A1) each satisfy the above requirements.

[Polycarbonate resin (A2)]
The polycarbonate resin (A) used in the present invention may further contain a polycarbonate resin (A2) other than (A1). The polycarbonate-based resin (A2) is preferably an aromatic polycarbonate-based resin, and more preferably an aromatic homopolycarbonate-based resin consisting only of repeating units represented by the following general formula (III).

[Wherein, 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- is shown. d and e each independently represent an integer of 0 to 4; ]

Specific examples of R ³⁰ and R ³¹ include the same as the aforementioned R ¹ and R ^2, and preferable ones are also the same. More preferably, R ³⁰ and R ³¹ are an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. As a specific example of X ', the same thing as said X is mentioned, A preferable thing is also the same. Each of d and e independently is preferably 0 to 2, more preferably 0 or 1.

The content of the PC-POS copolymer (A1) in the polycarbonate resin (A) is preferably 10% by mass to 100% by mass, more preferably 20% by mass from the viewpoint of obtaining better impact resistance. The content is 100% by mass or less, more preferably 50% by mass to 100% by mass, and particularly preferably 70% by mass to 100% by mass.

The content of the polyorganosiloxane in the polycarbonate resin (A) is preferably 0.1% by mass to 25% by mass, and more preferably 0.5% by mass or more, from the viewpoint of obtaining better impact resistance. % By mass or less, more preferably 1.0% by mass or more and 10% by mass or less, particularly preferably 4.0% by mass or more and 8.0% by mass or less.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) can be appropriately adjusted to achieve the target molecular weight depending on the application and product to be used, but preferably 12,000 or more and 50,000 or less, more preferably Is 15,000 or more and 30,000 or less, more preferably 16,000 or more and 25,000 or less, and further preferably 16,000 or more and 22,000 or less. When the viscosity average molecular weight is 12,000 or more, sufficient strength of the molded article can be obtained. If the viscosity average molecular weight is 50,000 or less, the flowability is not too low, the moldability is good, and injection molding or extrusion molding can be performed at a temperature at which thermal degradation does not occur.
The viscosity average molecular weight (Mv) can be determined by the same method as described above.

[Method for producing PC-POS copolymer (A1)]
The PC-POS copolymer (A1) in the polycarbonate resin composition of the present invention can be produced by a known production method such as an interfacial polymerization method (phosgene method), a pyridine method, and a transesterification method. In the case of the interfacial polymerization method, in particular, the step of separating the organic phase containing the PC-POS copolymer from the aqueous phase containing the unreacted material, catalyst residue, etc. becomes easy, and each step by alkali washing, acid washing and pure water washing The separation of the organic phase containing the PC-POS copolymer and the aqueous phase in the washing step is facilitated. Therefore, a PC-POS copolymer can be obtained efficiently. As a method for producing a PC-POS copolymer, for example, the method described in JP-A-2014-80462 can be referred to.

Specifically, an alkaline compound such as a dihydric phenol compound (such as bisphenol A) is dissolved in a non-water-soluble organic solvent (such as methylene chloride) by dissolving an aromatic polycarbonate oligomer prepared in advance and polyorganosiloxane described later. An aqueous solution (sodium hydroxide aqueous solution etc.) is added, and a tertiary amine (triethylamine etc.) or a quaternary ammonium salt (trimethylbenzyl ammonium chloride etc.) is used as a polymerization catalyst, and an end terminator (p-tert-butylphenol etc.) 1 It can be produced by interfacial polycondensation reaction in the presence of The PC-POS copolymer (A1) can also be produced by copolymerizing a polyorganosiloxane, a dihydric phenol, and phosgene, a carbonic ester or chloroformate.

When the PC-POS copolymer (A1) is produced by, for example, reacting a polycarbonate oligomer and a polyorganosiloxane raw material in an organic solvent followed by reacting with dihydric phenol, etc., the above organic solvent and the polycarbonate oligomer The solid content mass (g / L) of the polycarbonate oligomer in 1 L of the mixed solution thereof is preferably in the range of 80 to 200 g / L. More preferably, it is 90 to 180 g / L, more preferably 100 to 170 g / L.

As polyorganosiloxane used as a raw material of PC-POS copolymer (A1), what is shown to the following general formula (i), (ii) and / or (iii) can be used.

In the formula, R ³ to R ⁶ , Y, β, n-1, p and q are as described above, and so are the specific examples and preferable ones.
Z represents a hydrogen atom or a halogen atom, and a plurality of Z may be the same as or different from each other.

For example, as the polyorganosiloxane represented by the general formula (i), compounds of the following general formulas (ii) to (i-xi) can be mentioned.

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

In addition, you may use what has the following general formula (xii) as a polyorganosiloxane raw material.

In the formula, R ³ and R ⁴ are as defined above. The average chain length of the polyorganosiloxane block represented by the general formula (xii) is (r × m), and the range of (r × m) is the same as the above n.

When the above (xii) is used as a polyorganosiloxane raw material, the polyorganosiloxane block (II) preferably has a unit represented by the following general formula (II-IV).

[Wherein R ³ , R ⁴ , r and m are as described above]

Other polyorganosiloxane raw materials represented by the following general formula (xiii) may be used as the polyorganosiloxane raw material.

[Wherein, R ¹⁸ to R ²¹ each independently represent 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 represents an average chain length and is 30 to 70. ]

As a C1-C13 alkyl group which R < ¹⁸ > -R < ²¹ > shows each independently in general formula (xiii), a methyl group, an ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups are mentioned. And 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, and all of them are more preferably a methyl group.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ²² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups and various hexyl groups. The halogen atom R ²² represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms represented by R ²² include the case where the alkyl group moiety is the above-mentioned alkyl group. Examples of the aryl group having 6 to 14 carbon atoms represented by R ²² include a phenyl group, a toluyl group, a dimethylphenyl group and a 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 further preferably a hydrogen atom.
As the divalent aliphatic group having 1 to 10 carbon atoms represented by Q ² , a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms is preferable. The carbon number of the saturated aliphatic group is preferably 1 to 8, more preferably 2 to 6, still more preferably 3 to 6, and still more preferably 4 to 6. The average chain length n is as described above.

When used as a polyorganosiloxane raw material represented by the above formula (xiii), the polyorganosiloxane block (A-2) preferably has a unit represented by the following general formula (II-V).

[Wherein, R ¹⁸ to R ²² , Q ² and n are as described above. ]

As a preferable embodiment of the structural unit (II-V), a structure represented by the following formula (II-VI) can be mentioned.

[Wherein n 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, and then An addition reaction of a phenolic compound (eg, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) with the α, ω-dihydrogenorganopentasiloxane in the presence of a catalyst for hydrosilylation reaction is carried out Thus, a crude polyorganosiloxane can be obtained. According to the method described in Japanese Patent No. 2662310, the α, ω-dihydrogenorganopolysiloxane obtained by reacting octamethylcyclotetrasiloxane and tetramethyldisiloxane in the presence of sulfuric acid (acid catalyst) In the same manner as described above, a crude polyorganosiloxane can be obtained by subjecting a phenolic compound or the like to an addition reaction in the presence of a hydrosilylation reaction catalyst. The α, ω-dihydrogen organopolysiloxane may be used by appropriately adjusting the average chain length n according to the polymerization conditions, or a commercially available α, ω-dihydrogen organopolysiloxane may be used. Specifically, those described in JP-A-2016-098292 can be used.

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

As dihydric phenol, it is preferable to use dihydric phenol represented by the following general formula (iv).

In the formula, R ¹ , R ² , a, b and X are as described above.

Examples of dihydric phenols represented by the above general formula (iv) include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides, Dihydroxy diaryl sulfones, dihydroxy diphenyls, dihydroxy diaryl fluorenes, dihydroxy diaryl adamantane etc. are mentioned. These dihydric phenols may be used alone 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) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy) -3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dime Tylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,3 5-dibromophenyl) propane and the like.

As bis (hydroxyaryl) cycloalkanes, for example, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) Examples thereof include -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, 1,1-bis (4-hydroxyphenyl) cyclododecane and the like. Examples of dihydroxy aryl ethers include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether and the like.
Examples of dihydroxy diaryl sulfides include 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide and the like. Examples of dihydroxydiaryl sulfoxides include 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyl diphenyl sulfoxide and the like. Examples of dihydroxy diaryl sulfones include 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyl diphenyl sulfone and the like.

Examples of dihydroxydiphenyls include 4,4′-dihydroxydiphenyl and the like. Examples of dihydroxydiaryl fluorenes include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and the like. Examples of dihydroxydiaryladamantanes include 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7- Dimethyl adamantane etc. are mentioned.
As dihydric phenols other than the above, for example, 4,4 ′-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5 And -bis (4-hydroxyphenylthio) -2,3-dioxapentane and the like.

Among these, bis (hydroxyaryl) alkanes are preferable as dihydric phenol, bis (hydroxyphenyl) alkanes are more preferable, and bisphenol A is more preferable. When bisphenol A is used as the dihydric phenol, a polycarbonate-polyorganosiloxane copolymer in which X is an isopropylidene group and a = b = 0 in the general formula (iv) is obtained.

An endcapping agent can be used to adjust the molecular weight of the resulting PC-POS copolymer. Examples of the 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 alone or in combination of two or more.
After the above interfacial polycondensation reaction, the reaction solution is allowed to stand as appropriate to separate into an aqueous phase and an organic solvent phase, and the organic solvent phase is washed (preferably, washed in order of basic aqueous solution, acidic aqueous solution, water) By concentrating and drying, a PC-POS copolymer can be obtained.

[Manufacturing method of polycarbonate resin (A2) other than (A1)]
Polycarbonate resins (A2) other than the above (A1) can be produced, for example, by reacting a dihydric phenol compound and phosgene in the presence of an organic solvent inert to the reaction, an alkaline aqueous solution, and then a tertiary amine or Surface polymerization method in which a polymerization catalyst such as a secondary ammonium salt is added for polymerization, or a pyridine method in which a dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgene is introduced to produce a polycarbonate resin directly. Etc. can be obtained by conventional polycarbonate production methods. In the above reaction, if necessary, a molecular weight modifier (end stopper), a branching agent, etc. are used.

As said dihydric phenol type compound, what is represented with the following general formula (v) is mentioned.

