JP2021028350A - Polycarbonate-based resin composition and molded product thereof - Google Patents

Abstract

To provide a polycarbonate-based resin composition that contains a PC-POS copolymer, a styrene-based resin, a white pigment and a metal deactivating agent, and suppresses the occurrence of an appearance defect such as black streaks during molding.SOLUTION: Provided is a polycarbonate-based resin composition that contains: a polycarbonate-based resin composition (S) containing a particular polycarbonate-polyorganosiloxane copolymer (A1)-containing polycarbonate-based resin (A) by 50 mass% or more and 99 mass% or less, and a styrene-based resin (B) by 1 mass% or more and 50 mass% or less; a white pigment (C); and a metal deactivating agent (D), and in which the white pigment (C) is contained by 0.1 pts.mass or more and 40 pts.mass or less relative to 100 pts.mass of the polycarbonate-based resin composition (S), and the metal deactivating agent (D) is contained by 0.005 pts.mass or more and 1.0 pts.mass or less relative to 100 pts.mass of the polycarbonate-based resin composition (S).SELECTED DRAWING: None

Description

The present invention relates to a polycarbonate resin composition and a molded product thereof. More specifically, a polycarbonate resin composition containing a polycarbonate-polyorganosiloxane copolymer, a styrene resin, a white pigment, and a metal inactivating agent to suppress the occurrence of appearance defects such as black streaks during molding, and a polycarbonate resin composition. Regarding the molded product.

Polycarbonate resin is excellent in mechanical strength, electrical properties, transparency, etc., and is widely used as an engineering plastic in various fields such as electric and electronic equipment fields and automobile fields. Polycarbonate resin is also used for housings of mobile phones, mobile personal computers, digital cameras, video cameras, power tools, etc. In these applications, impact resistance is important because it may fall during handling. , Design (especially color) is also an important factor.
A resin material such as a polycarbonate resin can be relatively easily imparted with a desired color by blending a colorant such as a pigment. Among the polycarbonate-based resins, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane (hereinafter, may be referred to as a PC-POS copolymer) has excellent impact resistance, and thus is suitable for the above-mentioned applications. Expected to be applied.

The PC-POS copolymer has high impact resistance in addition to the heat resistance and hydrolysis resistance of general homopolycarbonate resins, so that it is a thin-walled molded product with severe usage conditions and environment and high strength. Application to members is progressing. However, the 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 streaks) is generated during molding. .. Therefore, in the white-colored polycarbonate resin material, it is necessary to shorten the average chain length of the polyorganosiloxane portion in the PC-POS copolymer and reduce the blending amount of the PC-POS copolymer, which is impact resistant. It was difficult to further improve.

Patent Document 1 describes a PC-POS copolymer having a short average chain length of a polyorganosiloxane moiety and a PC having a long average chain length in a polycarbonate resin composition containing a PC-POS copolymer and titanium oxide. It is described that by using the −POS copolymer in combination, the generation of black streaks during molding is suppressed, and a polycarbonate resin composition having excellent impact resistance can be obtained. However, the resin composition disclosed in Patent Document 1 requires the use of a PC-POS copolymer having a short average chain length of the polyorganosiloxane moiety.

In addition, ordinary polycarbonate is used for white pigments such as titanium oxide, zinc sulfide, and zinc oxide used in white-colored polycarbonate-based resin compositions such as white reflectors attached to the backlight unit of a liquid crystal display (LCD). Even if the product is sufficiently dehumidified and dried at 100 to 120 ° C., which is a preliminary drying condition performed before molding, moisture that cannot be completely removed remains. It is known that when the resin composition containing this water is injection-molded, the water evaporates due to the molding heat to generate silver streaks. In order to overcome this problem, a polycarbonate resin composition containing a combination of a polycarbonate-based polymer and titanium oxide in which the difference in water concentration by the Karl Fischer method at 100 ° C. and 300 ° C. is reduced to 2700 mass ppm or less is used for silver. A technique for suppressing the occurrence of streaks is known (for example, Patent Document 2). However, Patent Document 2 does not disclose a technique for suppressing the generation of black streaks during molding, which is a peculiar phenomenon in a polycarbonate resin composition containing a PC-POS copolymer and a white pigment.

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

The present invention contains a PC-POS copolymer, a styrene resin, a white pigment, and a metal inactivating agent, and suppresses the occurrence of appearance defects such as black streaks during molding, and a polycarbonate resin composition and molding thereof. The purpose is to provide goods.

The present inventors have made a polycarbonate resin composition containing a predetermined PC-POS copolymer and a styrene resin, a white pigment, and a metal inactivating agent in a predetermined amount. , Found that the above task is achieved.
That is, the present invention relates to the following 1 to 17.
1. 1. Contains a polycarbonate-polyorganosiloxane copolymer (A1) containing a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II). A polycarbonate resin composition (S) containing 50% by mass or more and 99% by mass or less of the polycarbonate resin (A) and 1% by mass or more and 50% by mass or less of the styrene resin (B), and a white pigment (C). , With a metal inactivating agent (D)
The white pigment (C) is contained in an amount of 0.1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S).
A polycarbonate resin composition containing the metal inactivating agent (D) in an amount of 0.005 part by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S).

[In the formula, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorinatedyl group, and carbon. It shows an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or -CO-. R ³ and R ⁴ 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. 2. The polycarbonate-based resin composition according to 1 above, wherein the styrene-based resin (B) is an acrylonitrile-butadiene-styrene copolymer.
3. 3. The resin composition according to 1 or 2 above, wherein the polyorganosiloxane block has an average chain length of 50 or more.
4. The polycarbonate resin composition according to any one of 1 to 3 above, 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-based resin composition according to any one of 1 to 4, wherein the polycarbonate-based resin (A) has a viscosity average molecular weight of 12,000 or more and 50,000 or less.
6. The polycarbonate system according to any one of 1 to 5 above, 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.
7. The metal inactivating agent (D) is at least one selected from the group consisting of hydrazine-based compounds, triazole-based compounds, triazine-based compounds, and aminocarboxylate-based compounds, according to any one of 1 to 6 above. The polycarbonate-based resin composition according to the above.
8. The polycarbonate resin according to any one of 1 to 7 above, 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.
9. The resin composition according to 8 above, wherein the white pigment (C) is a titanium oxide pigment.
10. 9. The polycarbonate-based resin according to 9 above, 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.
11. The polycarbonate-based resin composition according to 10 above, wherein the titanium oxide pigment further has an organic layer on the surface of the inorganic oxide layer.
12. 11. The polycarbonate-based resin composition according to 11 above, wherein the maximum peak temperature of the generated gas analysis curve obtained by the generated gas analysis of the organic layer using a pyrolysis gas chromatograph device and a FID detector is 380 ° C. or higher.
13. The value obtained by subtracting the water concentration of the white pigment (C) measured by the Karl Fischer method at 0 ° C. or higher and 300 ° C. or lower from the water concentration measured by the Karl Fischer method at 0 ° C. or higher and 120 ° C. or lower is 8,000. The polycarbonate-based resin composition according to any one of 1 to 12 above, which has a mass of ppm or less.
14. The polycarbonate-based resin composition according to any one of 1 to 13 above, wherein the viscosity average molecular weight is 12,000 or more and 50,000 or less.
15. 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 for the molded product made of the polycarbonate resin composition is 0.18 or less. The polycarbonate resin composition according to any one of 1 to 14.
Light source: D65 light source Viewing angle: 10 °
Measuring method: On a molded product of length 150 mm × width 150 mm, the vertical axis is the end along the resin flow direction from the gate position of the injection molding machine at the time of molding, and the horizontal axis is the end orthogonal to the vertical axis. , 15 × 15 positioning is performed at intervals of 1 cm (vertical) × 1 cm (horizontal) in order from the point where the vertical axis and the horizontal axis are orthogonal to each other. The L value of the following reference point after the position division and the measurement symmetric position is measured.
Reference point: Position of 3 horizontal x 8 vertical Measurement symmetrical position: Position from 8 horizontal x 3 vertical to 8 horizontal x 14 vertical 16. A molded product comprising the polycarbonate-based resin composition according to any one of 1 to 15 above.
17. The molded product according to 16 above, wherein the difference (ΔL) between the L value of the measurement target position and the L value of the reference point measured under the following conditions with a colorimeter is 0.18 or less.
Light source: D65 light source Viewing angle: 10 °
Measuring method: On a molded product of length 150 mm × width 150 mm, the vertical axis is the end along the resin flow direction from the gate position of the injection molding machine at the time of molding, and the horizontal axis is the end orthogonal to the vertical axis. , 15 × 15 positioning is performed at intervals of 1 cm (vertical) × 1 cm (horizontal) in order from the point where the vertical axis and the horizontal axis are orthogonal to each other. The L value of the following reference point after the position division and the measurement symmetric position is measured.
Reference point: Position of horizontal 3 x vertical 8 Measurement symmetric position: Position from horizontal 8 x vertical 3 to horizontal 8 x vertical 14

The polycarbonate-based resin composition of the present invention can provide a white molded product in which the occurrence of appearance defects such as black streaks during molding is suppressed even if the resin composition contains a white pigment.

FIG. 6 is a schematic view showing a reference point and a measurement target position when measuring the L value of a molded product made of the polycarbonate resin composition of the present invention. The conceptual diagram which shows the black streak formed on a molded product.

Hereinafter, the polycarbonate-based resin composition of the present invention will be described in detail. In addition, in this specification, the preferable provision can be arbitrarily adopted, and it can be said that the combination of preferable ones is more preferable. Further, in the present specification, the description of "XX to YY" means "XX or more and YY or less".

The polycarbonate-based resin composition of the present invention is a polycarbonate-poly containing a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II). A polycarbonate resin composition containing 50% by mass or more and 99% by mass or less of a polycarbonate resin (A) containing an organosiloxane copolymer (A1) and 1% by mass or more and 50% by mass or less of a styrene resin (B). S), a white pigment (C), and a metal inactivating agent (D) are contained, and the white pigment (C) is added to 0.1 parts by mass of the polycarbonate resin composition (S). The metal inactivating agent (D) is contained in an amount of 0.005 part by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S). It is characterized by.

[In the formula, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorinatedyl group, and carbon. It shows an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or -CO-. R ³ and R ⁴ 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. ]

<Polycarbonate resin (A)>
The polycarbonate-based resin composition of the present invention contains a polycarbonate-based resin (A) containing a predetermined polycarbonate-polyorganosiloxane copolymer (A1).

[Polycarbonate-polyorganosiloxane copolymer (A1)]
The polycarbonate-polyorganosiloxane copolymer (A1) includes a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II). ..

