JP2016028168A - Polycarbonate-based resin composition and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate-based resin composition capable of obtaining a molded body excellent in transparency, weather resistance and impact resistance.SOLUTION: There is provided a polycarbonate-based resin composition obtained by blending (B) an additive with (A) a polycarbonate-based resin composed of 10 to 100 mass% of a specific polycarbonate-polyorganosiloxane copolymer (A-1) and 0 to 90 mass% of a polycarbonate (A-2) other than (A-1), wherein the (B) component contains an ultraviolet absorbent and the amount of sodium contained in the polycarbonate-based resin composition is 0.5 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a polycarbonate resin composition and a molded body formed by molding the same.

  Polycarbonate resins are used in a wide range of applications because they have excellent properties such as transparency, high impact properties, and flame retardancy. However, when it is used in applications that are exposed to ultraviolet rays such as outdoors, there is a problem of yellowing by ultraviolet rays. Various techniques for suppressing yellowing by blending an ultraviolet absorber have been developed.

On the other hand, in recent years, polycarbonate-polydimethylsiloxane copolymer (PC-PDMS copolymer) can be used as a suitable polycarbonate resin material for demands for high-temperature impact characteristics, excellent flame retardancy and transparency. There is). However, it is difficult to meet the high demands of the market only with the PC-PDMS copolymer, and it has become necessary to add various additives and impart high functions.
When adding various additives to this PC-PDMS copolymer and imparting advanced functions, a problem arises that white turbidity occurs and the transparency and weather resistance of the PC-PDMS copolymer are impaired. There was a point.
When a homopolycarbonate resin containing bisphenol A as a monomer component is used as an optical disk substrate, an optical information recording medium having a low bit error rate is obtained by setting the amount of sodium remaining in the polycarbonate resin to 1 ppm or less. It is known from Patent Document 1 and Patent Document 2 that this can be done. However, the effect of sodium remaining in the resin composition when various additives are added to the PC-PDMS copolymer has not been known.
As a result of diligent research, the present inventors have found that a white turbidity phenomenon occurs in the PC-PDMS copolymer when the content of sodium in various additives is large, and have completed the present invention.

Japanese Patent Publication No. 8-27978 Japanese Patent No. 2666209

  The present invention reduces the white turbidity phenomenon of a polycarbonate resin composition in which an additive is added to a polycarbonate resin containing a polycarbonate-polyorganosiloxane copolymer (sometimes referred to as a PC-POS copolymer). An object of the present invention is to provide a polycarbonate resin composition having excellent properties, weather resistance, and impact resistance, and a molded article formed by molding the polycarbonate resin composition.

As a result of extensive research, the present inventor has made the content of sodium contained in a polycarbonate resin composition in which an additive is added to a polycarbonate resin containing a PC-POS copolymer to be a specific amount or less. The present invention has been completed.
That is, the present invention relates to the following [1] to [12].

[1] (A) The main chain includes a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) (where n = 10 to 500), Polycarbonate-polyorganosiloxane copolymer (A-1) having a repeating unit content of 1.0 to 10.0% by mass, 10 to 100% by mass, and a polycarbonate other than (A-1) (A -2) A polycarbonate resin composition obtained by adding (B) an additive to a polycarbonate resin composed of 0 to 90% by mass, wherein the sodium contained in the polycarbonate resin composition is 0.5 ppm or less. A polycarbonate-based resin composition.