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

As specific examples of the dihydric phenol compound, those described above in the method for producing the PC-POS copolymer (A1) can be mentioned, and the preferable ones are also the same. Among them, bis (hydroxyphenyl) alkane-based dihydric phenol is preferable, and bisphenol A is more preferable.

<Styrenic resin (B)>
By including the styrenic resin (B), molding processability of the resin composition, in particular, fluidity can be improved. By containing the styrene resin (B), the flowability of the polycarbonate resin composition at the time of molding becomes high, so the shear stress received in the molding machine is alleviated and heat generation is suppressed, thereby suppressing black streaks. It is thought that

Both amorphous styrenic resins and crystalline styrenic resins can be used. As a styrene resin (B), 1 type described concretely below may be used, and 2 or more types may be combined and used.
The amorphous styrenic resin includes 20 to 100% by mass of a monovinyl aromatic monomer such as styrene and α-methylstyrene, 0 to 60% by mass of a vinyl cyanide monomer such as acrylonitrile and methacrylonitrile, And monomers having 0 to 50% by mass of other vinyl monomers such as maleimide, methyl (meth) acrylate and the like copolymerizable with these, or having a crystal structure obtained by polymerizing a monomer mixture Not polymers.
Examples of these polymers include general purpose polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin) and the like.

As the amorphous styrenic resin, a rubber-modified styrenic resin reinforced with a rubbery polymer can be preferably used. Examples of the rubber-modified styrenic resin include high-impact polystyrene (HIPS) in which styrene is polymerized in rubber such as polybutadiene, acrylonitrile-butadiene-styrene copolymer (ABS resin) in which polybutadiene and acrylonitrile are polymerized in polybutadiene, polybutadiene And methyl methacrylate-butadiene-styrene copolymer (MBS resin) obtained by polymerizing methyl methacrylate and styrene, etc., and rubber-modified styrenic resin can be used in combination of two or more, and It can also be used as a mixture with an amorphous styrenic resin.

The content of rubber in the rubber-modified styrenic resin is preferably 2% by mass to 50% by mass, more preferably 5% by mass to 30% by mass, and still more preferably 5% by mass to 15% by mass. If the proportion of rubber in the resin is 2% by mass or more, the impact resistance is sufficient, and if it is 50% by mass or less, the thermal stability is reduced, the melt flowability is reduced, gel generation, coloring There is no problem.
Specific examples of the above-mentioned rubber include rubbery polymers containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SBS), styrene-butadiene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, isoprene Styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like. Among them, particularly preferred is polybutadiene. The polybutadiene used herein is a low cis polybutadiene (for example, one containing 1 to 30 mol% of 1,2-vinyl bonds and 30 to 42 mol% of 1,4-cis bonds), high cis Any of polybutadienes (for example, those containing 20 mol% or less of 1,2-vinyl bonds and 78 mol% or more of 1,4-cis bonds) may be used, or a mixture of these may be used.

Examples of crystalline styrenic resins include styrenic (co) polymers having a syndiotactic structure and an isotactic structure, but in the present invention, an amorphous styrenic resin is used for the purpose of further improving the fluidity. It is preferred to use. Further, among the amorphous styrenic resins, the melt flow rate (MFR) at 200 ° C. and 5 kg load is preferably 0.5 to 100 g / 10 min, more preferably 2 to 80 g / 10 min, still more preferably 2 to 50 g / 10 min is used. If the melt flow rate (MFR) is 0.5 g / 10 min or more, sufficient flowability will be obtained, and if 100 g / 10 min or less, the impact resistance of the flame retardant polycarbonate resin composition will be good.

Among amorphous styrenic resins, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-styrene copolymer (MS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-methyl acrylate-styrene copolymer (AAS resin), acrylonitrile- (ethylene / propylene / diene copolymer) -styrene copolymer At least one selected from polymers (AES resin) is preferable, and acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable.
As an example of these particularly preferable ones, as the AS resin, 290FF (manufactured by Techno Polymer Co., Ltd.), S100N, S200N, S101 (manufactured by UMG ABS Co., Ltd.), PN-117C (manufactured by Kokishinsha Co., Ltd.), ABS Examples of the resin include Santac AT-05 and SXH-330 (all manufactured by Nippon A & L Co., Ltd.), Toyorac 500 and 700 (manufactured by Toray Industries, Inc.), and PA-756 (manufactured by Kakumi Business Co., Ltd.). As the MBS resin, C223A (manufactured by Mitsubishi Rayon Co., Ltd.) can be mentioned.

<Polycarbonate-based resin composition (S)>
The polycarbonate-based resin composition of the present invention includes the polycarbonate-based resin composition (S) containing the polycarbonate-based resin (A) and the styrene-based resin (B) described above as resin components.
The polycarbonate resin composition (S) contains 50% by mass or more and 92% by mass or less of the polycarbonate resin (A) and 8% by mass or more and 50% by mass or less of the styrene resin (B). If the proportion of the polycarbonate resin (A) is in the above range, excellent impact resistance can be obtained. If the proportion of the styrene-based resin (B) is in the above-mentioned range, it is possible to suppress the generation of black streaks during molding without impairing the heat resistance. Here, in the polycarbonate resin composition (S), the total proportion of the polycarbonate resin (A) and the styrene resin (B) is 100% by mass.

The proportion of the polycarbonate resin (A) in the polycarbonate resin composition (S) is preferably 60% by mass to 90% by mass, more preferably 65% by mass to 85% by mass, and still more preferably 70% by mass or more It is 80 mass% or less.
The proportion of the styrenic resin (B) in the polycarbonate resin composition (S) is preferably 10% by mass to 40% by mass, more preferably 15% by mass to 35% by mass, and still more preferably 20% by mass or more It is 30 mass% or less.

<White pigment (C)>
The polycarbonate resin composition of the present invention contains a white pigment (C). The white pigment (C) is used as a toning color material for an intermediate color such as white or gray color tone of the polycarbonate resin composition of the present invention. The white pigment (C) is not particularly limited, but it is preferable to use one or more selected from the group consisting of titanium oxide pigments, zinc sulfide pigments, zinc oxide pigments, and barium sulfate pigments, and titanium oxide One or more selected from the group consisting of a pigment, a zinc sulfide pigment, and a zinc oxide pigment is more preferable. Among these white pigments, it is preferable to use a titanium oxide pigment from the viewpoint of making the color tone whiter. Hereinafter, titanium oxide will be described in more detail as a representative, but the same applies to the above-mentioned white pigment other than titanium oxide.

The titanium oxide particles to be the core of the titanium oxide pigment (hereinafter, the titanium oxide particles to be the core of the titanium oxide pigment are also referred to as "titanium oxide particles" or simply "core particles") are produced by either the chlorine method or the sulfuric acid method In the light of color tone, those produced by the chlorine method are more preferred. The crystal structure of the titanium oxide may be either rutile type or anatase type, but from the viewpoint of the thermal stability and light resistance of the polycarbonate resin composition, the rutile type structure is preferable.
The average particle diameter of the core particle is preferably 0.10 μm to 0.45 μm, and more preferably 0.15 μm to 0.25 μm from the viewpoint of making the color tone whiter. The average particle size of the core particles is determined from the average value of the particle sizes of the primary particles of single particles.

The titanium oxide pigment generally has an inorganic oxide layer composed of one or more inorganic oxides selected from the group consisting of silica, zirconia, and alumina on the surface of titanium oxide particles. The said inorganic oxide layer can suppress the catalyst activity of the titanium oxide which is core particle, and can provide light resistance. Furthermore, the effect of alleviating the aggregation of the titanium oxide pigment in the resin composition and improving the dispersibility is also exhibited.

The titanium oxide pigment may have two or more layers of the inorganic oxide layer. In this case, the inorganic oxide layer located on the side closer to the core particle mainly contributes to the suppression of the catalytic activity of the titanium oxide particles as the core particle and the provision of light resistance, and the inorganic oxide layer located on the side far from the core particle Contributes mainly to the relaxation of the aggregation of the titanium oxide pigment in the resin composition and the improvement of the dispersibility.
When the titanium oxide pigment has two or more inorganic oxide layers, the inorganic oxide layer located on the side close to the core particle comprises one or more selected from the group consisting of silica and zirconia, and is located on the side far from the core particle The inorganic oxide layer to be formed is preferably made of alumina.

The inorganic oxide layer has the function of suppressing the catalytic activity of titanium oxide which is the core particle, while silica, zirconia and alumina which are inorganic oxides are hydratable inorganic substances, so the water absorption is high and the water in the molding machine It is easy to transpiration. The evaporated water causes the hydrolysis of the polycarbonate resin to be induced. From such a thing, in order to suppress the catalytic action of titanium oxide, it is preferable that the inorganic oxide layer be thicker, and in order to suppress the hydrolysis of the polycarbonate resin, it is preferable that the thickness of the inorganic oxide layer be smaller. Become.
Because of this contradictory relationship, the coating amount of the titanium oxide pigment for coloring of the polycarbonate resin composition by the inorganic oxide layer is in the range of 3% by mass to 10% by mass in mass ratio to the entire titanium oxide pigment. It is common. In white reflector applications such as smartphones where white pigment concentration is high and hydrolysis is easy, the coverage of the titanium oxide pigment by the inorganic oxide layer is 3% by mass or more and 5% by mass with respect to the entire titanium oxide pigment % Or less is a preferable range. On the other hand, in the use of colored molded articles for outdoor use where light resistance is required, the coating amount of the titanium oxide pigment by the inorganic oxide layer is preferably in the range of 5% by mass to 10% by mass in mass ratio to the entire titanium oxide pigment . However, even with this mass ratio, it is difficult to completely suppress the catalytic action of titanium oxide, and weathering deterioration by the catalytic action of titanium oxide occurs. Most of the factors that cause black streaks in injection molding of a polycarbonate resin composition containing a PC-POS copolymer and a white pigment such as a titanium oxide pigment are the unrestrained catalytic action of this titanium oxide.