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

In the above general formula (I), ^{examples of the halogen atom represented by R 1} and R ² independently include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Alkyl groups indicated by R ¹ and R ² independently include methyl group, ethyl group, n-propyl group, isopropyl group, and various butyl groups (“various” means linear or all branched chains. The same applies hereinafter), various pentyl groups, and various hexyl groups. Examples of the ^{alkoxy group represented by R 1} and R ² independently include the case where the alkyl group moiety is the alkyl group.
Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a 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 and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, a cyclooctanediyl group and the like, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, a 3,5,5-trimethylcyclohexylidene group, a 2-adamantylidene group and the like, and a cycloalkylidene group having 5 to 10 carbon atoms is preferable. , A cycloalkylidene group having 5 to 8 carbon atoms is more preferable. Examples of the aryl moiety of the arylalkylene group represented by X include an aryl group having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group and an anthryl group. Examples of the aryl moiety of the arylalkylidene group represented by X include an aryl group having 6 to 14 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group and an 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 an isopropylidene group are preferable. Is.

In the above general formula (II), ^{examples of the halogen atom represented by R 3} or R ⁴ independently include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the ^{alkyl group represented by R 3} or R ⁴ independently 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 indicated by R 3} or R ⁴ independently include the case where the alkyl group moiety is the alkyl group. Examples of the ^{aryl group independently represented by R 3} or R ⁴ include a phenyl group and a naphthyl group.
The R ³ and R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and all of them are preferable. It is more preferably a methyl group.

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

[In the formula, R ^{3 to} R ⁶ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. A plurality of R ^{3 to} R ⁶ may be the same as or different from each other. 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 Indicates O-R ^10- O-, and the plurality of Ys may be the same or different from each other. The R ⁷ represents a divalent organic residue containing a single bond, linear, branched or cyclic alkylene group, an aliphatic group and an aromatic group, a substituted or unsubstituted arylene group, or a dialylene group. R ⁸ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ⁹ represents a dialylene group. R ¹⁰ represents a straight chain, branched chain or cyclic alkylene group, or dialylene group. β represents a divalent group derived from a diisocyanate compound, or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid. n indicates the average chain length of the polyorganosiloxane. Each of p and q is an integer of 1 or more, and the sum of p and q is n-2. ]

Examples of the halogen atom independently indicated by R ^{3 to} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group represented by R ^{3 to R 6} independently 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 alkyl group. Examples of the aryl group represented by R ^{3 to R 6} independently include a phenyl group and a naphthyl group.
The R ^{3 to} R ⁶ are preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
^{It is preferable that R 3 to} R ^{6 in the} general formulas (II-I), (II-II) and / or (II-III) are all 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- Examples of the linear or branched alkylene group represented by R ^{7 in the above} include alkylene groups having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms, and cyclic alkylene groups having 5 to 15 carbon atoms, preferably carbon atoms. The number 5 to 10 cycloalkylene groups can be mentioned.

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

(C in the formula indicates a positive integer, usually an integer of 1 to 6)

The ^{dialylene group represented by R 7} , R ⁹ and R ¹⁰ is a group in which two arylene groups are directly linked or via a divalent organic group, and specifically -Ar ^1- W-. It is a group having a structure represented by Ar ^2-. Here, Ar ¹ and Ar ² represent an arylene group, and W represents a single bond or a divalent organic group. The divalent organic group indicated by W is, for example, an isopropylidene group, a methylene group, a dimethylene group, or a trimethylene group.
Examples of the arylene group represented by R ⁷ , Ar ¹ and Ar ² include an arylene group having 6 to 14 ring-forming carbon atoms such as a phenylene group, a naphthylene group, a biphenylene group and an anthrylene group. These arylene groups may have any substituent such as an alkoxy group and an alkyl group.
The ^{alkyl group represented by R 8} is a linear or branched chain having 1 to 8 carbon atoms, preferably 1 to 5 carbon atoms. Examples of the alkenyl group include a linear or branched chain having 2 to 8 carbon atoms, preferably 2 to 5 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the aralkyl group include a phenylmethyl group and a phenylethyl group.
The straight chain, branched chain or cyclic alkylene group indicated by ^{R 10} is the same as that of ^{R 7.}

Y is preferably −R ⁷ O—, where 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 for example, a divalent organic residue derived from allylphenol or a divalent organic residue derived from eugenol is more preferable. Specifically, R ⁷ preferably has a structure represented by the above general formula (x) or (xi).

Regarding p and q in the formula (II-II), it is preferable that p = q, that is, p = (n-2) / 2 and q = (n-2) / 2.

Further, β represents a divalent group derived from a diisocyanate compound or a divalent group derived from a dicarboxylic acid or a halide of a dicarboxylic acid, and is represented by, for example, the following general formulas (xiii) to (xvii) 2 The basis of the value is 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, it is preferable that n in the formulas (II-I) and (II-III) is 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. Is preferable. 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 product is good. The average chain length n is more preferably 55 or more, still more preferably 60 or more, even more preferably 80 or more, most preferably 85 or more, still 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. If the average chain length n exceeds 500, it becomes difficult to handle when producing the PC-POS copolymer (A1) and the economy is inferior. Therefore, 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 1.0% by mass or more and 30% by mass or less, further preferably 2.0% by mass or more and 10% by mass or less, still more preferably 4.0% by mass or more and 8.0% by mass or less.

The viscosity average molecular weight (Mv) of the PC-POS copolymer (A1) used in the present invention can be appropriately adjusted by using a molecular weight adjusting agent or the like so as to obtain the desired molecular weight depending on the intended use and product. However, it is preferably 12,000 or more and 50,000 or less, more preferably 15,000 or more and 30,000 or less, further 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 product having sufficient impact strength can be obtained. When the viscosity average molecular weight is 50,000 or less, the fluidity is not too low and the moldability is good, and injection molding or extrusion molding can be performed at a temperature that does not cause thermal deterioration.
The viscosity average molecular weight (Mv) is a value calculated from the following Schnell formula by measuring the ultimate viscosity [η] of a methylene chloride solution (concentration: g / L) at 20 ° C.

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 types of PC-POS copolymers (A1) are used, for example, PC-POS copolymers having different average chain lengths of the polyorganosiloxane blocks, contents of the polyorganosiloxane blocks, or viscosity average molecular weights are used. An example of combining two or more kinds of polymers can be mentioned. Each of the plurality of PC-POS copolymers (A1) shall satisfy the above requirements.

[Polycarbonate resin (A2)]
The polycarbonate-based resin (A) used in the present invention may further contain a polycarbonate-based 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).

[In the formula, R ³⁰ and R ³¹ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X'is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, and -SO. Indicates −, −SO ₂₋ , −O− or −CO−. d and e each independently represent an integer of 0 to 4. ]

Specific examples of R ³⁰ and R ^{31 include the same as those of R 1} and R ^2, and the preferred ones are also the same. The R ³⁰ and R ³¹ are more preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Specific examples of X'include the same as X, and preferred ones are also the same. d and e are independently, preferably 0 to 2, more preferably 0 or 1, respectively.

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

The content of the polyorganosiloxane in the polycarbonate resin (A) is preferably 0.1% by mass or more and 25% by mass or less, more preferably 0.5% by mass or more and 20 from the viewpoint of obtaining better impact resistance. It is mass% or less, more preferably 1.0 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 polycarbonate resin (A) can be appropriately adjusted so as to have the desired molecular weight depending on the intended use and product, but is 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, still more 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 product can be obtained. When the viscosity average molecular weight is 50,000 or less, the fluidity is not too low and the moldability is good, and injection molding or extrusion molding can be performed at a temperature that does not cause thermal deterioration.
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, or a transesterification method. Especially in the case of the interfacial polymerization method, the separation step between the organic phase containing the PC-POS copolymer and the aqueous phase containing the unreacted material, the catalyst residue, etc. becomes easy, and each of them is performed by alkali cleaning, acid cleaning, and pure water cleaning. The organic phase containing the PC-POS copolymer and the aqueous phase can be easily separated in the washing step. Therefore, a PC-POS copolymer can be efficiently obtained. As a method for producing a PC-POS copolymer, for example, the method described in JP-A-2014-80462 can be referred to.

Specifically, a pre-produced aromatic polycarbonate oligomer described later and polyorganosiloxane are dissolved in a water-insoluble organic solvent (methylene chloride, etc.), and an alkaline compound of a dihydric phenolic compound (bisphenol A, etc.) is dissolved. Add an aqueous solution (sodium hydroxide aqueous solution, etc.), use a tertiary amine (triethylamine, etc.) or a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.) as a polymerization catalyst, and use a terminal terminator (pt-butylphenol, etc. 1). It can be produced by subjecting it to an interfacial polycondensation reaction in the presence of (valent phenol). The PC-POS copolymer (A1) can also be produced by copolymerizing polyorganosiloxane, dihydric phenol, and phosgene, carbonic acid ester, or chlorohomete.

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

As the polyorganosiloxane used as a raw material for the PC-POS copolymer (A1), those represented by the following general formulas (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 specific examples and preferable ones are also the same.
Z represents a hydrogen atom or a halogen atom, and a plurality of Zs may be the same as or different from each other.

For example, examples of the polyorganosiloxane represented by the general formula (i) include compounds of the following general formulas (i-i) to (i-xi).

In the 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, usually an integer of 1-6.
Among these, from the viewpoint of ease of polymerization, the phenol-modified polyorganosiloxane represented by the above general formula (i-i) is preferable. From the viewpoint of easy availability, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds represented by the above general formula (i-ii), is described above. Α, ω-bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane, which is one of the compounds represented by the general formula (i-iii), is preferable.

In addition, a polyorganosiloxane raw material having the following general formula (xii) may be used.

In the formula, R ³ and R ⁴ are the same as those described 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 n above.

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).

^{[R 3} , R ⁴ , r and m in the equation are as described above]

In addition, as the polyorganosiloxane raw material, a polyorganosiloxane raw material represented by the following general formula (xiii) may be used.

[In the formula, R ^{18 to} R ²¹ are each independently a hydrogen atom or an alkyl group having 1 to 13 carbon atoms. R ²² is an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms. Q ² is a divalent aliphatic group having 1 to 10 carbon atoms. n indicates the average chain length, which is 30 to 70. ]

In the general formula (xiii), ^{the alkyl groups having 1 to 13 carbon atoms represented independently by R 18 to} R ²¹ are methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, and various pentyl groups. , 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 methyl groups.
Examples of the alkyl group having 1 to 6 carbon atoms indicated 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. Examples of the halogen atom indicated by R ²² include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkoxy group having 1 to 6 carbon atoms indicated by R ^{22 include the case where the alkyl group moiety is the alkyl group.} Examples of the aryl group having 6 to 14 carbon atoms indicated by R22 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 even more preferably a hydrogen atom.
As the ^{divalent aliphatic group having 1 to 10 carbon atoms indicated by Q 2} , a linear or branched divalent saturated aliphatic group having 1 to 10 carbon atoms is preferable. The saturated aliphatic group preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 3 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms. The 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).