[Wherein, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon arylalkyl group having 7 to 15, aryl alkylidene group having 7 to 15 carbon atoms, -S -, - SO -, - SO 2 -, - indicating O- or -CO- a. a and b each independently represent an integer of 0 to 4.
R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n is the average number of repetitions. ]
[2] The polycarbonate resin composition according to [1], wherein the amount of the component (B) is 0.01 to 5 parts by mass with respect to 100 parts by mass of the polycarbonate resin.
[3] The polycarbonate resin composition according to the above [1] or [2], wherein the component (B) contains sodium.
[4] A flat plate test piece having a thickness of 2 mm was formed by molding a cylinder temperature of the molding machine at 280 ° C., a mold temperature of 80 ° C., and a molding cycle in 30 seconds, and measurement was performed using the flat plate test piece. The polycarbonate-type resin composition in any one of said [1]-[3] whose L ^* value in CIE1976 (L ^* , a ^* , b ^* ) color space is 50 or more.
[5] The polycarbonate resin composition according to any one of [1] to [4], wherein the component (B) is an ultraviolet absorber.
[6] The polycarbonate resin composition according to the above [5], wherein the ultraviolet absorber is a compound represented by the following general formula (1), and the sodium content is 40 ppm or less.

[Wherein, R ₁ represents a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule. R ₂ represents hydrogen, a halogen group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. n represents an integer of 2 to 3, and m represents an integer of 1 to 4. ]
[7] The polycarbonate resin composition according to the above [5] or [6], wherein the ultraviolet absorber is p-phenylenebis (1,3-benzoxazin-4-one).
[8] The polycarbonate type according to any one of [5] to [7], wherein the blending amount of the ultraviolet absorber is 0.05 to 0.5 parts by mass with respect to 100 parts by mass of the polycarbonate resin. Resin composition.
[9] The polycarbonate resin composition according to any one of [5] to [7], wherein the blending amount of the ultraviolet absorber is 0.2 to 3 parts by mass with respect to 100 parts by mass of the polycarbonate resin. object.
[10] A molded article obtained by molding the polycarbonate resin composition according to any one of [1] to [9].
[11] An injection-molded article obtained by injection-molding the polycarbonate resin composition according to [8].
[12] A sheet-like molded product obtained by extrusion molding the polycarbonate resin composition according to [9].

  The polycarbonate-type resin composition of this invention can obtain the molded object excellent in transparency, a weather resistance, and impact resistance.

The polycarbonate-based resin composition of the present invention is a polycarbonate-based resin composition comprising a polycarbonate-based resin composed of the following specific component (A) and (B) an additive, and is included in the polycarbonate-based resin composition. It is a polycarbonate-type resin composition whose sodium is 0.5 ppm or less.
Hereafter, the component which the polycarbonate-type resin composition of this invention contains is demonstrated in detail. In the present specification, it is possible to arbitrarily adopt provisions that are preferable, and it can be said that a combination of preferable ones is more preferable.

[(A) Polycarbonate resin]
<PC-POS copolymer (A-1)>
The polycarbonate-based resin as the component (A) includes a repeating unit having a main chain represented by the general formula (I) and a repeating unit represented by the general formula (II) (where n = 10 to 500). Polycarbonate other than PC-POS copolymer (A-1) 10 to 100% by mass and (A-1) containing 1.0 to 10.0% by mass of the repeating unit represented by (II) (A-2) It consists of 0-90 mass%. Hereinafter, the PC-POS copolymer (A-1) will be described.

[Wherein, R ^{1 to} R ⁴ , X, a, b and n are the same as described above. ]

In general formula (I), examples of the halogen atom independently represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group independently represented by R ¹ and R ² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and various butyl groups (“various” means linear and all branched ones). And the same applies hereinafter), various pentyl groups, and various hexyl groups. Examples of the alkoxy group independently represented by R ¹ and R ² include a case where the alkyl group moiety is the alkyl group.
R ¹ and R ² are each preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
Examples of the alkylene group represented by X include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group, and an alkylene group having 1 to 5 carbon atoms is preferable. Examples of the alkylidene group represented by X include an ethylidene group and an isopropylidene group. Examples of the cycloalkylene group represented by X include a cyclopentanediyl group, a cyclohexanediyl group, and a cyclooctanediyl group, and a cycloalkylene group having 5 to 10 carbon atoms is preferable. Examples of the cycloalkylidene group represented by X include a cyclohexylidene group, 3,5,5-trimethylcyclohexylidene group, 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. The arylalkyl group represented by X is a divalent linking group in which an aryl moiety and an alkyl moiety are bonded. Examples of the aryl moiety include 6 ring-forming carbon atoms such as a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. -14 aryl groups. Examples of the aryl moiety of the arylalkylidene group represented by X include aryl groups having 6 to 14 ring 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.