Heretofore, titanium oxide pigments have been considered to cause molecular weight reduction of polycarbonate resins, since the water in the titanium oxide pigments induces hydrolysis of the polycarbonate resins under high temperature and high pressure in a molding machine. In order to confirm this fact, researchers add a plurality of titanium oxide pigments having different water content to the polycarbonate resin in the same amount, respectively, and knead them with a twin-screw kneader, and from the molecular weight difference before and after kneading, The correlation between the molecular weight reduction amount and the water content in the added titanium oxide pigment was examined. As a result, it has been found that the two do not necessarily have a correlation, and it is considered that the molecular weight is reduced by the catalytic action of the titanium oxide pigment from the assumption that there is a factor that reduces the molecular weight other than hydrolysis.

The moisture in the titanium oxide pigment can be one of the causes of decomposition of the polycarbonate resin. Furthermore, since it is known that the high-temperature and high-pressure steam which evaporates in the molding machine accelerates the oxidation of an organic substance such as a polycarbonate resin, a titanium oxide pigment having a small amount of water is preferable. The water content (chemically bound water content) contained in the titanium oxide pigment is the water content measured by the Karl Fischer method at 0 ° C. or more and 120 ° C. or less from the water concentration measured by the Karl Fischer method at 0 ° C. or more and 300 ° C. or less It is preferable that the value which deducted the concentration is 8,000 mass ppm or less. If the water concentration difference of the titanium oxide pigment is 8,000 ppm by mass or less, the molecular weight of the polycarbonate resin is not adversely affected. The value is more preferably 6,000 mass ppm or less, still more preferably 4,000 mass ppm or less, still more preferably 3,000 mass ppm or less.

The titanium oxide pigment preferably has an organic layer on the surface of the inorganic oxide layer. The organic layer has the effect of alleviating the aggregation of the titanium oxide pigment in the resin composition and improving the dispersibility. Moreover, the said inorganic oxide layer surface which a titanium oxide pigment has has a solid acid or solid base characteristic. This fact is described in Ishihara Sangyo Co., Ltd. "New ・ Typek News Vo. 1 Titanium oxide colored particles Basic physical properties edition" p.15. The solid acid or solid basic property is similar to the acid-base property in solution, and this property is not preferable because the polycarbonate resin tends to promote hydrolysis under both acidity and basicity. This solid acid or solid basic property is a property of only the surface of the inorganic oxide layer possessed by the titanium oxide pigment. Therefore, by covering the inorganic oxide layer with the organic layer, the direct contact between the inorganic oxide layer and the polycarbonate resin can be suppressed, and the influence of the action of promoting the hydrolysis by the acid and basic characteristics can be reduced. In this respect, the organic layer is effective in suppressing the hydrolysis of PC-POS.

The organic layer is not particularly limited as long as it contains a siloxane structure, but evolved gas analysis (Evolved Gas Analysis) using a pyrolysis gas chromatograph and a FID detector (Flame Ionization Detector). The maximum peak temperature of the generated gas analysis curve obtained by the following “EGA” is preferably 380 ° C. or more. When the maximum peak temperature of the organic layer is 380 ° C. or higher, the organic layer is difficult to be decomposed even when melt-kneading or molding of the polycarbonate resin composition is performed under high temperature conditions. Therefore, since the action of solid acid or solid basicity on the surface of the inorganic oxide layer possessed by the titanium oxide pigment can be effectively suppressed, black due to hydrolysis of the PC-POS copolymer at the time of molding of the resin composition Occurrence of streaks can be suppressed. From the viewpoint of the black streak suppressing effect, the maximum peak temperature of the organic layer is more preferably 400 ° C. or more, and still more preferably 410 ° C. or more. The upper limit value of the maximum peak temperature of the organic layer is not particularly limited, but in consideration of the general decomposition temperature of the organic layer, it is preferably 500 ° C. or less, more preferably 480 ° C. or less, and 450 It is further preferable that the temperature is not higher than ° C.
The said maximum peak temperature can be specifically measured by the method as described in an Example.

As a compound which forms the said organic layer, silane type compounds, such as a silane coupling agent, are mentioned as a preferable thing. As a silane coupling agent, a vinyl-type silane coupling agent, an epoxy-type silane coupling agent, a methacryl-type silane coupling agent, an acryl-type silane coupling agent, an amino type silane coupling agent etc. are mentioned. These compounds can be used singly or in combination of two or more.

In addition, as a compound which forms the said organic layer, an alkyl hydrogen silicone, an alkoxy silicone etc. are mentioned specifically ,. Examples of the alkyl hydrogen silicone include methyl hydrogen silicone and ethyl hydrogen silicone. Examples of alkoxysilicone include methoxysilicone and ethoxysilicone. The preferred alkoxysilicone is a silicone compound specifically including an alkoxysilyl group in which an alkoxy group is bonded to a silicon atom directly or via a divalent hydrocarbon group, and, for example, a linear, cyclic, network and partially branched chain And linear organopolysiloxanes having, and in particular, linear organopolysiloxanes are preferred. More specifically, polyorganosiloxanes having a molecular structure in which an alkoxy group is bonded to a silicone main chain via a methylene chain are preferred.

From the viewpoint of the effect of suppressing appearance defects such as black streaks during molding, the organic layer is selected from the group consisting of cyclic siloxane compounds and silane compounds as components detected by gas chromatography-mass spectrometry (GC-MS) It is preferable to include one or more of the above, and it is more preferable to include a silane compound. More specifically, it is preferable that the said organic layer is an organic layer in which the component detected by gas chromatography mass spectrometry contains the following A group, or an organic layer containing the following B group. More preferably, it is an organic layer containing group A.
[Group A]

[Group B]

The above description of the titanium oxide pigment is similarly applied to white pigments such as zinc sulfide pigment, zinc oxide pigment, and barium sulfate pigment.
The shape of the white pigment (C) is not particularly limited, and may be scaly, spherical, plate-like, indeterminate or the like. The average particle size of the white pigment (C) is preferably 0.05 μm or more and 0.50 μm or less, more preferably 0.10 μm or more and 0.45 μm or less, and still more preferably 0. 15 μm or more and 0.25 μm or less. The average particle size of the white pigment (C) is determined from the average value of the particle sizes of primary particles of single particles.

The content of the white pigment (C) in the polycarbonate resin composition of the present invention is 100 parts by mass of the polycarbonate resin composition (S) containing the polycarbonate resin (A) and the styrene resin (B), 0.1 parts by weight or more and 40 parts by weight or less, preferably 0.1 parts by weight or more and 20 parts by weight or less, more preferably 1.0 parts by weight or more and 10 parts by weight or less, still more preferably 1.0 parts by weight or more .0 part by mass or less. If the white pigment (C) is less than 0.1 parts by mass, the whiteness is insufficient, and if it exceeds 40 parts by mass, the impact resistance is lowered.

<Other additives>
Other additives can be further added to the polycarbonate resin composition of the present invention as long as the effects of the present invention are not impaired. Other components include, for example, metal deactivators, hydrolysis inhibitors, antioxidants, UV absorbers, flame retardants, flame retardant aids, mold release agents, reinforcing materials, fillers, elastomers for improving impact resistance. And dyes. Some components are described in detail.
<Metal deactivator>
The polycarbonate resin composition of the present invention may contain a metal deactivator (D). The metal deactivator serves to suppress the oxidative degradation of the PC-POS copolymer (A1) by the catalytic action of the white pigment such as the titanium oxide pigment in the molding machine as described above.

In the present invention, the metal deactivator is a substance having a function of deactivating metal or metal ion. For example, a compound having a function of chemically inactivating a metal surface, or adsorbing on a metal surface to inhibit catalysis by the metal, or forming a complex with a metal ion which is an elution product from the metal And compounds having the function of converting into inert substances such as chelate compounds.

Examples of the metal deactivator include hydrazine compounds, triazole compounds, triazine compounds, oxalic acid compounds, guanidine compounds, aminocarboxylate compounds, phosphonate compounds, and clathrates.
Examples of hydrazine compounds include N, N'-diformylhydrazine, N, N'-diacetylhydrazine, N, N'-dipropionylhydrazine, N, N'-butyrylhydrazine, N-formyl-N'- Acetylhydrazine, N, N'-dibenzoylhydrazine, N, N'-ditoluylhydrazine, N, N'-disalicyloylhydrazine, N-formyl-N'-salicyloylhydrazine, N-formyl-N ' -Butyl substituted salicyloylhydrazine, N-acetyl-N'-salicyloylhydrazine, N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, oxalic acid Acid-di- (N'-salicyloyl) hydrazine, adipic acid-di- (N'-salicyloyl) hydrazine, disalicyloyldecamethylenedicarboxylate Hydrazide, and the like. Among the above, hydrazine compounds having a salicyloyl group are preferable, and decamethylenedicarboxylic acid disalicyloylhydrazide is more preferable.
Commercially available hydrazine compounds include “ADEKA STAB CDA-6” (decamethylenedicarboxylic acid disalicyloyl hydrazide) manufactured by ADEKA CORPORATION, “ADEKA STAB CDA-10” (N, N′-bis [3- (3 (3) , 5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine) and the like.

Examples of the triazole compounds include benzotriazole compounds and aminotriazole compounds. For example, benzotriazole, tolyltriazole, 3-amino-1,2,4-triazole, 3-amino-1,2,4-triazole-carboxylic acid, 3-amino-5-methyl-1,2,4-triazole , 3-amino-5-heptyl-1,2,4-triazole, 3- (N-salicyloyl) amino-1,2,4-triazole, 3- (N-salicyloyl) amino-5-methyl-1,2 And 4-triazole, 3- (N-acetyl) amino-1,2,4-triazole-5-carboxylic acid and the like. Among the above, aminotriazole compounds are preferable.
Examples of commercial products of the triazole compounds include "ADEKA STAB CDA-1" (3- (N-salicyloyl) amino-1,2,4-triazole), "ADEKA STAB CDA-1M", etc. .

Examples of triazine compounds include 1,3,5-triazine, 2,4,6-trihydroxy-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine and the like. . Examples of commercially available products include "Adekastab ZS-27" (2,4,6-triamino-1,3,5-triazine) manufactured by ADEKA Corporation.

Examples of oxalic acid compounds include 2,2'-oxamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. Examples of guanidine compounds include guanidine hydrochloride, guanidine nitrate, guanidine carbonate, guanidine phosphate, guanidine sulfamate and the like.