[In the formula, R ^{18 to} R ²² , Q ² and n are as described above. ]

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

[In the formula, 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-dihydrogen organopentasiloxane, and then, In the presence of a hydrosilylation reaction catalyst, a phenolic compound (for example, 2-allylphenol, 4-allylphenol, eugenol, 2-propenylphenol, etc.) is added to the α, ω-dihydrogen organopentasiloxane to carry out an addition reaction. As a result, crude polyorganosiloxane can be obtained. Further, according to the method described in Japanese Patent No. 2662310, the obtained α, ω-dihydrogen organodone obtained by reacting octamethylcyclotetrasiloxane and tetramethyldisiloxane in the presence of sulfuric acid (acid catalyst). A crude polyorganosiloxane can be obtained by subjecting polysiloxane to an addition reaction of a phenolic compound or the like in the presence of a catalyst for hydrosilylation reaction in the same manner as described above. The α, ω-dihydrogen organopolysiloxane can be used by appropriately adjusting its average chain length n depending on the polymerization conditions, or a commercially available α, ω-dihydrogen organopolysiloxane can be used. Good. Specifically, those described in JP-A-2016-098292 can be used.

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

As the divalent phenol, it is preferable to use the divalent 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 the dihydric phenol represented by the above general formula (iv) include bis (hydroxyaryl) alkanes, bis (hydroxyaryl) cycloalkanes, dihydroxyaryl ethers, dihydroxydiarylsulfides, dihydroxydiarylsulfoxides, and the like. Examples thereof include dihydroxydiarylsulfones, dihydroxydiphenyls, dihydroxydiarylfluorenes, dihydroxydiaryladamantans and the like. These divalent 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], and the like. 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-t-butylphenyl) propane, 2,2-bis (4-hydroxy) -3-Bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4) Examples thereof include -hydroxy-3,5-dichlorophenyl) propane and 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane.

Examples of bis (hydroxyaryl) cycloalkanes include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and 1,1-bis (4-hydroxyphenyl). Examples thereof include -3,5,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) norbornane, and 1,1-bis (4-hydroxyphenyl) cyclododecane. Examples of dihydroxyaryl ethers include 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether and the like.
Examples of dihydroxydiarylsulfides include 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide and the like. Examples of the dihydroxydiaryl sulfoxides include 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and the like. Examples of dihydroxydiaryl sulfones include 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone and the like.

Examples of dihydroxydiphenyls include 4,4'-dihydroxydiphenyl and the like. Examples of dihydroxydiarylfluorenes include 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. Examples of dihydroxydiaryl adamantanes include 1,3-bis (4-hydroxyphenyl) adamantane, 2,2-bis (4-hydroxyphenyl) adamantane, and 1,3-bis (4-hydroxyphenyl) -5,7-. Examples thereof include dimethyl adamantane.
Examples of divalent phenols other than the above include 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5. -Bis (4-hydroxyphenylthio) -2,3-dioxapentane and the like can be mentioned.

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

A point-of-sale agent can be used to adjust the molecular weight of the resulting PC-POS copolymer. Examples of the terminal terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, m-pentadecylphenol and p-tert-amylphenol. Monovalent phenol can be mentioned. One of these monovalent phenols may be used alone, or two or more thereof may be used in combination.
After the above interfacial polycondensation reaction, the mixture is appropriately allowed to stand to separate into an aqueous phase and an organic solvent phase, and the organic solvent phase is washed (preferably a basic aqueous solution, an acidic aqueous solution, and water in this order) to obtain the obtained organic phase. A PC-POS copolymer can be obtained by concentrating and drying.

[Manufacturing method of polycarbonate resin (A2) other than (A1)]
The polycarbonate-based resin (A2) other than the above (A1) is, for example, reacted with a divalent phenol-based compound and phosgen in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution, and then a tertiary amine or a fourth. Conventional methods such as an interfacial polymerization method in which a polymerization catalyst such as a grade ammonium salt is added to polymerize, or a pyridine method in which a divalent phenolic compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgen is introduced to directly produce the compound. It can be obtained by a method for producing polycarbonate. In the above reaction, a molecular weight modifier (terminal terminator), a branching agent, or the like is used, if necessary.

Examples of the divalent phenolic compound include those represented by the following general formula (v).

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

Specific examples of the divalent phenolic compound include those described above in the method for producing a PC-POS copolymer (A1), and preferred ones are also the same. Among them, bis (hydroxyphenyl) alkane-based divalent phenol is preferable, and bisphenol A is more preferable.

<Styrene resin (B)>
By containing the styrene resin (B), the moldability of the resin composition, particularly the fluidity, can be improved. Further, by containing the styrene resin (B), the fluidity of the polycarbonate resin composition at the time of molding is increased, the shear stress received in the molding machine is relaxed, and the heat generation is suppressed, so that black streaks are suppressed. It is thought that it will be done.

Both an amorphous styrene resin and a crystalline styrene resin can be used. As the styrene resin (B), one type described specifically below may be used, or two or more types may be used in combination.
Examples of the amorphous styrene resin include 20 to 100% by mass of monovinyl aromatic monomers such as styrene and α-methylstyrene, and 0 to 60% by mass of vinyl cyanide monomers such as acrylonitrile and methacrylonitrile. It has a crystal structure obtained by polymerizing a monomer composed of 0 to 50% by mass of other vinyl-based monomers such as maleimide and methyl (meth) acrylate that can be copolymerized with these, or a monomer mixture. Examples include non-polymers.
Examples of these polymers include general-purpose polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), and the like.

As the amorphous styrene resin, a rubber-modified styrene resin reinforced with a rubber-like polymer can be preferably used. Examples of the rubber-modified styrene resin include impact-resistant polystyrene (HIPS) in which styrene is polymerized on rubber such as polybutadiene, and acrylonitrile-butadiene-styrene copolymer (ABS resin) in which acrylonitrile and styrene are polymerized on polybutadiene. There are methyl methacrylate-butadiene-styrene copolymer (MBS resin) in which methyl methacrylate and styrene are polymerized in polybutadiene, and two or more types of rubber-modified styrene resin can be used in combination, and the above-mentioned rubber is not used. It can also be used as a mixture with a modified amorphous styrene resin.

The content of rubber in the rubber-modified styrene resin is preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and further preferably 5% by mass or more and 15% by mass or less. If the proportion of rubber is 2% by mass or more, the impact resistance is sufficient, and if it is 50% by mass or less, there are problems such as a decrease in thermal stability, a decrease in melt fluidity, gel generation, and coloring. Does not occur.
Specific examples of the above rubber include a rubbery polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SBS), styrene-butadiene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, and isoprene. -Styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like can be mentioned. Of these, polybutadiene is particularly preferable. The polybutadiene used here is low cis polybutadiene (for example, one containing 1 mol% or more and 30 mol% or less of 1,2-vinyl bond and 30 mol% or more and 42 mol% or less of 1,4-cis bond) and high cis. Any of polybutadiene (for example, one containing 20 mol% or less of 1,2-vinyl bond and 78 mol% or more of 1,4-cis bond) may be used, or a mixture thereof may be used.

Examples of the crystalline styrene resin include styrene (co) polymers having a syndiotactic structure and an isotactic structure. In the present invention, an amorphous styrene resin is used for the purpose of further improving fluidity. It is preferable to use it. Further, among the amorphous styrene resins, the melt flow rate (MFR) at 200 ° C. and a load of 5 kg is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 80 g / 10 minutes, still more preferably 2 to 2. The one of 50 g / 10 minutes is used. When the melt flow rate (MFR) is 5 g / 10 minutes or more, sufficient fluidity is obtained, and when it is 100 g / 10 minutes or less, the impact resistance of the flame-retardant polycarbonate resin composition is good.

Among the amorphous styrene resins, impact-resistant 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 At least one selected from the polymer (AES resin) is preferable, and the acrylonitrile-butadiene-styrene copolymer (ABS resin) is particularly preferable.
To give an example of these particularly preferable ones, as AS resins, 290FF (manufactured by Techno Polymer Co., Ltd.), S100N, S200N, S101 (manufactured by UMG ABS Co., Ltd.), PN-117C (manufactured by Chi Mei Corporation), ABS Examples of the resin include Santac AT-05, SXH-330 (all manufactured by Nippon A & L Inc.), Toyorak 500, 700 (manufactured by Toray Industries, Inc.), and PA-756 (manufactured by Chi Mei Corporation). Examples of the MBS resin include C223A (manufactured by Mitsubishi Rayon Corporation).

<Polycarbonate resin composition (S)>
The polycarbonate-based resin composition of the present invention contains a polycarbonate-based resin composition (S) containing the above-mentioned polycarbonate-based resin (A) and styrene-based resin (B) as a resin component.
The polycarbonate resin composition (S) contains 50% by mass or more and 99% by mass or less of the polycarbonate resin (A) and 1% by mass or more and 50% by mass or less of the styrene resin (B). When the ratio of the polycarbonate resin (A) is in the above range, excellent impact resistance can be obtained. When the ratio of the styrene resin (B) is in the above 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 ratio of the polycarbonate resin (A) and the styrene resin (B) is assumed to be 100% by mass.

The ratio of the polycarbonate resin (A) in the polycarbonate resin composition (S) is preferably 70% by mass or more and 98% by mass or less, more preferably 80% by mass or more and 97% by mass or less, and further preferably 90% by mass or more. It is 95% by mass or less.
The ratio of the styrene resin (B) in the polycarbonate resin composition (S) is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more. It is 10% by mass or less.

<White pigment (C)>
The polycarbonate-based resin composition of the present invention contains a white pigment (C). The white pigment (C) is used as a toning material for a neutral color such as white or gray in the 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. More preferably, one or more selected from the group consisting of pigments, zinc sulfide pigments, and zinc oxide pigments. Among these white pigments, it is preferable to use a titanium oxide pigment from the viewpoint of making the color tone more white. Hereinafter, the description will be made in more detail on behalf of titanium oxide, but the same applies to the white pigments other than titanium oxide.

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

The titanium oxide pigment usually 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 inorganic oxide layer can suppress the catalytic activity of titanium oxide, which is a core particle, and can impart light resistance. Further, it also has the effect of alleviating the aggregation of the titanium oxide pigment in the resin composition and improving the dispersibility.

The titanium oxide pigment may have two or more layers of the inorganic oxide layers. In this case, the inorganic oxide layer located on the side closer to the core particles mainly contributes to the suppression of the catalytic activity of the titanium oxide particles, which are the core particles, and the impartation of light resistance, and the inorganic oxide layer located on the side farther from the core particles. Mainly contributes to alleviating aggregation of titanium oxide pigments in the resin composition and improving dispersibility.
When the titanium oxide pigment has two or more inorganic oxide layers, the inorganic oxide layer located on the side closer to the core particles is composed of one or more selected from the group consisting of silica and zirconia, and is located on the side farther from the core particles. The inorganic oxide layer to be formed is preferably made of alumina.