In general formula (II), examples of the halogen atom independently represented by R ³ and R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group and alkoxy group independently represented by R ³ and R ⁴ include the same groups as those for R ¹ and R ² . Examples of the aryl group independently represented by R ³ and R ⁴ include a phenyl group and a naphthyl group.
As the ^{R 3} and ^{R 4,} either, preferably, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group or an aryl group having 6 to 12 carbon atoms having 1 to 6 carbon atoms, both More preferred is a methyl group.

  The PC-POS copolymer used in the present invention requires a content of the repeating unit represented by the general formula (II) of 1.0 to 10.0% by mass, preferably 2.2 to 8. It is 2 mass%, More preferably, it is 3.2-6.7 mass%. When the content of the block portion is less than 1.0% by mass, the effect on the notch sensitivity is small, and the effect of improving the drop impact strength (particularly low temperature impact resistance) is insufficient, and when the content exceeds 10% by mass. Decrease in heat resistance increases.

  The chain length of the polyorganosiloxane block portion having the structural unit of the general formula (II) requires 10 to 500, preferably 22 to 127, and more preferably 32 to 97. If it is less than 10, the effect on the notch sensitivity is small and the effect of improving the drop impact strength (particularly low temperature impact resistance) is not sufficient, and if it exceeds 500, the transparency of the PC-POS copolymer is adversely affected and obtained The transparency of the polycarbonate resin composition of the present invention may be reduced.

The structure containing the repeating unit represented by the general formula (II) is preferably represented by the following general formula (II ′).

In the formula (II ′), R ^{3 to} R ⁶ are each independently 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 having 6 to 12 carbon atoms. Indicates a group. Y represents an organic residue containing a single bond, aliphatic group or aromatic group. n is the average number of repetitions.
R ^{3 to} R ⁶ are each 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. Y is preferably a residue of a phenol compound having an alkyl group, more preferably an organic residue derived from allylphenol or an organic residue derived from eugenol.
Moreover, as a structure containing the repeating unit represented by general formula (II), it is also preferable that it is following formula (II '').

In said formula (II ''), R < ³ > -R < ⁶ >, Y and n are the same as that of the said general formula (II '), and a preferable thing is also the same.
m represents 0 or 1.
Z, like Z in the general formula (2) in which infra, indicates ^{halogen, -R 7 OH, -R 7 COOH} , -R 7 NH 2, a -COOH or -SH, said ^{R 7} is a linear, A branched or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on the ring, and an arylene group are shown.
Β represents a divalent group derived from a diisocyanate compound. Specific examples of the divalent group derived from the diisocyanate compound will be described later.

The viscosity average molecular weight (Mv) of the PC-POS copolymer (A-1) is preferably 14,000 to 28,000, more preferably 15,500 to 25,500, still more preferably 16, 000 to 23,500, particularly preferably 16,200 to 22,500. When the viscosity average molecular weight of the PC-POS copolymer (A-1) is within this range, the impact resistance of the molded article is sufficient, and the viscosity of the PC-POS copolymer does not become too high, and the production during production The stability becomes stable, and it becomes easy to form a thin wall.
The viscosity average molecular weight (Mv) was calculated from the intrinsic viscosity [η] of a methylene chloride solution at 20 ° C. and calculated from the Schnell equation ([η] = 1.23 × 10 ⁻⁵ × Mv ^0.83 ). Value.