Examples of aminocarboxylate compounds include EDTA (ethylenediaminetetraacetic acid), CDTA (cyclohexanediaminetetraacetic acid), NTA (nitrilotriacetic acid), hydroxyethylethylenediaminetriacetic acid, TMDTA (trimethylenediaminetetraacetic acid), DMPDTA (2,2 Dimethylpropanediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), and salts thereof.

Examples of phosphonate compounds include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine tetramethylene phosphonic acid (EDTMP), nitrilotris methylene phosphonic acid (NTMP), aminotri (one) having at least one phosphate group in the molecule. Methylene phosphonic acid), 1,2-ethanediphosphonic acid, tris (phosphonomethyl) amine-N-oxide, 1-hydroxypropane-1,1,3-triphosphonic acid, diethylene triamine penta (methylene phosphonic acid), N, N- Bis (phosphonomethyl) butylamine, N, N-bis (phosphonomethyl) propylamine, 2-hydroxyethyl bis (phosphonomethyl) amine, N, N-bis (phosphonomethyl) methylamine, N, N, N ′, N′-tetrakis ( Phosphonomethyl) -1 2-propanediamine, 2-carboxyethane-1-phosphonic acid, N- (carboxymethyl) -N- (phosphonomethyl) glycine, (carboxymethyl) phosphonic acid, 2- (phosphonooxy) benzoic acid, ethylenediamine-N, N ' And phosphonates such as -bis (acetic acid) -N, N '-(methylene phosphonic acid) and salts thereof.
Examples of the inclusion compound include porphyrin and crown ether.

As the metal deactivator, one of the above-described compounds can be used alone, or two or more can be used in combination. Above all, from the viewpoint of suppressing appearance defects such as black streaks and the like during molding of a polycarbonate resin composition containing a PC-POS copolymer, and suppressing molecular weight reduction, hydrazine compounds, triazole compounds, triazine compounds And at least one member selected from the group consisting of aminocarboxylate compounds, more preferably one or more members selected from the group consisting of hydrazine compounds, triazole compounds, and aminocarboxylate compounds, hydrazine compounds and One or more selected from the group consisting of aminocarboxylate compounds is more preferable, and one or more selected from the group consisting of decamethylenedicarboxylic acid disalicyloylhydrazide and ethylenediaminetetraacetic acid is even more preferable.
When the polycarbonate resin composition of the present invention contains a metal deactivator, it suppresses or deactivates the catalytic action associated with a white pigment (C) such as a titanium oxide pigment contained in the polycarbonate resin composition Therefore, metal deactivators other than the compounds exemplified above can also be used.

The content of the metal deactivator in the polycarbonate resin composition of the present invention is 100 parts by mass of the polycarbonate resin composition (S) containing the polycarbonate resin (A) and the styrene resin (B), The content is preferably 0.005 parts by mass or more and 1.0 parts by mass or less, more preferably 0.01 parts by mass or more and 0.3 parts by mass or less, still more preferably 0.02 parts by mass or more and 0.2 parts by mass or less And more preferably 0.03 parts by mass or more and 0.15 parts by mass or less. When the content of the metal deactivator is less than 0.005 parts by mass with respect to 100 parts by mass of the polycarbonate resin composition (S), the effect of suppressing the generation of black streaks at the time of molding of the resin composition is small; If it exceeds 0 parts by mass, the physical properties are reduced.

The polycarbonate resin composition containing the white pigment (C) is derived from the water content in the white pigment (C) to cause hydrolysis of the PC-POS copolymer to some extent. In order to prevent this more, a hydrolysis resistant agent may be added to the polycarbonate resin composition of the present invention. By further blending the hydrolysis resistant agent, the generation of black streaks at the time of molding can be further suppressed.

In the present invention, the hydrolysis resistant agent is an agent having a function of suppressing hydrolysis of a carbonate group or a siloxane bond in the PC-POS copolymer (A1), and more specifically, water or an acid generated. It is preferable that it is an agent which has one or more functional groups which can react with it.
Specific examples of the hydrolysis resistance that can be used in the present invention include an amide compound (e1), an imide compound (e2), an epoxy compound (e3), an acid anhydride (e4), an oxazoline compound (e5), Examples include oxazine compounds (e6) and ketene compounds (e7).

<Amide Compound (e1)>
The amide compound (e1) may be a compound having at least one amide group in the molecule.
From the viewpoint of the effect as a hydrolysis resistance and the dispersibility, the amide compound (e1) is preferably an amide compound having at least one linear aliphatic group having 6 to 24 carbon atoms in the molecule. The linear aliphatic group may be linear or branched, and may be a saturated aliphatic group or an unsaturated aliphatic group. From the viewpoint of suppressing the generation of black streaks during molding and from the viewpoint of having a dispersing action on the polycarbonate resin, a saturated chain aliphatic group is preferable, and an alkyl group is more preferable. The carbon number of the linear aliphatic group is preferably 8 to 22, more preferably 10 to 22, and further preferably 12 to 22. The linear aliphatic group may have a substituent such as a hydroxyl group.

Among the amide compounds (e1), as an amide compound having one amide group in the molecule (hereinafter also referred to as "monoamide"), a compound represented by the following general formula (e1-a) is preferable.

In the above formulae, R ¹¹ is a linear aliphatic group having 6 to 24 carbon atoms. R ¹² is a hydrogen atom or a linear aliphatic group having 6 to 24 carbon atoms. Preferred embodiments of the linear aliphatic group are the same as described above, and may have a substituent such as a hydroxyl group.

As a compound represented by the above general formula (e1-a), a fatty acid monoamide, and a monoamide in which an amide hydrogen of the fatty acid monoamide is substituted with a linear aliphatic group having 6 to 24 carbon atoms (a linear aliphatic group substitution Type fatty acid monoamides). Among the above, fatty acid monoamide is preferred.
Specific examples of fatty acid monoamides include caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide, hydroxystearic acid amide, 12-hydroxystearic acid amide, behenic acid amide, montanic acid Amide, undecylenic acid amide, oleic acid amide, erucic acid amide, linoleic acid amide and the like can be mentioned.

Specific examples of the linear aliphatic group-substituted fatty acid monoamide include N-lauryl lauric acid amide, N-palmityl palmitic acid amide, N-stearyl stearic acid amide, N-behenyl behenic acid amide, N-oleyl oleic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N-stearyl erucic acid amide, N-oleyl palmitic acid amide, methylose stearic acid amide, methylose behenic acid amide, N-stearyl 12-hydroxy stearic acid amide, N And oleyl-12-hydroxystearic acid amide and the like.

Among the amide compounds (e1), as a compound having two amide groups in the molecule, a compound represented by any one of the following general formulas (e1-b) or (e1-c) is preferable, and a compound represented by general formula (e1) The compound represented by -b) is more preferable.

In the above formulae, R ¹³ and R ¹⁴ are each independently a C6-C24 linear aliphatic group which may have a hydroxyl group. Z ¹ is a divalent group having 1 to 12 carbon atoms.
Preferred embodiments of the linear aliphatic group are the same as described above, and may have a substituent such as a hydroxyl group. R ¹³ and R ¹⁴ may be the same as or different from each other, but are preferably the same.
The carbon number of Z ¹ is preferably 1 to 8, more preferably 2 to 6, and further preferably 2 to 4. Z ¹ may be any of a chain aliphatic group, an alicyclic structure-containing group, and an aromatic ring-containing group, but is preferably a chain aliphatic group, and more preferably an alkylene group.

In the above formula, R ¹⁵ and R ¹⁶ are each independently represent a chain aliphatic group having 6 to 24 carbon atoms. Z ² is a divalent group having 1 to 12 carbon atoms.
Preferred embodiments of the linear aliphatic group are the same as described above, and may have a substituent such as a hydroxyl group. R ¹⁵ and R ¹⁶ may be the same as or different from each other, but are preferably the same.
Preferred embodiments of Z ² are the same as the aforementioned Z ¹ .

Specific examples of the compound represented by the general formula (e1-b) include fatty acid bisamides, such as methylenebiscaprylic acid amide, methylenebiscapric acid amide, methylenebislauric acid amide, methylenebismyristic acid amide, Methylenebispalmitic acid amide, Methylenebisstearic acid amide, Methylenebisisostearic acid amide, Methylenebisbehenic acid amide, Methylenebisoleic acid amide, Methylenebiserucic acid amide, Ethylenebiscaprylic acid amide, Ethylenebiscapric acid amide, Ethylene bis Lauric acid amide, ethylene bis myristic acid amide, ethylene bis palmitic acid amide, ethylene bis stearic acid amide, ethylene bis isostearic acid amide, ethylene bis behenic acid amide, ethylene bis oley Acid amide, ethylenebiserucic acid amide, butylenebisstearic acid amide, butylenebisbehenic acid amide, butylenebisoleic acid amide, butylenebiserucic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbehenic acid amide, hexamethylene bis Oleic acid amide, hexamethylene biserucic acid amide, m-xylylene bis-stearic acid amide, m-xylylene bis-12-hydroxystearic acid amide, p-xylylene bis-stearic acid amide, p-phenylene bis-stearic acid amide, methylene bis Examples thereof include hydroxystearic acid amide, ethylene bishydroxystearic acid amide, butylene bishydroxystearic acid amide, hexamethylene bishydroxystearic acid amide and the like.

Specific examples of the compound represented by the general formula (e1-c) include N, N'-distearyl adipic acid amide, N, N'-distearyl sebacic acid amide, N, N'-dioleyl adipic acid amide And N, N'-dioleyl sebacic acid amide, N, N'-distearyl isophthalic acid amide, N, N'-distearyl terephthalic acid amide and the like.

Among the amide compounds (e1), compounds having three or more amide groups in the molecule include dicarboxylic acids, diamines, and heavy compounds with monocarboxylic acids or monoamines having a linear aliphatic group having 6 to 24 carbon atoms. Condensates are mentioned as a preferred example. Preferred embodiments of the linear aliphatic group having 6 to 24 carbon atoms are the same as described above, and may have a substituent such as a hydroxyl group.