The inorganic oxide layer has the effect of suppressing the catalytic activity of titanium oxide, which is the core particle, while the inorganic oxides silica, zirconia, and alumina are hydrated inorganic substances and therefore have a high water absorption rate, so that the water content in the molding machine is high. Is easy to evaporate. The evaporated water causes hydrolysis of the polycarbonate resin. Therefore, in order to suppress the catalytic action of titanium oxide, it is preferable that the inorganic oxide layer is thick, and in order to suppress the hydrolysis of the polycarbonate resin, it is preferable that the thickness of the inorganic oxide layer is thin. Become.
Due to this contradictory relationship, the amount of the titanium oxide pigment for coloring the polycarbonate resin composition coated with the inorganic oxide layer is in the range of 3% by mass or more and 10% by mass or less in terms of the mass ratio with respect to the entire titanium oxide pigment. It is common. In white reflective material applications with high white pigment concentration and easy hydrolysis, such as those used in smartphones, the amount of titanium oxide pigment covered by the inorganic oxide layer is 3% by mass or more and 5% by mass as a mass ratio to the entire titanium oxide pigment. % Or less is a preferable range. On the other hand, in the use of colored molded products 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 or more and 10% by mass or less in terms of the mass ratio with respect 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 weather resistance deterioration due to the catalytic action of titanium oxide occurs. Most of the factors that cause black streaks in the injection molding of a polycarbonate resin composition containing a PC-POS copolymer and a white pigment such as a titanium oxide pigment are the unsuppressed catalytic action of the titanium oxide.

Conventionally, it has been said that the titanium oxide pigment causes a decrease in the molecular weight of the polycarbonate resin because the water content in the titanium oxide pigment induces hydrolysis of the polycarbonate resin under high temperature and high pressure in the molding machine. To confirm this fact, researchers added the same amount of titanium oxide pigments with different water contents to the polycarbonate resin and kneaded them with a twin-screw kneader, and based on the difference in molecular weight between before and after kneading, the molecular weight The correlation between the amount of decrease and the amount of water in the added titanium oxide pigment was examined. As a result, it was found that there is not necessarily a correlation between the two, and it is presumed that there is a factor for lowering the molecular weight other than hydrolysis, and it is considered that the molecular weight is lowered by the catalytic action of the titanium oxide pigment.

Moisture in the titanium oxide pigment can be one of the factors for decomposition of the polycarbonate resin. Furthermore, since it is known that the high-temperature and high-pressure steam that evaporates in the molding machine promotes the oxidation of organic substances such as polycarbonate resins, titanium oxide pigments having a low water content are preferable. The amount of water contained in the titanium oxide pigment (chemically bound water amount) is the water content measured by the Karl Fischer method at 0 ° C or higher and 120 ° C or lower from the water concentration measured by the Karl Fischer method at 0 ° C or higher and 300 ° C or lower. The value obtained by subtracting the concentration is preferably 8,000 mass ppm or less. When the difference in water concentration of the titanium oxide pigment is 8,000 mass ppm or less, it does not adversely affect the decrease in the molecular weight of the polycarbonate resin. The value is more preferably 6,000 mass ppm or less, further 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. Further, the surface of the inorganic oxide layer of the titanium oxide pigment has solid acid or solid base properties. This fact is as described on page 15 of "New Thai Pake News Vo.1 Titanium Oxide Colored Particle Basic Physical Properties" by Ishihara Sangyo Co., Ltd. The solid acid or solid base property has the same properties as the acid-base property in the solution, and this property is not preferable because hydrolysis of the polycarbonate resin is likely to be promoted both under acidic and basic conditions. This solid acid or solid base property is a property of the titanium oxide pigment only on the surface of the inorganic oxide layer. Therefore, by covering the inorganic oxide layer with the organic layer, it is possible to suppress the direct contact between the inorganic oxide layer and the polycarbonate resin and reduce the influence of the action of promoting hydrolysis due to acidity or basicity. 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 using a pyrolysis gas chromatograph device and a FID detector (Flame Ionization Detector). , Hereinafter also referred to as “EGA”), the maximum peak temperature of the generated gas analysis curve is preferably 380 ° C. or higher. When the maximum peak temperature of the organic layer is 380 ° C. or higher, the organic layer is difficult to decompose even when the polycarbonate resin composition is melt-kneaded or molded under high temperature conditions. Therefore, the solid acid or solid basic action on the surface of the inorganic oxide layer of the titanium oxide pigment can be effectively suppressed, so that black due to hydrolysis of the PC-POS copolymer during molding of the resin composition can be effectively suppressed. The occurrence of streaks can be suppressed. From the viewpoint of the effect of suppressing black streaks, the maximum peak temperature of the organic layer is more preferably 400 ° C. or higher, further preferably 410 ° C. or higher. The upper limit of the maximum peak temperature of the organic layer is not particularly limited, but considering the general decomposition temperature of the organic layer, it is preferably 500 ° C. or lower, more preferably 480 ° C. or lower, 450 ° C. It is more preferably ° C. or lower.
Specifically, the maximum peak temperature can be measured by the method described in Examples.

As the compound forming the organic layer, a silane compound such as a silane coupling agent is preferable. Examples of the silane coupling agent include vinyl-based silane coupling agents, epoxy-based silane coupling agents, methacrylic-based silane coupling agents, acrylic-based silane coupling agents, and amino-based silane coupling agents. These compounds may be used alone or in combination of two or more.

In addition, specific examples of the compound forming the organic layer include alkyl hydrogen silicone and alkoxy silicone. Examples of the alkyl hydrogen silicone include methyl hydrogen silicone and ethyl hydrogen silicone. Examples of the alkoxy silicone include methoxy silicone and ethoxy silicone. Preferred alkoxysilicone is specifically a silicone compound containing an alkoxysilyl group in which an alkoxy group is directly bonded to a silicon atom via a divalent hydrocarbon group, and for example, linear, cyclic, reticulated and partially branched. Examples thereof include linear organopolysiloxanes, and linear organopolysiloxanes are particularly preferable. More specifically, a polyorganosiloxane having a molecular structure that binds to an alkoxy group with respect to the silicone main chain via a methylene chain is preferable.

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

[Group B]

The above description of titanium oxide pigments is similarly applied to white pigments such as zinc sulfide pigments, zinc oxide pigments, and barium sulfate pigments.
The shape of the white pigment (C) is not particularly limited, and examples thereof include scale-like, spherical, plate-like, and amorphous shapes. 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 further preferably 0. from the viewpoint of making the color tone more excellent white. It is 15 μm or more and 0.25 μm or less. The average particle size of the white pigment (C) is determined from the average particle size of the primary particles of a single particle.

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 part by mass or more and 40 parts by mass or less, preferably 0.1 part by mass or more and 20 parts by mass or less, more preferably 1.0 part by mass or more and 10 parts by mass or less, still more preferably 1.0 part by mass or more and 5 parts by mass. It is 0.0 parts by mass or less. If the amount of 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.

<Metal inactivating agent (D)>
The polycarbonate-based resin composition of the present invention contains the metal inactivating agent (D). The metal inactivating agent (D) suppresses oxidative deterioration of the PC-POS copolymer (A1) due to the above-mentioned phenomenon and the catalytic action of a white pigment such as a titanium oxide pigment in the molding machine. As a result, the occurrence of black streaks on the surface of the molded product during molding can be significantly suppressed.

In the present invention, the metal inactivating agent is a substance having a function of inactivating a metal or a metal ion. For example, it forms a complex with a compound having a function of chemically inactivating the metal surface or adsorbing on the metal surface to suppress the catalytic action of the metal, or a metal ion which is an eluate from the metal. Examples thereof include compounds having a function of converting into an inert substance such as a chelate compound.

Examples of the metal inactivating agent (D) include hydrazine compounds, triazole compounds, triazine compounds, oxalic acid compounds, guanidine compounds, aminocarboxylate compounds, phosphonate compounds, inclusion compounds and the like. ..
Examples of the hydrazine-based compound include N, N'-diformylhydrazine, N, N'-diacetylhydrazine, N, N'-dipropionylhydrazine, N, N'-butyrylhydrazine, and N-formyl-N'-. Acetylhydrazine, N, N'-dibenzoyl hydrazine, N, N'-ditoluyl hydrazine, N, N'-disalicyloyl hydrazine, N-formyl-N'-salicyloyl hydrazine, N-formyl-N' -Butyl-substituted salicyloyl hydrazine, N-acetyl-N'-salicyloyl hydrazine, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, shu Examples thereof include acid-di- (N'-salicyloyl) hydrazine, adipate-di- (N'-salicyloyl) hydrazine, and decamethylene dicarboxylic acid disalicyloyl hydrazine. Among the above, a hydrazine compound having a salicyloyl group is preferable, and decamethylene dicarboxylic acid disalicyloyl hydrazide is more preferable.
Commercially available hydrazine compounds include "ADEKA STAB CDA-6" (decamethylene dicarboxylic acid disalicyloyl hydrazide) and "ADEKA STAB CDA-10" (N, N'-bis [3- (3) "manufactured by ADEKA Corporation. , 5-Di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine) and the like are exemplified.

Examples of the triazole-based compound include benzotriazole-based compounds and aminotriazole-based 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 , 4-Triazole, 3- (N-acetyl) amino-1,2,4-Triazole-5-carboxylic acid and the like. Among the above, aminotriazole-based compounds are preferable.
Examples of commercially available products of the triazole compound include "ADEKA STAB CDA-1" (3- (N-salicyloyl) amino-1,2,4-triazole) and "ADEKA STAB CDA-1M" manufactured by ADEKA Corporation. ..

Examples of the triazine-based compound 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 "ADEKA STAB ZS-27" (2,4,6-triamino-1,3,5-triazine) manufactured by ADEKA Corporation.

Examples of the oxalic acid compound include 2,2'-oxamidbis [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like. Examples of the guanidine compound 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), and DMPTDA (2,2). -Dimethylpropanediaminetetraacetic acid), DTPA (diethylenetriaminetetraacetic acid), and salts thereof.

Phosphonate compounds include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid (EDTMP), nitrilotrismethylenephosphonic acid (NTMP), and aminotri (2) having at least one phosphate group in the molecule. Methylenephosphonic acid), 1,2-ethanediphosphonic acid, tris (phosphonomethyl) amine-N-oxide, 1-hydroxypropane-1,1,3-triphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid), N, N- Bis (phosphonomethyl) butylamine, N, N-bis (phosphonomethyl) propylamine, 2-hydroxyethylbis (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 Phosphonates such as -N, N'-bis (acetic acid) -N, N'- (methylenephosphonic acid), and salts thereof can be mentioned.
Examples of the clathrate compound include porphyrins and crown ethers.

As the metal inactivating agent (D), one of the above-mentioned compounds can be used alone or in combination of two or more. Above all, from the viewpoint of suppressing appearance defects such as black streaks during molding of a polycarbonate resin composition containing a PC-POS copolymer and suppressing a decrease in molecular weight, hydrazine compounds, triazole compounds, and triazine compounds , And one or more selected from the group consisting of aminocarboxylate compounds are preferable, and one or more selected from the group consisting of hydrazine compounds, triazole compounds, and aminocarboxylate compounds are more preferable. One or more selected from the group consisting of aminocarboxylate compounds is further preferable, and one or more selected from the group consisting of decamethylene dicarboxylic acid disalicyloyl hydrazide and ethylenediaminetetraacetic acid are even more preferable.
In the present invention, the metal inactivating agent (D) is any that suppresses or deactivates the catalytic action associated with the white pigment (C) such as the titanium oxide pigment contained in the polycarbonate resin composition. , A metal inactivating agent other than the compounds exemplified above can also be used.