Among the amide compounds (e1), from the point of the effect of the present invention, from the compounds represented by the general formula (e1-a), the general formula (e1-b), and the general formula (e1-c) 1 or more types of amide compounds selected from the group consisting of is more preferable, the compound represented by the said general formula (e1-b) is still more preferable, and ethylene bis-stearic-acid amide is still more preferable. Among the amide compounds (e1), compounds having a melting point of 100 ° C. or more, preferably 150 ° C. or more are preferable because they have high suitability to the molding temperature of the polycarbonate resin composition.
Commercially available products of the above amide compound (e1) include “Light Amide WH-255” (manufactured by Kyoeisha Chemical Co., Ltd., N, N′-ethylenebisstearoamide [ethylenebisstearic acid amide]), “amide AP- 1) (made by Nippon Kasei Co., Ltd., stearic acid amide), "Suripax E" (made by Nippon Kasei Co., Ltd., ethylenebisstearic acid amide), "Suripax H" (made by Nippon Kasei Co., Ltd., ethylene bishydroxystearin Acid amide) and the like.

<Imide Compound (e2)>
As the imide compound (e2), carbodiimide compounds are preferable. The carbodiimide compound is a compound having at least one carbodiimide group in the molecule, and includes a monocarbodiimide compound having one carbodiimide group in the molecule and a polycarbodiimide compound having two or more carbodiimide groups in the molecule. From the viewpoint of suppressing the generation of black streaks during molding of the resin composition, polycarbodiimide compounds are preferable.
Examples of the carbodiimide compound include an aliphatic carbodiimide compound, an aromatic carbodiimide compound, a cyclic carbodiimide compound, and a compound obtained by subjecting a part of an isocyanate compound to carbodiimide formation (hereinafter, also referred to as a “carbodiimide modified compound”).

Specific examples of the aliphatic monocarbodiimide compound include diisopropyl carbodiimide, dioctyl decyl carbodiimide, dicyclohexyl carbodiimide, N, N'-dioctyl decyl carbodiimide and the like.
Specific examples of aliphatic polycarbodiimides include ethylene bis (dicyclohexyl carbodiimide), hexamethylene bis (dicyclohexyl carbodiimide), poly (diisopropyl carbodiimide), poly (1,6-hexamethylene carbodiimide), poly (4,4'-methylene Biscyclohexyl carbodiimide), poly (1, 3-cyclohexyl carbodiimide), poly (1, 4- cyclohexyl carbodiimide), etc. are mentioned.

Specific examples of the aromatic monocarbodiimide compound include di-p-chlorophenyl carbodiimide, di-o-chlorophenyl carbodiimide, di-3,4-dichlorophenyl carbodiimide, di-2,5-dichlorophenyl carbodiimide, 2,6,2 ′, 6'-tetraisopropyldiphenyl carbodiimide, N, N'-diphenyl carbodiimide, N, N'-di-o-toluyl carbodiimide, N, N'-di-2,6-dimethylphenyl carbodiimide, N-toluyl-N'- Cyclohexyl carbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-di-2,6-di-tert-butylphenyl carbodiimide, N-toluyl-N'-phenyl carbodiimide, N, N'-di-p-nitrophenyl carbo Diimide, N, N'-di-p-aminophenyl carbodiimide, N, N'-di-p-hydroxyphenyl carbodiimide, N, N'-di-o-toluyl carbodiimide, N, N'-di-p-toluyl Carbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolyl carbodiimide, N-benzyl-N'-tolyl carbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenyl carbodiimide, N, N ' -Di-o-isopropylphenyl carbodiimide, N, N'-di-p- Sopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide, N, N ' -Di-2-ethyl-6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4,6-trimethylphenylcarbodiimide, N, N Examples thereof include '-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2,4,6-triisobutylphenylcarbodiimide and the like.

Specific examples of the aromatic polycarbodiimide compound include p-phenylene bis (o-toluyl carbodiimide), p-phenylene bis (cyclohexyl carbodiimide), p-phenylene bis (p-chlorophenyl carbodiimide), ethylene bis (diphenyl carbodiimide), and poly (4,4'-Diphenylmethanecarbodiimide), Poly (3,3'-Dimethyl-4,4'-diphenylmethanecarbodiimide), Poly (naphthylene carbodiimide), Poly (p-phenylene carbodiimide), Poly (m-phenylene carbodiimide) , Poly (tolyl carbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triethyl phenylene carbodiimide), poly (triisopropyl phenylene carbodiimide), etc. It is.

The cyclic structure of the cyclic carbodiimide compound has one carbodiimide group (-N = C = N-), and its first nitrogen and second nitrogen are linked by a linking group. In one cyclic structure, it has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and further preferably 10 to 20. Here, the number of atoms in the cyclic structure means the number of atoms directly constituting the cyclic structure, and is, for example, 8 for a 8-membered ring, and 50 for a 50-membered ring.

Examples of the cyclic structure include structures represented by the following formula (e2-a).

In the formula, Q is a divalent to tetravalent organic group.

As an isocyanate compound used for the compound (carbodiimide modified compound) which carried out carbodiimide formation of a part of isocyanate compound, tolylene diisocyanate, phenylene diisocyanate, 4,4'- diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, dimethyl biphenylene diisocyanate, Dimethoxybiphenylene diisocyanate, naphthalene diisocyanate, tetrahydronaphthalene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethyl xylylene Diisocyanate, lysine diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, etc. may be mentioned, and one kind may be used alone, or two or more kinds may be used in combination. Among the above-mentioned isocyanate compounds, isocyanate compounds containing 4,4′-diphenylmethane diisocyanate as a main component are preferable.
A publicly known method can be used as a method of carrying out the carbodiimidization of a part of isocyanate compound.

The carbodiimide group / isocyanate group molar ratio of the carbodiimide-modified compound is preferably in the range of 0.01 to 0.5, and preferably in the range of 0.1 to 0.2. By using a compound having a carbodiimide group / isocyanate group molar ratio of 0.01 or more, the effect as a hydrolysis resistant agent can be exhibited, and generation of black streaks at the time of molding of the resin composition can be suppressed.

The imide compounds (e2) can be used alone or in combination of two or more. Among the above, aliphatic carbodiimides are preferable, and aliphatic polycarbodiimides are more preferable from the viewpoint of the effect as a hydrolysis resistance.

<Epoxy Compound (e3)>
The epoxy compound (e3) may be a compound having at least one epoxy group in the molecule. Examples of the epoxy compound (e3) include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, cyclic epoxy compounds, and epoxidized oils.

As glycidyl ether compounds, butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylol propane triglycol With bisphenols such as di-zyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane and bis (4-hydroxyphenyl) sulfone Examples thereof include bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin obtained from condensation reaction with epichlorohydrin.

Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester, Linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalenedicarboxylic acid diglycidyl ester, bisbenzoic acid diglycidyl ester, methylterephthalic acid diglycidyl ester, hexa Hydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, Shik Hexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester A glycidyl ester etc. can be mentioned.

Examples of glycidyl amine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidyl aniline, diglycidyl toluidine, N, N, N ', N'-tetraglycidyl metaxylylene. Amines, diglycidyl tribromoaniline, tetraglycidyl bisaminomethyl cyclohexane, triglycidyl cyanurate, triglycidyl isocyanurate and the like can be mentioned.

As a glycidyl imide compound, N-glycidyl phthalimide, N-glycidyl 4-methyl phthalimide, N-glycidyl-4,5-dimethyl phthalimide, N-glycidyl 3-methyl phthalimide, N-glycidyl 3, 6- dimethyl phthalimide N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N-glycidyl- 4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N-glycidyl-α, β-Dimethyls There may be mentioned succinimide, N-glycidyl-α-ethyl succinimide, N-glycidyl-α-propyl succinimide and the like.

Examples of cyclic epoxy compounds include 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4,5- Epoxycyclohexane-1,2-dicarboximide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboximide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboximide, N And -naphthyl-4,5-epoxycyclohexane-1,2-dicarboximide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboximide and the like can be mentioned. Among these, 3 ', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferred.

Epoxidized oils can include epoxidized natural oils and epoxidized synthetic oils. Specific examples of the epoxidized natural oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, epoxidized tung oil and the like. As specific examples of the epoxidized synthetic oil, epoxy hexahydrophthalic acid diepoxystearyl, epoxidized fatty acid butyl and the like can be mentioned. Among these, epoxidized soybean oil and epoxidized linseed oil have high affinity with the polycarbonate resin, and easily exhibit the hydrolysis resistance effect.

An epoxy compound (e3) can be used individually by 1 type or in combination of 2 or more types. Among the above, as the epoxy compound (e3), a cyclic epoxy compound, or at least one epoxidized oil selected from the group consisting of an epoxidized natural oil and an epoxidized synthetic oil is preferable.

<Acid anhydride (e4)>
The acid anhydride (e4) may be a compound having at least one acid anhydride group in the molecule, and examples thereof include succinic anhydride, maleic anhydride, and phthalic anhydride. Furthermore, the polymer etc. which contain the above-mentioned compound as a monomer unit can also be mentioned.

<Oxazoline compound (e5)>
The oxazoline compound (e5) may be a compound having at least one oxazoline group in the molecule, and examples include monooxazoline, bisoxazoline, and polyoxazoline containing an oxazoline group-containing compound as a monomer unit.

<Oxazine Compound (e6)>
The oxazine compound (e6) may be a compound having at least one oxazine group in the molecule, and examples include monooxazine, bisoxazine, and polyoxazine containing an oxazine group-containing compound as a monomer unit.

<Ketene compound (e7)>
As the ketene compound (e7), ketene represented by the following formula:

And diketene represented by the following formula;

And aldoketenes in which the substituent of the β carbon of ketene is monosubstituted, ketoketenes in which di substitution is made, and the like.

The said hydrolysis resistant agent can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of suppressing the generation of black streaks at the time of molding of a resin composition due to hydrolysis of a PC-POS copolymer, the hydrolysis resistant agent is an amide compound (e1), an imide compound (e2) and an epoxy compound One or more selected from the group consisting of (e3) is preferable, and one or more selected from the group consisting of the amide compound (e1) and the epoxy compound (e3) is more preferable, and epoxidized natural oil, epoxidized synthetic oil, and More preferably, it is at least one epoxy compound (e3) selected from the group consisting of cyclic epoxy compounds.