The content of the metal inactivating agent (D) 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). On the other hand, it is 0.005 part by mass or more and 1.0 part by mass or less, preferably 0.01 part by mass or more and 0.3 part by mass or less, and more preferably 0.02 part by mass or more and 0.2 part by mass or less. More preferably, it is 0.03 part by mass or more and 0.15 part by mass or less. When the content of the metal inactivating agent (D) 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 during molding of the resin composition is effective. If it is small and exceeds 1.0 part by mass, the physical properties will deteriorate.
When the content of the metal inactivating agent (D) is 0.05 parts by mass or more, black streaks generated in the molded product molded under a constant back pressure are more suppressed, which is preferable. Further, if it is 0.1 part by mass or more, black streaks generated in the molded product molded with a higher back pressure are further suppressed, which is more preferable.

<Other additives>
Other additives can be further added to the polycarbonate-based resin composition of the present invention as long as the effects of the present invention are not impaired. Examples of other components include hydrolyzants, antioxidants, ultraviolet absorbers, flame retardants, flame retardants, mold release agents, reinforcing materials, fillers, elastomers for improving impact resistance, dyes and the like. Can be done. Some components will be described in detail.

In the polycarbonate resin composition containing the white pigment (C), the water content in the white pigment (C) causes not a little hydrolysis of the PC-POS copolymer. In order to further suppress this, a hydrolysis resistant agent may be added to the polycarbonate resin composition of the present invention. By further blending a hydrolysis resistant agent, it is possible to further suppress the generation of black streaks during molding.

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 a producting acid. It is preferable that the agent has one or more functional groups capable of reacting with.
Specific examples of the hydrolysis resistant agent 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), and an oxazine compound ( Examples thereof include e6) and a keten compound (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 resistant agent and the dispersibility, the amide compound (e1) is preferably an amide compound having at least one chain aliphatic group having 6 to 24 carbon atoms in the molecule. The chain aliphatic group may be a straight chain or a branched chain, and may be a saturated aliphatic group or an unsaturated aliphatic group. A saturated chain aliphatic group is preferable, and an alkyl group is more preferable, from the viewpoint of suppressing the generation of black streaks during molding and having a dispersing action on the polycarbonate resin. The chain aliphatic group preferably has 8 to 22, more preferably 10 to 22, and even more preferably 12 to 22 carbon atoms. The chain aliphatic group may have a substituent such as a hydroxyl group.

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

In the above formula, R ¹¹ is a chain aliphatic group having 6 to 24 carbon atoms. R ¹² is a hydrogen atom or a chain aliphatic group having 6 to 24 carbon atoms. The preferred embodiment of the chain aliphatic group is the same as described above, and may have a substituent such as a hydroxyl group.

Examples of the compound represented by the general formula (e1-a) include fatty acid monoamide and monoamide (chain aliphatic group substitution) in which the amide hydrogen of the fatty acid monoamide is substituted with a chain aliphatic group having 6 to 24 carbon atoms. Type fatty acid monoamide). Among the above, fatty acid monoamide is preferable.
Specific examples of the fatty acid monoamide 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, bechenic acid amide, and montanic acid. Examples thereof include amides, undecylene acid amides, oleic acid amides, erucic acid amides, and linoleic acid amides.

Specific examples of the chain aliphatic group-substituted fatty acid monoamide include N-lauryl lauric acid amide, N-palmityl palmitate amide, N-stearyl stealic acid amide, N-behenyl behenic acid amide, and N-oleyl oleic acid amide. N-stearyl oleic acid amide, N-oleyl stealic acid amide, N-stearyl erucate amide, N-oleyl palmitate amide, methylose stearic acid amide, methylose behenic acid amide, N-stearyl-12-hydroxystearic acid amide, N -Oleyl-12-hydroxystearic acid amide and the like.

Among the amide compounds (e1), the compound having two amide groups in the molecule is preferably a compound represented by either the following general formula (e1-b) or (e1-c), and the general formula (e1). The compound represented by −b) is more preferable.

In the above formula, R ¹³ and R ¹⁴ are each independently a chain aliphatic group having 6 to 24 carbon atoms which may have a hydroxyl group. Z ¹ is a divalent group having 1 to 12 carbon atoms.
The preferred embodiment of the chain aliphatic group is the same as described above, and may have a substituent such as a hydroxyl group. R ¹³ and R ¹⁴ may be the same 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 even more 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 it is preferably a chain aliphatic group, and more preferably an alkylene group.

In the above formula, R ¹⁵ and R ¹⁶ are independently chain aliphatic groups having 6 to 24 carbon atoms. Z ² is a divalent group having 1 to 12 carbon atoms.
The preferred embodiment of the chain aliphatic group is the same as described above, and may have a substituent such as a hydroxyl group. R ¹⁵ and R ¹⁶ may be the same or different from each other, but are preferably the same.
A preferred embodiment of Z ² is the same as that of ^{Z 1.}

Specific examples of the compound represented by the general formula (e1-b) include fatty acid stearic acid amide, and examples thereof include methylene biscaprylic acid amide, methylene biscapric acid amide, methylene bislauric acid amide, methylene bismyristic acid amide, and the like. Methylenebis palmitate amide, methylene bisstearic acid amide, methylenebis isostearic acid amide, methylene bisbechenic acid amide, methylene bisoleic acid amide, methylene biserucate amide, ethylene biscaprylic acid amide, ethylene biscapric acid amide, ethylene bis Lauric acid amide, ethylene bismyristic acid amide, ethylene bispalmitic acid amide, ethylene bisstearic acid amide, ethylene bisisostearic acid amide, ethylene bisbechenic acid amide, ethylene bisoleic acid amide, ethylene bisercaic acid amide, butylene bisstearic acid Amido, butylene bisbechenic acid amide, butylene bisoleic acid amide, butylene bisercaic acid amide, hexamethylene bisstearic acid amide, hexamethylene bisbechenic acid amide, hexamethylene bisoleic acid amide, hexamethylene biserucate amide, m- Xylylenebis stearic acid amide, m-xylylenebis-12-hydroxystearic acid amide, p-xylylenebis stearic acid amide, p-phenylene bisstearic acid amide, methylenebishydroxystearic acid amide, ethylenebishydroxystearic acid amide, butylene Examples thereof include bishydroxystearic acid amide and hexamethylene bishydroxystearic acid amide.

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

Among the amide compounds (e1), the compound having three or more amide groups in the molecule includes a dicarboxylic acid, a diamine, and a monocarboxylic acid or a monoamine having a chain aliphatic group having 6 to 24 carbon atoms. A polycondensate is a preferred example. The preferred embodiment of the chain aliphatic group having 6 to 24 carbon atoms is the same as described above, and may have a substituent such as a hydroxyl group.

Among the amide compounds (e1), from the viewpoint 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). One or more amide compounds selected from the above group are more preferable, the compound represented by the general formula (e1-b) is further preferable, and ethylene bisstearic acid amide is further preferable. Among the amide compounds (e1), a compound having a melting point of 100 ° C. or higher, preferably 150 ° C. or higher is preferable because it has high suitability for the molding temperature of the polycarbonate resin composition.
Commercially available products of the amide compound (e1) include "Light Amide WH-255" (manufactured by Kyoeisha Chemical Co., Ltd., N, N'-ethylene bisstearoamide [ethylene bisstearic acid amide]) and "Amide AP-". 1 "(Nihon Kasei Co., Ltd., stearic acid amide)," Slipax E "(Nihon Kasei Co., Ltd., ethylene bisstearic acid amide)," Slipax H "(Nihon Kasei Co., Ltd., ethylene bishydroxystearic) Acid amide) and the like.

<Imide compound (e2)>
As the imide compound (e2) used in the present invention, a carbodiimide compound is preferable. The carbodiimide compound is a compound having at least one carbodiimide group in the molecule, and examples thereof include a monocarbodiimide compound having one carbodiimide group in the molecule and a polycarbodiimide compound having two or more carbodiimide groups in the molecule. A polycarbodiimide compound is preferable from the viewpoint of suppressing the generation of black streaks during molding of the resin composition.
Examples of the carbodiimide compound include an aliphatic carbodiimide compound, an aromatic carbodiimide compound, a cyclic carbodiimide compound, and a compound in which a part of the isocyanate compound is carbodiimided (hereinafter, also referred to as “carbodiimide-modified compound”).

Specific examples of the aliphatic monocarbodiimide compound include diisopropylcarbodiimide, dioctyldecylcarbodiimide, dicyclohexylcarbodiimide, N, N'-dioctyldecylcarbodiimide and the like.
Specific examples of the aliphatic polycarbodiimide include ethylenebis (dicyclohexylcarbodiimide), hexamethylenebis (dicyclohexylcarbodiimide), poly (diisopropylcarbodiimide), poly (1,6-hexamethylenecarbodiimide), and poly (4,4'-methylene). Biscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide) and the like.

Specific examples of aromatic monocarbodiimide compounds include di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2,5-dichlorophenylcarbodiimide, 2,6,2', 6'-tetraisopropyldiphenylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-o-toluyl carbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-toluyl-N'- Cyclohexylcarbodiimide, N, N'-bis (2,6-diisopropylphenyl) carbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-di-o-toluyl carbodiimide, N , N'-di-p-toluyl carbodiimide, N, N'-benzyl carbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-octadecil-N'-tolylcarbodiimide, N -Cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p -Ethylphenylcarbodiimide, N, N'-di-o-isopropylphenylcarbodiimide, N, N'-di-p-isopropylphenylcarbodiimide, 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'-di-2,4,6-triisopropylphenylcarbodiimide, N, N'-di-2, Examples thereof include 4,6-triisobutylphenylcarbodiimide.

Specific examples of the aromatic polycarbodiimide compound include p-phenylenebis (o-toluyl carbodiimide), p-phenylenebis (cyclohexylcarbodiimide), p-phenylenebis (p-chlorophenylcarbodiimide), ethylenebis (diphenylcarbodiimide), and poly. (4,4'-diphenylmethanecarbodiimide), poly (3,3'-dimethyl-4,4'-diphenylmethanecarbodiimide), poly (naphthylene carbodiimide), poly (p-phenylene carbodiimide), poly (m-phenylene carbodiimide) , Poly (trilcarbodiimide), poly (methyl-diisopropylphenylene carbodiimide), poly (triethylphenylene carbodiimide), poly (triisopropylphenylene carbodiimide) and the like.

The cyclic structure of the cyclic carbodiimide compound has one carbodiimide group (-N = C = N-), and its primary nitrogen and secondary nitrogen are bonded by a bonding group. One cyclic structure has only one carbodiimide group. The number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and even more preferably 10 to 20. Here, the number of atoms in the cyclic structure means the number of atoms that directly constitute the ring structure, for example, 8 for an 8-membered ring and 50 for a 50-membered ring.

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

In the formula, Q is a 2- to tetravalent organic group.

Examples of the isocyanate compound used for the compound in which a part of the isocyanate compound is carbodiimided (carbodiimide-modified compound) include tolylene diisocyanate, phenylenedi isocyanate, 4,4'-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, and dimethyl biphenylenedi isocyanate. Dimethoxybiphenylenediocyanate, naphthalenediocyanate, tetrahydronaphthalenediocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexylene diisocyanate, xylylene diisocyanate, hydride xylylene diisocyanate, tetramethylxylylene diisocyanate, lysine diisocyanate , Isophorone diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate and the like, and one kind or a combination of two or more kinds is used. Among the above isocyanate compounds, an isocyanate compound containing 4,4'-diphenylmethane diisocyanate as a main component is preferable.
A known method can be used as a method for carbodiimidizing a part of the isocyanate compound.

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

The imide compound (e2) may be used alone or in combination of two or more. Among the above, an aliphatic carbodiimide is preferable, and an aliphatic polycarbodiimide is more preferable from the viewpoint of the effect as a hydrolysis resistant agent.

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

Examples of the glycidyl ether compound include 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, and polyethylene glycol diglycidyl. Ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol With bisphenols such as polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone and epichlorohydrin Examples thereof include bisphenol A diglycidyl ether type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, and bisphenol S diglycidyl ether type epoxy resin obtained from the condensation reaction of bisphenol A.

Examples of the glycidyl ester compound include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearate glycidyl ester, laurate glycidyl ester, palmitate glycidyl ester, versatic acid glycidyl ester, and oleate glycidyl ester. Linol acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalenedicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methylterephthalic acid diglycidyl ester, hexa Hydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipate diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecandioic acid diglycidyl ester, octadecanedicarboxylic acid di Examples thereof include glycidyl ester, trimellitic acid triglycidyl ester, and pyromellitic acid tetraglycidyl ester.

Examples of the glycidyl amine compound include tetraglycidyl aminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidyl aniline, diglycidyl toluidine, N, N, N', N'-tetraglycidyl metaxylylene. Examples thereof include amines, diglycidyl tribromoaniline, tetraglycidyl bisaminomethylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

Examples of the glycidylimide compound include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, and N-glycidyl-3,6-dimethylphthalimide. , 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 maleinimide, N-glycidyl-α, Examples thereof include β-dimethylsuccinimide, N-glycidyl-α-ethylsuccinimide, and N-glycidyl-α-propylsuccinimide.

As the cyclic epoxy compound, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexenediepoxide, N-methyl-4,5- Epoxidecyclohexane-1,2-dicarboxylic acid imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic acid imide, N Examples thereof include −naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic acidimide, and N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic acidimide. Of these, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate is preferable.

Examples of the epoxidized oil include epoxidized natural oil and epoxidized synthetic oil. Specific examples of the epoxidized natural oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized rapeseed oil, and epoxidized whale oil. Specific examples of the epoxidized synthetic oil include diepoxystearyl epoxyhexahydrophthalate and butyl epoxidized fatty acid. Among these, epoxidized soybean oil and epoxidized linseed oil have a high affinity with polycarbonate-based resins and are likely to exhibit a hydrolysis-resistant effect.

The epoxy compound (e3) may be used alone or in combination of two or more. Among the above, as the epoxy compound (e3), a cyclic epoxy compound or one or more epoxidized oils selected from the group consisting of epoxidized natural oils and epoxidized synthetic oils are preferable.

<Acid anhydride (e4)>
The acid anhydride (e4) used in the present invention 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. Further, a polymer containing the above-mentioned compound as a monomer unit can also be mentioned.

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

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

<Ketene compound (e7)>
The ketene compound (e7) used in the present invention includes ketene represented by the following formula;

And the diketene represented by the following formula;

Examples thereof include aldoketen in which the β-carbon substituent of ketene is mono-substituted, and keto-keten in which the β-carbon substituent is substituted.

The above-mentioned hydrolysis resistant agent may be used alone or in combination of two or more. Above all, from the viewpoint of suppressing the generation of black streaks during molding of the resin composition due to the hydrolysis of the PC-POS copolymer, the hydrolysis resistant agents are the amide compound (e1), the imide compound (e2) and the 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 one or more epoxy compounds (e3) selected from the group consisting of cyclic epoxy compounds.

When the hydrolysis resistant agent is blended with the polycarbonate resin composition of the present invention, the blending amount is preferably 0.02 parts by mass or more and 5.0 parts by mass with respect to 100 parts by mass of the polycarbonate resin composition (S). It is more preferably 0.05 part by mass or more and 1.0 part by mass or less, and further preferably 0.1 part by mass or more and 0.5 part by mass or less. When the blending 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 during molding of the resin composition due to hydrolysis of the PC-POS copolymer The generation of streaks can be suppressed more effectively. Further, when the amount is 5.0 parts by mass or less, gas is generated during molding of the resin composition, and problems such as mold adhesion do not occur, which is preferable in terms of economy.
When the blending amount of the hydrolysis resistant agent is 0.05 parts by mass or more, black streaks generated inside the molded body molded under a constant back pressure are more suppressed, which is preferable, and further 0.1 parts by mass. The above is more preferable because the black streaks generated inside the molded body formed with a higher back pressure are further suppressed.

<Antioxidant>
The polycarbonate-based resin composition of the present invention preferably further contains an antioxidant. By adding an antioxidant to the polycarbonate-based resin composition, it is possible to suppress oxidative deterioration of the polycarbonate-based resin composition at the time of melting, and it is possible to suppress coloring and the like due to oxidative deterioration. As the antioxidant, a phosphorus-based antioxidant and / or a phenol-based antioxidant and the like are preferably used, and a phosphorus-based antioxidant is more preferable.

Examples of phosphorus-based antioxidants include triphenylphosphine, diphenylnonylphosphine, diphenyl (2-ethylhexyl) phosphine, tris (2,4-di-t-butylphenyl) phosphine, and tris (nonylphenyl). Phosphite, diphenylisooctylphosphine, 2,2'-methylenebis (4,6-di-t-butylphenyl) octylphosphine, diphenylisodecylphosphine, diphenylmono (tridecyl) phosphine, phenyldiisodecylphosphine, Phenoldi (tridecyl) phosphine, tris (2-ethylhexyl) phosphine, tris (isodecyl) phosphine, tris (tridecyl) phosphine, dibutylhydrogenphosphine, trilauryltrithiophosphine, tetrakis (2,4-di-) t-Butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropyridene diphenol dodecylphosphine, 4,4'-isopropyridene diphenol tridecylphosphine, 4,4'-isopropyri Dendiphenol tetradecylphosphine, 4,4'-isopropyridene diphenol pentadecylphosphine, 4,4'-butylidenebis (3-methyl-6-t-butylphenyl) ditridecylphosphine, bis (2,4- Di-t-butylphenyl) pentaerythritol diphosphine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphine, bis (nonylphenyl) pentaerythritol diphosphine, distearyl- Pentaerythritol diphosphine, phenylbisphenol A pentaerythritol diphosphine, tetraphenyldipropylene glycol diphosphine, 1,1,3-tris (2-methyl-4-di-tridecylphosphine-5-t-butyl) Phenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphine, triphenylphosphine, diphenylbutylphosphine, diphenyloctadecylphosphine, 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-full) Examples thereof include orophenyl) phosphine, benzyldiphenylphosphine, diphenyl (β-cyanoethyl) phosphine, diphenyl (p-hydroxyphenyl) phosphine, diphenyl (1,4-dihydroxyphenyl) -2-phosphine, and phenylnaphthylbenzylphosphine.

Further, as phosphorus-based antioxidants, for example, Irgafos168 (manufactured by BASF Japan Co., Ltd., trademark), Irgafos12 (manufactured by BASF Japan Co., Ltd., trademark), Irgafos38 (manufactured by BASF Japan Co., Ltd., trademark), Adecastab 2112 ( ADEKA Co., Ltd. (Trademark), Adecastab C (ADEKA Co., Ltd., trademark), Adecastab 329K (ADEKA Co., Ltd., trademark), Adecastab PEP36 (ADEKA Co., Ltd., trademark), JC263 (Johoku Chemical Industry Co., Ltd.) (Trademark), Sandstab P-EPQ (Clariant, trademark), Weston618 (GE, trademark), Weston619G (GE, trademark) and Weston 624 (GE, trademark), Doverphos S. Commercial products such as −9228PC (manufactured by Dover Chemical, trademark) can be mentioned.

Examples of the phenolic antioxidant include n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4-methylphenol, and 2, , 2'-Methylenebis (4-methyl-6-t-butylphenol), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and other hindered phenols Can be mentioned.
Among these antioxidants, bis (2,6-di-tert-butyl4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and the like Those having a pentaerythritol diphosphite structure and triphenylphosphine are preferable.

Examples of the phenolic antioxidant include Irganox1010 (manufactured by BASF Japan Ltd., trademark), Irganox1076 (manufactured by BASF Japan Ltd., trademark), Irganox1330 (manufactured by BASF Japan Ltd., trademark), Irganox3114 (BASF Japan Ltd.). (Trademark), Irganox3125 (BASF Japan Ltd., trademark), BHT (Takeda Yakuhin Kogyo Co., Ltd., trademark), Cyanox1790 (Cyanamide, trademark) and Sumitomo Chemical Co., Ltd. Manufactured, trademark) and other commercially available products can be mentioned.

The above-mentioned antioxidant may be used alone or in combination of two or more.
The amount of the antioxidant in the polycarbonate resin composition of the present invention is preferably 0.001 part by mass or more and 0.5 part by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S). Is 0.01 part by mass or more and 0.3 part by mass or less, more preferably 0.05 part by mass or more and 0.3 part by mass or less. When the amount of the antioxidant with respect to 100 parts by mass of the polycarbonate resin composition (S) is within the above range, a sufficient antioxidant effect can be obtained and mold contamination during molding can be suppressed.

The polycarbonate-based resin composition of the present invention can be obtained by blending each of the above components in the above proportions and further adding various optional components used as necessary in an appropriate proportion and kneading.
Formulation and kneading are performed by premixing with commonly used equipment such as ribbon blenders, drum tumblers, etc., and then Henschel mixers, Banbury mixers, single-screw screw extruders, twin-screw screw extruders, multi-screw screw extruders and This can be done by a method using a conider or the like. The heating temperature at the time of kneading is usually appropriately selected in the range of 240 ° C. or higher and 320 ° C. or lower. As this melt-kneading molding, it is preferable to use an extrusion molding machine, particularly a vent type extrusion molding machine.

The polycarbonate-based resin composition of the present invention containing a white pigment can provide a white molded product in which the occurrence of appearance defects such as black streaks during molding is suppressed. The black streaks are more visually recognized as the average value of the difference "ΔL value" of the brightness L values when the molded product is color-measured under the following conditions is larger. The color measurement 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 portion along the resin flow direction from the gate position of the injection molding machine at the time of molding is the vertical axis, and the end portion orthogonal to the vertical axis. Is used as the horizontal axis, and 15 × 15 positioning is performed at intervals of 1 cm (vertical) × 1 cm (horizontal) in order from the point where the vertical axis and the horizontal axis are orthogonal to each other.
<Measurement conditions>
A D65 light source is used as a light source, and measurement is performed at a viewing angle of 10 °.
<Measurement point>
The position of 3 horizontal × 8 vertical after the position allocation is set as the reference point, and the position from 8 horizontal × 3 vertical to 8 × 14 vertical is the measurement target position.
<ΔL value>
The difference between the L value of the measurement target position and the L value of the reference point is defined as the ΔL value, and the ΔL value is preferably 0.18 or less. The ΔL value is more preferably 0.17 or less, still more preferably 0.15 or less.
When the ΔL value of the molded product made of the polycarbonate resin composition is within the above range, it is possible to obtain a molded product having an excellent appearance in which the generation of black streaks is suppressed. An image of black streaks that can be formed on the molded product is shown in FIG. In the present application, this black streak can be suppressed.