The compounding quantity in the case of mix | blending a hydrolysis resistant agent with the polycarbonate-type resin composition of this invention, Preferably it is 0.02 mass part or more 5.0 mass parts with respect to 100 mass parts of polycarbonate resin composition (S) Or less, more preferably 0.05 parts by mass or more and 1.0 parts by mass or less, still more preferably 0.1 parts by mass or more and 0.5 parts by mass or less. When the compounding amount of the hydrolysis resistant agent is 0.02 parts by mass or more with respect to 100 parts by mass of the polycarbonate resin (A), black at the time of molding of the resin composition resulting from hydrolysis of the PC-POS copolymer Occurrence of streaks can be suppressed more effectively. If it is 5.0 parts by mass or less, gas is generated during molding of the resin composition, and problems such as adhesion to a mold do not occur, which is preferable from the aspect of economy.
If the blending amount of the hydrolysis resistant agent is 0.05 parts by mass or more, it is preferable because black streaks generated in the inside of a molded article formed with a constant back pressure are further suppressed, and further 0.1 part by mass If it is the above, since the black streak which generate | occur | produces inside the molded object shape | molded by still higher back pressure is suppressed more, it is further preferable.

<Antioxidant>
The polycarbonate resin composition of the present invention preferably further contains an antioxidant. By mix | blending antioxidant with a polycarbonate-type resin composition, the oxidation degradation at the time of melting of a polycarbonate-type resin composition can be suppressed, and coloring etc. by oxidation degradation can be suppressed. As the antioxidant, a phosphorus-based antioxidant and / or a phenol-based antioxidant and the like are suitably used, and a phosphorus-based antioxidant is more preferable.

Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenylnonyl phosphite, diphenyl (2-ethylhexyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (nonylphenyl) Phosphite, diphenylisooctyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono (tridecyl) phosphite, phenyl diisodecyl phosphite, Phenyldi (tridecyl) phosphite, tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite , Tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 4,4'-isopropylidene diphenol dodecyl phosphite, 4,4'-isopropylidene diphenol tridecyl Phosphite, 4,4'-isopropylidene diphenol tetradecyl phosphite, 4,4'-isopropylidene diphenol pentadecyl phosphite, 4,4'-butylidene bis (3-methyl-6-tert-butylphenyl) ditrile Decyl phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) ) Pentaerythritol diphosphite, distearyl-pe Taerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetraphenyl dipropylene glycol diphosphite, 1,1,3-tris (2-methyl-4-di-tridecyl phosphite-5-tert-butyl) Phenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphane, triphenylphosphine, diphenylbutyl phosphine, diphenyloctadecyl phosphine, tris (p-tolyl) phosphine, tris (p-nonylphenyl) phosphine Tris (naphthyl) phosphine, diphenyl (hydroxymethyl) phosphine, diphenyl (acetoxymethyl) phosphine, diphenyl (β-ethylcarboxyethyl) phosphine, tris (p-chlorophenyl) phosphine, tris (p And -fluorophenyl) phosphine, benzyl diphenyl phosphine, diphenyl (β-cyanoethyl) phosphine, diphenyl (p-hydroxyphenyl) phosphine, diphenyl (1, 4-dihydroxyphenyl) -2- phosphine, phenylnaphthyl benzyl phosphine and the like.

Examples of phosphorus-based antioxidants include Irgafos 168 (trademark of BASF Japan Ltd.), Irgafos 12 (trademark of BASF Japan Ltd., trade mark), Irgafos 38 (trademark of BASF Japan Ltd., trade mark), Adekastab 2112 (trade name ADEKA made trademarks, Adekastab C (trade made by ADEKA), Adekastab 329K (trade made by ADEKA), Adekastab PEP 36 (trade made by ADEKA), JC 263 (Johoku Chemical Industry Co., Ltd.) ), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by GE), Weston 619 G (manufactured by GE), Weston 624 (manufactured by GE), Doverphos S-9228 PC (Dover Chemical Co., Ltd., mention may be made of a commercially available product of the trademark), and the like.

Examples of phenolic antioxidants include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-methylphenol, 2 Hindered phenols such as 2,2'-methylenebis (4-methyl-6-tert-butylphenol) and pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] It can be mentioned.
Among these antioxidants, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and the like And those having a pentaerythritol diphosphite structure or triphenylphosphine are preferable.

As a phenolic antioxidant, Irganox 1010 (BASF Japan KK-made trademark), Irganox 1076 (BASF Japan KK-made trademark), Irganox 1330 (BASF Japan KK made trademark), Irganox 3114 (BASF Japan) are mentioned, for example. Co., Ltd., trademark, Irganox 3125 (BASF Japan Ltd., trademark), BHT (Takeda Pharmaceutical Co., Ltd., trademark), Cyanox 1790 (Cyanamid, trademark) and Sumilizer GA-80 (Sumitomo Chemical Co., Ltd.) Commercially available products such as manufactured products, trademarks) can be mentioned.

The said antioxidant can be used individually by 1 type or in combination of 2 or more types.
The blending amount of the antioxidant in the polycarbonate resin composition of the present invention is preferably 0.001 parts by mass or more and 0.5 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S), and is preferably Is 0.01 to 0.3 parts by mass, more preferably 0.05 to 0.3 parts by mass. If the amount of the antioxidant with respect to 100 parts by mass of the polycarbonate resin composition (S) is in the above range, a sufficient antioxidant action can be obtained, and mold contamination at the time of molding can be suppressed.

The polycarbonate-based resin composition of the present invention can be obtained by blending the above-mentioned components in the above proportions, and various optional components to be used if necessary, in appropriate proportions, and kneading them.
Compounding and kneading are carried out by premixing with a commonly used apparatus such as a ribbon blender, drum tumbler, etc. to obtain a Henschel mixer, Banbury mixer, single screw extruder, twin screw extruder, multiple screw extruder and It can be carried out by a method using Conida and the like. The heating temperature at the time of kneading | mixing is normally selected suitably in the range of 240 degreeC or more and 320 degrees C or less. As this melt-kneading molding, the use of an extruder, in particular, a vent-type extruder is preferable.

The polycarbonate resin composition of the present invention containing a white pigment can provide a white molded article in which the occurrence of appearance defects such as black streaks at the time of molding is suppressed. The black streaks are recognized more strongly as the average value of the difference “ΔL value” of the lightness L value when the molded product is measured by the colorimeter under the following conditions. The colorimetric conditions are as follows.
<Positioning>
Positioning is performed as shown in FIG. That is, on a 150 mm × 150 mm molded product molded under the molding conditions described later, the end along the flow direction of the resin from the gate position of the injection molding machine at molding is the vertical axis, With 15 as a horizontal axis, 15 × 15 position division is performed at intervals of 1 cm (longitudinal) × 1 cm (horizontal) in order from the point at which the vertical axis and the horizontal axis are orthogonal.
<Measurement conditions>
Measurement is performed at a viewing angle of 10 ° using a D65 light source as a light source.
<Measurement location>
The position of 3 horizontal x 8 vertical after position division is the reference point, and the position from 8 horizontal x 3 vertical to 8 horizontal x 14 vertical is the measurement target position.
<ΔL value>
Preferably, the difference between the L value of the measurement target position and the L value of the reference point is ΔL value, and the ΔL value is 0.18 or less. The ΔL value is more preferably 0.17 or less, and still more preferably 0.15 or less.
When the ΔL value of a molded article made of a polycarbonate resin composition is in the above range, a molded article excellent in appearance where generation of black streaks is suppressed can be obtained. An image of black streaks that can be formed on a molded article is shown in FIG. In the present invention, this black stripe can be suppressed.

The viscosity-average molecular weight (Mv) of the polycarbonate-based resin composition of the present invention can be appropriately adjusted to achieve the target molecular weight depending on the application and product used, preferably 12,000 or more and 50,000 or less, or more It is preferably 15,000 to 30,000, more preferably 16,000 to 25,000, and further preferably 16,000 to 22,000. When the viscosity average molecular weight is 12,000 or more, sufficient strength of the molded article can be obtained. If the viscosity average molecular weight is 50,000 or less, the flowability is not too low, the moldability is good, and injection molding or extrusion molding can be performed at a temperature at which thermal degradation does not occur.
The viscosity average molecular weight (Mv) can be determined by the method described above.

[Molding]
The molded article of the present invention contains the polycarbonate resin composition of the present invention. The said molded article uses the said melt-kneading molding machine or the obtained pellet as a raw material, The injection molding method, the injection compression molding method, the extrusion molding method, the blow molding method, the press molding method, the vacuum molding method, the foam molding method etc. It can be manufactured by In particular, it is preferable to produce a molded article by injection molding or injection compression molding using the obtained pellets.

In the production of a molded article containing a polycarbonate-based resin composition, the residence time of the polycarbonate-based resin composition in a molding machine is shortened from the viewpoint of suppressing the mixing of water in the production process and suppressing the generation of black streaks during molding. It is preferable to manufacture on the conditions which Preferred embodiments of the method for producing a molded article by injection molding or injection compression molding are, for example, as follows.

In the production of a molded article by an injection molding method or an injection compression molding method, it is preferable to melt and plasticize pellets made of a polycarbonate resin composition by an injection molding machine equipped with a screw. From the viewpoint of suppressing the generation of black streaks, the molding machine is preferably a low compression screw type, and the screw shape is preferably a full flight screw.
The screw back pressure is preferably set in a low range from the viewpoint of suppressing shear heat generation and suppressing the compression of the resin composition to suppress the generation of black streaks. The back pressure can be appropriately selected according to the apparatus used, for example, in the range of about 2 to 10 MPa in the case of molding by an electric injection molding machine capable of direct pressure control of the pressure in the cylinder (hydraulic type: hydraulic cylinder type) This is not a limitation because it is adjusted by). From the same point of view, it is desirable to carry out the screw rotation speed at 100 rpm so as to reduce the shear rate.

The temperature (cylinder temperature) at the time of molding is preferably set, for example, at 230 to 320 ° C. from the viewpoint of reducing the viscosity of the polycarbonate resin composition to smooth the flow.
The impact strength of the molded article of the present invention is such that the value of notched Izod at -40 ° C. measured by the method described in the Examples is 30 to 100 kJ /, from the viewpoint of exhibiting sufficient impact characteristics and from the viewpoint of manufacturing ease. it is preferably m ^2, more preferably from 35 ~ 80kJ / m ^2, more preferably from 40 ~ 70kJ / m ^2, and most preferably 45 ~ 60kJ / m ^2.

As described above, the molded article of the present invention preferably has an average value of “ΔL value” of the difference in lightness L value when the molded article is subjected to colorimetry with a colorimeter, preferably 0.18 or less, more preferably 0. Since it is as small as not more than 17 and more preferably not more than 0.15, it is a white molded article excellent in appearance, in which generation of black streaks is suppressed.

The molded article of the present invention is a television, radio cassette, video camera, video tape recorder, audio player, DVD player, air conditioner, mobile phone, display, computer, register, calculator, copier, printer, facsimile, etc. It can be suitably used for parts for electronic devices, housings for the devices, lighting equipment interior and exterior parts, vehicle interior and exterior parts, food trays and dishes. In particular, it is suitable as a material of a housing such as a mobile phone, a mobile personal computer, a digital camera, a video camera, and an electric power tool.

Examples of the present invention will be further described. The present invention is not limited at all by these examples. The measurement and evaluation in each example were performed by the method shown below.

<Measurement of chloroformate concentration>
It measured using oxidation / reduction titration and silver nitrate titration with reference to JIS K 8203: 1994 on the basis of chloride ion concentration.

<Measurement of Weight Average Molecular Weight (Mw)>
The weight average molecular weight (Mw) is detected using GPC as a developing solvent, using GPC [column: TOSOH TSK-GEL MULTIPORE HXL-M (two) + Shodex KF 801 (one), temperature 40 ° C., flow rate 1.0 mL / min, Container: RI] was measured as a standard polystyrene conversion molecular weight (weight average molecular weight: Mw).

<Average chain length and content of polydimethylsiloxane>
It was calculated from the integral value ratio of methyl groups of polydimethylsiloxane by NMR measurement.
1. Method of quantifying average chain length of polydimethylsiloxane ¹ H-NMR measurement conditions NMR apparatus: manufactured by JEOL RESONANCE ECA 500
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 to 40 mg
Solvent: Deuterated chloroform Measurement temperature: Room temperature Number of integrations: 256 times In the case of allylphenol-terminated polydimethylsiloxane A: Integral value of methyl group of dimethylsiloxane moiety observed around δ-0.02 to 0.5 B: δ 2. Integral 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: Integral value of methyl group of dimethylsiloxane moiety observed around δ-0.02 to 0.5 B: methylene group of eugenol observed around δ 2.40 to 2. 70 Integral value of polydimethylsiloxane chain length = (A / 6) / (B / 4)

2. Determination of polydimethylsiloxane content in PC-PDMS copolymer Determination of polydimethylsiloxane copolymerization amount in PTBP-terminated polycarbonate copolymerized with allylphenol-terminated polydimethylsiloxane NMR apparatus: ECA manufactured by JEOL RESONANCE -500
Probe: TH5 5φ NMR sample tube correspondence Observation range: -5 to 15 ppm
Observation center: 5 ppm
Pulse repetition time: 9 seconds Pulse width: 45 °
Integration number: 256 times NMR sample tube: 5φ
Sample amount: 30 to 40 mg
Solvent: Deuterated chloroform Measurement temperature: Room temperature A: Integral value of methyl group of BPA observed near δ 1.5 to 1.9 B: Dimethyl siloxane observed near δ-0.02 to 0.3 Integral value of methyl group C: Integral value of butyl group in p-tert-butylphenyl moiety observed around δ 1.2 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 × 74.1 / TW × 100

<Measurement of viscosity average molecular weight (Mv)>
The viscosity average molecular weight (Mv) is obtained by measuring the viscosity of a methylene chloride solution (concentration: g / L) at 20 ° C. using an Ubbelohde viscometer, and the limiting viscosity [粘度] is determined therefrom to obtain the following equation (Schnell's equation Calculated by).

Synthesis Example 1: Synthesis of Polycarbonate Oligomer To a 5.6 mass% aqueous sodium hydroxide solution, 2000 mass ppm of sodium dithionite was added with respect to bisphenol A to be dissolved later, and the bisphenol A concentration was 13.5 mass. Bisphenol A was dissolved to a concentration of 10% to prepare an aqueous sodium hydroxide solution of bisphenol A.
At a flow rate of 40 L / hr of an aqueous solution of sodium hydroxide of bisphenol A and 15 L / hr of methylene chloride, phosgene was continuously passed through a tubular reactor with an inner diameter of 6 mm and a tube length of 30 m at a flow of 4.0 kg / hr. The tubular reactor had a jacket portion, and cooling water was passed through the jacket to keep the temperature of the reaction solution below 40 ° C.
The reaction solution leaving the tubular reactor is continuously introduced into a baffled tank reactor with an internal volume of 40 L and equipped with a receding wing, and further an aqueous sodium hydroxide solution of bisphenol A 2.8 L / hr, 25 The reaction was carried out with the addition of 0.07 L / hr of a mass% aqueous solution of sodium hydroxide, 0.64 L / hr of a 1 mass% aqueous solution of triethylamine and 17 L / hr of water. The reaction liquid which overflowed from the tank reactor was continuously withdrawn, and the aqueous phase was separated and removed by leaving to stand, and the methylene chloride phase was collected.
The polycarbonate oligomer thus obtained had a concentration of 318 g / L and a chloroformate concentration of 0.75 mol / L. Moreover, the weight average molecular weight (Mw) was 1190.

<Production Examples 1 to 2 of polycarbonate-polyorganosiloxane copolymer (A)>
The values of (i) to (xiv) described below indicate the amounts used of the respective components and are as shown in Table 1.
Polycarbonate oligomer solution (PCO) (i) L, methylene chloride (MC) (ii) L and average chain length prepared as described above in a 50 L tank reactor equipped with baffles, paddle stirrers and cooling jackets A solution of allylphenol end-modified polydimethylsiloxane (wherein polydimethylsiloxane may be referred to as PDMS) (iv) where n = (iii) is dissolved in methylene chloride (MC) (v) L, and triethylamine ( TEA) (vi) mL was charged, and under stirring, 8.0% by mass aqueous sodium hydroxide solution (NaOHaq) (vii) g was added thereto, and a reaction of polycarbonate oligomer and allylphenol end-modified PDMS was performed for 20 minutes ( Prepolymerization step).
In this polymerization solution, a methylene chloride solution of p-tert-butylphenol (PTBP) (PTBP (viii) g dissolved in methylene chloride (MC) (ix) L), sodium hydroxide aqueous solution of BPA (NaOH (x) Add 40 g of sodium dithionite (Na ₂ S ₂ O ₄ ) (xi) g in water (xii) L to BPA (xiii) g) and add 40 minutes of polymerization reaction It implemented (this polymerization process).
After adding methylene chloride (MC) (xiv) L for dilution and stirring for 10 minutes, the mixture was separated into an organic phase containing PC-POS and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of PC-POS thus obtained is sequentially washed with 15% by volume of 0.03 mol / L aqueous NaOH solution and 0.2 mol / L hydrochloric acid with respect to the solution, and then the water in the aqueous phase after washing is washed. Washing with pure water was repeated until the conductivity became 0.01 μS / m or less.
The methylene chloride solution of polycarbonate obtained by washing was concentrated and crushed, and the obtained flakes were dried at 100 ° C. under reduced pressure. Table 1 shows the results of measurement of the PDMS concentration and viscosity average molecular weight of the obtained flakes.

Measurement of water concentration in white pigment (C) White pigment powder of a sample is left to stand at a temperature of 25 ° C. and a constant temperature and humidity of 55% relative humidity for 24 hours to make it equilibrated, and 0.3 g of the sample is Karl Fischer moisture Moisture was measured at a temperature of 0 to 300 ° C at a nitrogen flow rate of approximately 250 mL using the measuring device “Coulometric method moisture meter CA100” and the moisture vaporization device “VA-100” (all manufactured by Dia Instruments Co., Ltd.) attached thereto After the concentration was measured, the value obtained by subtracting the water concentration detected and accumulated at 0 to 120 ° C. was taken as the amount of chemically bound water maintained at 120 ° C. or higher (up to 300 ° C.).

Measurement of Maximum Peak Temperature of EGA Curve of Organic Layer by Pyrolysis Gas Chromatography <Use Device>
Thermal decomposition equipment: "PY-3030D" made by Frontier Lab
Gas chromatograph (GC) device: Agilent 7890B GC system column: Frontier Lab "UADTM-2.5N" (length 2.5 m x inner diameter 0.15 mm)
<Thermal decomposition furnace temperature rise condition>
100 ° C (0 min) → temperature rise 20 ° C / min → 800 ° C
<GC conditions>
Carrier gas (He) flow rate: 1 mL / min
Split ratio: 10: 1
Inlet temperature: 300 ° C
Oven: 300 ° C (constant)
Detector: FID (hydrogen flame ionization detector) 300 ° C
<Measurement procedure>
0.5 mg of a sample (titanium oxide pigment) was weighed into a sample cup and attached to a thermal decomposition apparatus. Next, the sample cup was dropped into the pyrolysis furnace, and immediately the heating of the pyrolysis furnace was started, and at the same time, GC measurement was started. The temperature at the peak top of the obtained EGA curve was taken as the maximum peak temperature.

GC-MS analysis of organic layer <using device>
Measuring equipment: Gerstel's small thermal desorber TDU and multifunctional auto sampler MPS, Agilent's GC / MS equipment "6890/5975 MSD"
Column: “DB-5 MS” (30 mm × 0.25 mm × 0.25 μm) manufactured by Agilent
<TDU section conditions>
TDU part: 50 ° C (0.01 min) → 720 ° C / min → 300 ° C (20 min) Splitless CIS part: -50 ° C (0.01 min) → 12 ° C / sec → 350 ° C (5 min), split 30: 1
<GC-MS conditions>
Carrier gas (He) flow rate: 1 mL / min
Oven: 50 ° C (5 min) → 10 ° C / min → 330 ° C (10 min)
Scan range m / z = 35-800
<Analytical procedure>
10 mg of the sample (titanium oxide pigment) was weighed in a dedicated container and attached to a TDU / GC-MS apparatus. Next, GC-MS measurement was performed under the conditions described above, and the resulting evolved gas components were identified using a National Institute of Standards and Technology (NIST) mass library.