The viscosity average molecular weight (Mv) of the polycarbonate-based resin composition of the present invention can be appropriately adjusted so as to have the desired molecular weight depending on the intended use and product, preferably 12,000 or more and 50,000 or less. It is preferably 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 product can be obtained. When the viscosity average molecular weight is 50,000 or less, the fluidity is not too low and the moldability is good, and injection molding or extrusion molding can be performed at a temperature that does not cause thermal deterioration.
The viscosity average molecular weight (Mv) can be determined by the method described above.

[Molding]
The molded product of the present invention contains the above-mentioned polycarbonate-based resin composition of the present invention. The molded product is an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum molding method and a foam molding method using the above melt-kneading molding machine or the obtained pellets as a raw material. It can be manufactured by such means. In particular, it is preferable to use the obtained pellets to produce a molded product by an injection molding method or an injection compression molding method.

In the production of molded products containing a polycarbonate-based resin composition, the residence time of the polycarbonate-based resin composition in the molding machine is shortened from the viewpoint of suppressing the mixing of water in the manufacturing process and suppressing the generation of black streaks during molding. It is preferable to manufacture under such conditions. A preferred embodiment of a method for producing a molded product by an injection molding method or an injection compression molding method is as follows, for example.

In the production of a molded product by an injection molding method or an injection compression molding method, it is preferable that pellets made of a polycarbonate resin composition are melt-plasticized 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, suppressing compression of the resin composition, and suppressing black streaks. The back pressure can be appropriately selected according to the equipment used, etc. For example, when molding with an electric injection molding machine capable of direct pressure control of the cylinder pressure, the range is about 2 to 10 MPa (the hydraulic type is a hydraulic cylinder type). This is not the case because it is adjusted by. From the same viewpoint, it is desirable to carry out the screw rotation speed at 100 rpm so that the shear rate becomes small.

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

In the molded product of the present invention, as described above, the average value of the difference "ΔL value" of the brightness L values when the molded product is measured is preferably 0.18 or less, more preferably 0.17 or less, and further. Since it is preferably as small as 0.15 or less, it is a white molded product having an excellent appearance in which the generation of black streaks is suppressed.

The molded product of the present invention includes electricity for televisions, radio cassettes, video cameras, video tape recorders, audio players, DVD players, air conditioners, mobile phones, displays, computers, registers, calculators, copiers, printers, facsimiles, etc. It can be suitably used for parts for electronic devices, housings for the devices, interior / exterior parts for lighting equipment, interior / exterior parts for vehicles, food trays and tableware. In particular, it is suitable as a material for housings of mobile phones, mobile personal computers, digital cameras, video cameras, power tools and the like.

Examples of the present invention will be further described. The present invention is not limited to these examples. The measurement and evaluation in each example were carried out by the methods shown below.

<Measurement of chlorohomet group concentration>
Measurement was performed using oxidation / reduction titration and silver nitrate titration with reference to JIS-K8203: 1994 based on the chlorine ion concentration.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was detected by using tetrahydrofuran as a developing solvent, GPC [column: TOSOH TSK-GEL MULTIPOLE HXL-M (2) + Shodex KF801 (1), temperature 40 ° C., flow velocity 1.0 mL / min. Instrument: RI] measured as a standard polystyrene-equivalent molecular weight (weight average molecular weight: Mw).

<Average chain length and content of polydimethylsiloxane>
It was calculated from the integral value ratio of the methyl group of polydimethylsiloxane by NMR measurement.
1. 1. Method for quantifying the average chain length of polydimethylsiloxane
^{1 1} H-NMR measurement conditions NMR equipment: ECA500 manufactured by JEOL RESONANCE Co., Ltd.
Probe: 50TH5AT / FG2
Observation range: -5 to 15 ppm
Observation center: 5ppm
Pulse repetition time: 9 seconds Pulse width: 45 °
NMR sample tube: 5φ
Sample amount: 30-40 mg
Solvent: Heavy chloroform Measurement temperature: Room temperature Cumulative number: 256 times In the case of allylphenol-terminated polydimethylsiloxane A: Integrated value of the methyl group of the dimethylsiloxane part observed near δ-0.02-0.5 B: δ2. Integrated value of methyl 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 the methyl group of the dimethylsiloxane part observed in the vicinity of δ-0.02-0.5 B: Methylene group of eugenol observed in the vicinity of δ2.40 to 2.70 Integral value of polydimethylsiloxane chain length = (A / 6) / (B / 4)

2. 2. Quantification method of polydimethylsiloxane content in PC-PDMS copolymer Example) Quantification method of polydimethylsiloxane copolymerization amount in PTBP-terminal polycarbonate copolymerized with allylphenol-terminal polydimethylsiloxane NMR device: JEOL RESONANCE Co., Ltd. Made by ECA-500
Probe: TH5 5φ NMR sample tube compatible Observation range: -5 to 15 ppm
Observation center: 5ppm
Pulse repetition time: 9 seconds Pulse width: 45 °
Number of integrations: 256 times NMR sample tube: 5φ
Sample amount: 30-40 mg
Solvent: Heavy chloroform Measurement temperature: Room temperature A: Integrated value of methyl group of BPA part observed around δ1.5 to 1.9 B: Of dimethylsiloxane part observed around δ-0.02 to 0.3 Methyl group integrated value C: Integrated value of butyl group in p-tert-butylphenyl portion observed near δ1.2 to 1.4 a = A / 6
b = B / 6
c = C / 9
T = a + b + c
f = a / T × 100
g = b / T × 100
h = c / T × 100
TW = f × 254 + g × 74.1 + h × 149
PDMS (wt%) = g x 74.1 / TW x 100

<Measurement of viscosity average molecular weight (Mv)>
For the viscosity average molecular weight (Mv), the viscosity of the methylene chloride solution (concentration: g / L) at 20 ° C. was measured using an Ubbelohde viscometer, and the ultimate viscosity [η] was obtained from this, and the following formula (Schnell formula) was obtained. ).

Synthesis Example 1: Synthesis of polycarbonate oligomer To a 5.6% by mass sodium hydroxide aqueous solution, 2000 mass ppm of sodium dithionate is added to bisphenol A to be dissolved later, and the concentration of bisphenol A is 13.5 mass. Bisphenol A was dissolved so as to be%, and an aqueous sodium hydroxide solution of bisphenol A was prepared.
Phosgene was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m at a flow rate of 4.0 kg / hr at a flow rate of 40 L / hr of an aqueous sodium hydroxide solution of bisphenol A and 15 L / hr of methylene chloride. The tubular reactor has a jacket portion, and cooling water is passed through the jacket to keep the temperature of the reaction solution at 40 ° C. or lower.
The reaction solution leaving the tubular reactor was continuously introduced into a tank reactor with a baffle having an internal volume of 40 L equipped with swept blades, and further, an aqueous sodium hydroxide solution of bisphenol A 2.8 L / hr, 25. The reaction was carried out by adding 0.07 L / hr of a mass% sodium hydroxide aqueous solution, 17 L / hr of water, and 0.64 L / hr of a 1 mass% triethylamine aqueous solution. The reaction solution overflowing from the tank reactor was continuously withdrawn and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected.
The polycarbonate oligomer thus obtained had a concentration of 318 g / L and a chlorohomete group concentration of 0.75 mol / L. The weight average molecular weight (Mw) was 1190.

<Production Examples 1 to 4 of Polycarbonate-Polyorganosiloxane Copolymer (A)>
The values (i) to (xiv) described below indicate the amounts used by each component, and are as shown in Table 1.
Polycarbonate oligomer solution (PCO) (i) L, methylene chloride (MC) (ii) L prepared as described above in a 50 L tank reactor equipped with a baffle plate, paddle type stirring blade and cooling jacket, and average chain length. N = (iii) allylphenol-terminated polydimethylsiloxane (hereinafter, polydimethylsiloxane may be referred to as PDMS) (iv) g dissolved in methylene chloride (MC) (v) L, and triethylamine ( TEA) (vi) mL was charged, 8.0% by mass of sodium hydroxide aqueous solution (NaOHaq) (vi) g was added thereto under stirring, and the reaction of the polycarbonate oligomer and the allylphenol terminal-modified PDMS was carried out for 20 minutes (). Prepolymerization step).
In this polymer solution, a methylene chloride solution of pt-butylphenol (PTBP) (PTBP (viii) g dissolved in methylene chloride (MC) (ix) L) and an aqueous sodium hydroxide solution of BPA (NaOH (x)) BPA (xiii) g was dissolved in an aqueous solution prepared by dissolving g and sodium dithioate (Na ₂ S ₂ O ₄ ) (xi) g in water (xii) L), and the polymerization reaction was carried out for 40 minutes. It was carried out (this polymerization step).
Methylene chloride (MC) (xiv) L was added for dilution and stirred for 10 minutes, then 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 was washed successively with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid, and then the electricity in the aqueous phase after washing. 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 pulverized, and the obtained flakes were dried under reduced pressure at 100 ° C. Table 1 shows the results of measuring the PDMS concentration and viscosity average molecular weight of the obtained flakes.

Measurement of Moisture Concentration in White Pigment (C) The white pigment powder of the sample was left at a constant temperature and constant humidity of 25 ° C. and a relative humidity of 55% for 24 hours to bring it into an equilibrium state, and then 0.3 g of the sample was subjected to curl fisher moisture. Using the measuring device "Coulometric Moisture Analyzer CA100" and the attached moisture vaporizer "VA-100" (both manufactured by Dia Instruments Co., Ltd.), moisture at a nitrogen flow rate of about 250 mL and a temperature of 0 to 300 ° C. After measuring the concentration, the value obtained by subtracting the water concentration detected and integrated 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 chromatograph <Device used>
Pyrolysis device: "PY-3030D" manufactured by Frontier Lab
Gas chromatograph (GC) device: Agilent 7890BGC system column: Frontier Lab "UADTM-2.5N" (length 2.5 m x inner diameter 0.15 mm)
<Pyrolysis furnace heating conditions>
100 ° C (0 min) → temperature rise 20 ° C / min → 800 ° C
<GC conditions>
Carrier gas (He) flow velocity: 1 mL / min
Split ratio: 10: 1
Injection port 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 measured in a sample cup and attached to a thermal decomposition device. Next, the sample cup was dropped into the pyrolysis furnace, the temperature of the pyrolysis furnace was immediately started, and the GC measurement was started at the same time. The temperature at the peak top of the obtained EGA curve was defined as the maximum peak temperature.