In the following description of the organic layer of the white pigment (C), the component detected by GC-MS analysis of the organic layer is the following group A as “organic layer A”, and the following group B It is called "organic layer B".
[Group A]

[Group B]

Examples 1 to 5 and Comparative Examples 1 to 3
The components listed in Tables 2-1 and 2-2 are compounded in the amounts described, and supplied to a vented twin-screw extruder ("TEM 35B" manufactured by Toshiba Machine Co., Ltd.), screw rotation speed 150 rpm, discharge The mixture was melt-kneaded at a barrel setting temperature of 280 ° C. (measured extrusion: 295 to 300 ° C.) at an amount of 20 kg / hr to obtain pellets.

(1) Observation of appearance defect (black streaks) of molded product After the above-mentioned pellets are preliminarily dried in a dryer at 120 ° C. for 8 hours, an injection molding machine (“MD350Wi15 HP-AP” manufactured by NIIGATA MACHINE Techno, Ltd.) Injection molding was performed for 20 shots under the following conditions using. The appearance of the obtained molded article was visually observed and evaluated according to the following criteria.
Specifically, pellets were fed from the hopper into the cylinder, and the number of revolutions of the screw for plasticizing and kneading was 100 rpm, and the setting of the screw back pressure was 40 MPa, and injection molding was performed under the following conditions. When the screw back pressure is increased, appearance defects on black streaks tend to occur. The appearance of black streaks was evaluated for the obtained molded product. In the table, the "AA" evaluation particularly indicates that a black stripe pattern is less likely to occur, and the evaluation result is good.
AA: No black streaky pattern is observed on the surface of the molded article.
A: A black streak pattern is observed very slightly on the surface of the molded article.
B: A black streak pattern is observed on the surface of the molded article at an intermediate level between the above A and the following C.
C: A black stripe pattern is clearly observed on the surface of the molded article.

(2) Observation of black streaks (transmission) A frame obtained by opening the above-mentioned molded product on a wooden board sufficiently larger than the molded product size with the same size as the molded product is provided The molded product was observed from the opposite side by applying a light source from a 1.5 kW lamp and evaluated according to the following criteria.
AA: Black streaks are not observed at all.
A: A black streak pattern is slightly observed.
B: A black streak pattern is observed at an intermediate level between the above A and the following C.
C: Black streaks are clearly observed.

(3) Colorimetry of black streaks on the surface of a molded product On a 150 mm × 150 mm molded product molded under the same conditions as (1), as shown in FIG. 1, the resin from the gate position of the injection molding machine at molding The end along the flow direction is the vertical axis, the end orthogonal to the vertical axis is the horizontal axis, and 15 points at intervals of 1 cm (longitudinal) x 1 cm (horizontal) from the point at which the longitudinal and horizontal axes are orthogonal Perform position assignment of × 15.
The position to be measured 3 × 8 vertical position after dividing the position is the reference point, the position from 8 × 3 × 8 × 14 vertical position of the measurement target position, L value of the reference point and the measurement target position spectral spectrophotometer ( It is measured by Konica Minolta Co., Ltd. product, spectral colorimeter CM-600d, SCE (regular reflection light removal) mode, observation light source D65, observation visual field 10 °, aperture 5 mmφ).
The difference (ΔL) between the L value at the measurement symmetrical position and the L value at the reference point is calculated, and the average value of the ΔL values at the measurement symmetrical position is determined. The larger the average value of the ΔL values, the stronger the black streaks on the surface as shown in FIG.

<Injection molding conditions>
Mold: Flat plate mold of 150 mmW × 150 mmH × 2 mmt Mold temperature: 80 ° C.
Cylinder temperature setting: The temperature described in Tables 2-1 and 2-2 was set for each example and comparative example.
Injection speed: Two stages are set, and the resin is filled with the speed from the measurement position (60 mm) to 50 mm as V1, and the speed from 50 mm to 8 mm as V2. V1 = 30 mm / sec, V2 = 50 mm / sec Holding pressure condition: After filling the resin, pressure was applied for 3 seconds at 50 MPa.

The components used in the table are as follows.
(B1) Styrene-based resin: Nippon A & L Co., Ltd. product, "Clarastic SXH-330 (acrylonitrile-butadiene-styrene terpolymer (ABS))", content of structural unit derived from butadiene; 12% by mass
(C-1) Titanium oxide pigment: "CR-63" manufactured by Ishihara Sangyo Co., Ltd. (Crystal structure: rutile type, titanium dioxide surface-treated with silica-alumina 3% and dimethyl silicone, average particle size: 0. 21 μm, amount of chemically bonded water: 2,600 mass ppm, organic layer B, maximum peak temperature of EGA curve: 380 ° C.)
(C-2) Titanium oxide pigment: “PF-726” manufactured by Ishihara Sangyo Co., Ltd. (Crystal structure: rutile type, titanium dioxide surface-treated with only 8% silica-alumina, average particle size: 0.21 μm, Chemical bond water content: 5,100 mass ppm)
(C-3) Titanium oxide pigment: "R-TC30" manufactured by HUNTSMAN (crystal structure: rutile type, surface treated with titanium dioxide with siloxane, average particle size: 0.21 μm)
Antioxidant: "IRGAFOS 168" (Tris (2,4-di-tert-butylphenyl) phosphite) manufactured by BASF Japan

The polycarbonate-based resin composition of the present invention is a resin composition containing a white pigment, in which the occurrence of appearance defects such as black streaks at the time of molding is suppressed, and a white molded article having a good molding appearance is provided. Can. The molded article can be suitably used for parts for electric or electronic devices or housings for such devices, lighting equipment interior and exterior parts, vehicle interior and exterior parts, food trays and dishes. In particular, it is suitable as a material of a housing such as a mobile phone, a mobile personal computer, a digital camera, a video camera, and an electric power tool.

Claims

A polycarbonate-polyorganosiloxane copolymer (A1) containing a polycarbonate block consisting of repeating units represented by the following general formula (I) and a polyorganosiloxane block containing repeating units represented by the following general formula (II) And a white pigment (C), and a polycarbonate resin composition (S) containing 50% by mass or more and 92% by mass or less and 8% by mass or more and 50% by mass or less of a styrene resin (B) Including
The polycarbonate-type resin composition which contains the said white pigment (C) 0.1 mass part or more and 40 mass parts or less with respect to 100 mass parts of said polycarbonate-type resin composition (S).

[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 represents a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, carbon And an aryl alkylene 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 represent an integer of 0 to 4; ]
The polycarbonate resin composition according to claim 1, wherein the styrene resin (B) is an acrylonitrile-butadiene-styrene copolymer.
The polycarbonate resin composition according to claim 1 or 2, wherein the average chain length of the polyorganosiloxane block is 50 or more.
The polycarbonate resin composition according to any one of claims 1 to 3, wherein the content of polyorganosiloxane in the polycarbonate resin (A) is 0.1% by mass or more and 25% by mass or less.
The polycarbonate resin composition according to any one of claims 1 to 4, wherein the viscosity average molecular weight of the polycarbonate resin (A) is 12,000 or more and 50,000 or less.
The polycarbonate according to any one of claims 1 to 5, wherein the content of the polyorganosiloxane block in the polycarbonate-polyorganosiloxane copolymer (A1) is 1.0% by mass or more and 40% by mass or less. Resin composition.
The polycarbonate system according to any one of claims 1 to 6, wherein the white pigment (C) is at least one selected from the group consisting of titanium oxide pigments, zinc sulfide pigments, zinc oxide pigments, and barium sulfate pigments. Resin composition.
The polycarbonate resin composition according to claim 7, wherein the white pigment (C) is a titanium oxide pigment.
The polycarbonate system according to claim 8, wherein the titanium oxide pigment has an inorganic oxide layer comprising at least one inorganic oxide selected from the group consisting of silica, zirconia and alumina on the surface of titanium oxide particles. Resin composition.
The polycarbonate resin composition according to claim 9, wherein the titanium oxide pigment further has an organic layer on the surface of the inorganic oxide layer.
The polycarbonate resin composition according to claim 10, wherein the maximum peak temperature of the generated gas analysis curve obtained by the generated gas analysis using the pyrolysis gas chromatograph device and the FID detector of the organic layer is 390 ° C or more.
A value obtained by subtracting the water concentration measured by the Karl Fischer method at 0 ° C. or more and 120 ° C. or less from the water concentration measured by the Karl Fisher method at 0 ° C. or more and 300 ° C. or less of the white pigment (C) is 8,000. The polycarbonate resin composition according to any one of claims 1 to 11, having a mass ppm or less.
The polycarbonate resin composition according to any one of claims 1 to 12, which has a viscosity average molecular weight of 12,000 or more and 50,000 or less.
The difference (ΔL) between the L value of the measurement target position and the L value of the reference point measured with a colorimeter for the molded product of the polycarbonate resin composition is 0.18 or less. Item 14. The polycarbonate resin composition according to any one of items 1 to 13.
Light source: D65 light source Viewing angle: 10 °
Measurement method: The end along the flow direction of the resin from the gate position of the injection molding machine at the time of molding is on the vertical axis, and the end orthogonal to the vertical axis is on the horizontal axis The position division of 15 × 15 is performed at intervals of 1 cm (longitudinal) × 1 cm (lateral) in order from the point at which the vertical axis and the horizontal axis are orthogonal to each other. Measure the L value of the following reference point after position division and the measurement symmetrical position.
Reference point: 3 horizontal × 8 vertical position Measurement symmetrical position: 8 horizontal × 3 vertical × 8 horizontal × 14 position
A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 14.
The molded article according to claim 15, wherein the difference (ΔL) between the L value of the measurement target position and the L value of the reference point measured by the colorimeter under the following conditions is 0.18 or less.
Light source: D65 light source Viewing angle: 10 °
Measurement method: The end along the flow direction of the resin from the gate position of the injection molding machine at the time of molding is on the vertical axis, and the end orthogonal to the vertical axis is on the horizontal axis The position division of 15 × 15 is performed at intervals of 1 cm (longitudinal) × 1 cm (lateral) in order from the point at which the vertical axis and the horizontal axis are orthogonal to each other. Measure the L value of the following reference point after position division and the measurement symmetrical position.
Reference point: 3 horizontal × 8 vertical position Measurement symmetrical position: 8 horizontal × 3 vertical × 8 horizontal × 14 position