GC-MS analysis of organic layer <Device used>
Measuring device: Gesuteru small heating and desorption device TDU and multifunctional autosampler MPS, Agilent GC / MS device "6890/5975MSD"
Column: Agilent "DB-5MS" (30 mm x 0.25 mm x 0.25 μm)
<TDU section conditions>
TDU section: 50 ° C (0.01 min) → 720 ° C / min → 300 ° C (20 min) Splitless CIS section: -50 ° C (0.01 min) → 12 ° C / sec → 350 ° C (5 min), split 30: 1
<GC-MS conditions>
Carrier gas (He) flow velocity: 1 mL / min
Oven: 50 ° C (5 min) → 10 ° C / min → 330 ° C (10 min)
Scan range m / z = 35-800
<Analysis procedure>
A sample (titanium oxide pigment) of 10 mg was measured in a special container and attached to a TDU / GC-MS apparatus. Next, GC-MS measurement was performed under the above conditions, and the obtained generated gas component was identified using a mass library of NIST (National Institute of Standards and Technology).

In the description of the organic layer of the white pigment (C) below, the component detected by the GC-MS analysis of the organic layer was the following group A as the "organic layer A" and the following group B. Is referred to as "organic layer B".
[Group A]

[Group B]

Examples 1 to 13, Comparative Examples 1 to 4
The components shown in Tables 1 and 2 are blended in the listed blending amounts and supplied to a vent type twin-screw extruder (“TEM35B” manufactured by Toshiba Machine Co., Ltd.), the screw rotation speed is 150 rpm, and the discharge rate is 20 kg / hr. , The barrel was melt-kneaded at a set temperature of 280 ° C. (actually extruded 295 to 300 ° C.) to obtain pellets.

(1) Observation of poor appearance (black streaks) of molded product After pre-drying the pellet at 120 ° C. for 8 hours in a dryer, injection molding machine (“MD350Wi15 HP-AP” manufactured by Niigata Machine Techno Co., Ltd.) Was used to perform injection molding for 20 shots under the following conditions. The appearance of the obtained molded product was visually observed and evaluated according to the following criteria.
Specifically, the pellets were supplied from the hopper into the cylinder, the rotation speed of the screw for plasticizing and kneading was set to 100 rpm, the screw back pressure was set to 40 MPa, and injection molding was performed under the following conditions. If the screw back pressure is increased, poor appearance on the black streaks is likely to occur. The appearance of the black streaks was evaluated on the obtained molded product. In the table, the "AA" evaluation indicates that the black streak-like pattern is less likely to occur and the evaluation result is good.
AA: No black streak pattern is observed on the surface of the molded product.
A: A very slight black streak pattern is observed on the surface of the molded product.
B: A black streak-like pattern is observed on the surface of the molded product at an intermediate level between A above and C below.
C: A black streak pattern is clearly observed on the surface of the molded product.

(2) Observation of black streaks (transmission) The above-mentioned molded product is provided with a frame opened in the same size as the molded product on a wooden board sufficiently larger than the molded product size, and the molded product is fitted into the frame, and 110 V × from one of them. A light source from a 1.5 kW lamp was applied, and the molded product was observed from the opposite side and evaluated according to the following criteria.
AA: No black streaks are observed.
A: A slight black streak pattern is observed.
B: A black streak pattern is observed between A above and C below.
C: A black streak pattern is clearly observed.

(3) Color measurement of black streaks on the surface of the molded product As shown in FIG. 1, the resin from the gate position of the injection molding machine at the time of molding is placed on the molded product of 150 mm × 150 mm molded under the same conditions as in (1). With the vertical axis at the end along the flow direction and the horizontal axis at the end perpendicular to the vertical axis, the intervals of 1 cm (vertical) x 1 cm (horizontal) are 15 in order from the point where the vertical axis and the horizontal axis are orthogonal to each other. Positioning of × 15 is performed.
The position of 3 horizontal × 8 vertical is the reference point, the position from 8 × 3 vertical to 8 × 14 vertical is the measurement target position, and the L value of the reference point and the measurement target position is the spectrophotometer (spectrophotometer). Measured with a spectrocolorimeter CM-600d, SCE (specular reflection light removal) mode, observation light source D65, observation field of view 10 °, diameter 5 mmφ) manufactured by Konica Minolta Co., Ltd.
The difference (ΔL) between the L value at the measurement symmetric position and the L value at the reference point is calculated, and the average value of the ΔL values at the measurement symmetric position is obtained. The larger the average value of the ΔL values, the stronger the black streaks on the surface as shown in FIG. 2 appear.

<Injection molding conditions>
Mold: 150 mmW x 150 mmH x 2 mmt flat plate mold mold temperature: 80 ° C
Cylinder temperature setting: The temperatures shown in Tables 2-1, 2-2 and Table 3 were set for each Example and Comparative Example.
Injection speed: Two-step setting is set, and the resin is filled with the speed from the weighing 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, 50 MPa was applied for 3 seconds.

The ingredients used in the table are as follows.
(A2) Aromatic polycarbonate resin: "FN1700" manufactured by Idemitsu Kosan Co., Ltd. (Mv = 17,700)
(B1) Styrene-based resin: "Clarastic SXH-330 (acrylonitrile-butadiene-styrene ternary copolymer (ABS))" manufactured by Nippon A & L Inc., content of structural units derived from butadiene; 12% by mass
(C-1) Titanium oxide pigment: "CR-63" manufactured by Ishihara Sangyo Co., Ltd. (Crystal structure: rutile type, surface-treated titanium dioxide 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, surface-treated titanium dioxide with only 8% silica-alumina, average particle size: 0.21 μm, Chemical bond water volume: 5,100 mass ppm)
(C-3) Titanium oxide pigment: "R-TC30" manufactured by HUNTSMAN (crystal structure: rutile type, surface-treated titanium dioxide with siloxane, average particle size: 0.21 μm)

(D-1) Metal Inactivating Agent: "ADEKA STAB CDA-6" manufactured by ADEKA Corporation (decamethylene dicarboxylic acid disalicyloyl hydrazide)
(D-2) Metal inactivating agent: "ADEKA STAB CDA-1" manufactured by ADEKA Corporation (3- (N-salicyloyl) amino-1,2,4-triazole)
(D-3) Metal inactivating agent: "ADEKA STAB ZS-27" manufactured by ADEKA Corporation (main component: 2,4,6-triamino-1,3,5-triazine)
(D-4) Metal inactivating agent: "ADEKA STAB ZS-90" manufactured by ADEKA Corporation
Antioxidant: "IRGAFOS168" manufactured by BASF Japan (Tris (2,4-di-t-butylphenyl) phosphite)

The polycarbonate-based resin composition of the present invention provides a white molded product having a good molded appearance, in which the occurrence of appearance defects such as black streaks during molding is suppressed even in the resin composition containing a white pigment. Can be done. The molded product can be suitably used for electrical and electronic equipment parts or housings for the equipment, lighting equipment interior / exterior parts, vehicle interior / exterior parts, food trays and tableware. In particular, it is suitable as a material for housings of mobile phones, mobile personal computers, digital cameras, video cameras, power tools and the like.

Claims (17)

Contains a polycarbonate-polyorganosiloxane copolymer (A1) containing a polycarbonate block composed of a repeating unit represented by the following general formula (I) and a polyorganosiloxane block containing a repeating unit represented by the following general formula (II). A polycarbonate resin composition (S) containing 50% by mass or more and 99% by mass or less of the polycarbonate resin (A) and 1% by mass or more and 50% by mass or less of the styrene resin (B), and a white pigment (C). , With a metal inactivating agent (D)
The white pigment (C) is contained in an amount of 0.1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S).
A polycarbonate resin composition containing the metal inactivating agent (D) in an amount of 0.005 part by mass or more and 1.0 part by mass or less with respect to 100 parts by mass of the polycarbonate resin composition (S).

[In the formula, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorinatedyl group, and carbon. It shows an arylalkylene group having 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15 carbon atoms, -S-, -SO-, -SO _2- , -O- or -CO-. R ³ and R ⁴ 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-based resin composition according to claim 1 or 2, wherein the polyorganosiloxane block has an average chain length of 50 or more. The polycarbonate-based resin composition according to any one of claims 1 to 3, wherein the content of the polyorganosiloxane in the polycarbonate-based 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 polycarbonate resin (A) has a viscosity average molecular weight of 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. System resin composition. Any one of claims 1 to 6, wherein the metal inactivating agent (D) is at least one selected from the group consisting of hydrazine-based compounds, triazole-based compounds, triazine-based compounds, and aminocarboxylate-based compounds. The polycarbonate-based resin composition according to. The polycarbonate-based pigment according to any one of claims 1 to 7, 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-based resin composition according to claim 8, wherein the white pigment (C) is a titanium oxide pigment. The polycarbonate-based pigment according to claim 9, 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 the titanium oxide particles. Resin composition. The polycarbonate-based resin composition according to claim 10, wherein the titanium oxide pigment further has an organic layer on the surface of the inorganic oxide layer. The polycarbonate-based resin composition according to claim 11, wherein the maximum peak temperature of the generated gas analysis curve obtained by the generated gas analysis of the organic layer using a pyrolysis gas chromatograph device and a FID detector is 380 ° C. or higher. The value obtained by subtracting the water concentration of the white pigment (C) measured by the Karl Fischer method at 0 ° C. or higher and 300 ° C. or lower from the water concentration measured by the Karl Fischer method at 0 ° C. or higher and 120 ° C. or lower is 8,000. The polycarbonate-based resin composition according to any one of claims 1 to 12, which has a mass of ppm or less. The polycarbonate-based resin composition according to any one of claims 1 to 13, wherein the viscosity average molecular weight is 12,000 or more and 50,000 or less. Claimed that 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 for the molded product made of the polycarbonate resin composition is 0.18 or less. Item 2. The polycarbonate resin composition according to any one of Items 1 to 14.
Light source: D65 light source Viewing angle: 10 °
Measuring method: On a molded product of length 150 mm × width 150 mm, the vertical axis is the end along the resin flow direction from the gate position of the injection molding machine at the time of molding, and the horizontal axis is the end orthogonal to the vertical axis. , 15 × 15 positioning is performed at intervals of 1 cm (vertical) × 1 cm (horizontal) in order from the point where the vertical axis and the horizontal axis are orthogonal to each other. The L value of the following reference point after the position division and the measurement symmetric position is measured.
Reference point: Position of horizontal 3 x vertical 8 Measurement symmetric position: Position from horizontal 8 x vertical 3 to horizontal 8 x vertical 14 A molded product comprising the polycarbonate-based resin composition according to any one of claims 1 to 15. The molded product according to claim 16, 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 °
Measuring method: On a molded product of length 150 mm × width 150 mm, the vertical axis is the end along the resin flow direction from the gate position of the injection molding machine at the time of molding, and the horizontal axis is the end orthogonal to the vertical axis. , 15 × 15 positioning is performed at intervals of 1 cm (vertical) × 1 cm (horizontal) in order from the point where the vertical axis and the horizontal axis are orthogonal to each other. The L value of the following reference point after the position division and the measurement symmetric position is measured.
Reference point: Position of horizontal 3 x vertical 8 Measurement symmetric position: Position from horizontal 8 x vertical 3 to horizontal 8 x vertical 14