There is no restriction | limiting in particular in the manufacturing method of PC-POS copolymer (A-1), Refer to the manufacturing method of well-known PC-POS copolymer, for example, the method as described in Unexamined-Japanese-Patent No. 2010-241943 etc. It can be manufactured easily.
Specifically, an aromatic polycarbonate oligomer produced in advance and a polyorganosiloxane having a reactive group at a terminal are dissolved in a water-insoluble organic solvent (such as methylene chloride), and a dihydric phenol compound (bisphenol A) is dissolved. And the like, and a tertiary amine (triethylamine, etc.) or a quaternary ammonium salt (trimethylbenzylammonium chloride, etc.) is used as a polymerization catalyst. -Monovalent phenol such as butylphenol) can be produced by interfacial polycondensation reaction. In addition, content of the repeating unit containing the structure represented by general formula (II) can be adjusted in the said range by adjusting the usage-amount of the said polyorganosiloxane.
After the interfacial polycondensation reaction, the mixture is allowed to stand to separate into an aqueous phase and a water-insoluble organic solvent phase [separation step], and the water-insoluble organic solvent phase is washed (preferably a basic aqueous solution, acidic aqueous solution, The PC-POS copolymer (A-1) is obtained by concentrating [concentration step], pulverizing [pulverization step] and drying [drying step]. Can do.

  The PC-POS copolymer (A-1) is composed of a dihydric phenol represented by the following general formula (1), a polyorganosiloxane represented by the following general formula (2), phosgene, carbonate ester or It can also be produced by copolymerizing with chloroformate.

Here, in the general formula (1), R ¹ and R ² , X, a and b are the same as those in the general formula (I). In general formula (2), R ^{3 to} R ⁶ are the same as those in general formula (II ′), and n is the same as that in general formula (II). Y ′ is the same as Y in the general formula (II ′).
m represents 0 or 1, Z represents halogen, —R ⁷ OH, —R ⁷ COOH, —R ⁷ NH ₂ , —COOH or —SH, R ⁷ represents a linear, branched or cyclic alkylene group, aryl A substituted alkylene group, an aryl-substituted alkylene group that may have an alkoxy group on the ring, and an arylene group are shown.
Preferably, Y ′ represents a single bond, an aliphatic group or an aromatic group, and represents an organic residue bonded to Si and O or Si and Z. R ^{3 to} R ⁶ are each 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. n is the same as described above, and m represents 0 or 1.
Z is preferably —R ⁷ OH, —R ⁷ COOH, —R ⁷ NH ₂ , —COOH or —SH. R ⁷ represents a linear, branched or cyclic alkylene group, an aryl-substituted alkylene group, an aryl-substituted alkylene group which may have an alkoxy group on the ring, or an arylene group, as described above.

Although it does not specifically limit as a dihydric phenol represented by General formula (1) which is a raw material of PC-POS copolymer (A-1), 2, 2-bis (4-hydroxyphenyl) propane [common name: Bisphenol A] is preferred. When bisphenol A is used as the dihydric phenol, in general formula (I), X is an isopropylidene group and a PC-POS with a = b = 0.
Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2 -Bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4- Hydroxyphenyl) naphthylmethane, 1,1-bis (4-hydroxy-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) Bis (hydroxyaryl) alkanes such as propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane; 1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, 2,2- Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) norbornane and 1,1-bis (4-hydroxyphenyl) cyclododecane; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3, Dihydroxy aryl ethers such as 3′-dimethylphenyl ether; Dihydroxydiaryl sulfides such as loxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide Dihydroxydiaryl sulfoxides such as 4,4′-dihydroxydiphenylsulfone, dihydroxydiarylsulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl Dihydroxydiarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 1,3-bis (4-hydroxyphenyl) ada; Dihydroxydiaryladamantanes such as tantalum, 2,2-bis (4-hydroxyphenyl) adamantane, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane; 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. It is done.
These dihydric phenols may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The polyorganosiloxane represented by the general formula (2) is a compound having an olefinically unsaturated carbon-carbon bond (preferably vinylphenol, allylphenol, eugenol, isopropenylphenol, etc.) with a predetermined polymerization degree ( n: the number of repetitions) can be easily produced by hydrosilation reaction at the end of the polyorganosiloxane chain. The phenols are more preferably allylphenol or eugenol.

As the polyorganosiloxane represented by the general formula (2), those in which R ^{3 to} R ⁶ are all methyl groups are preferable.
Examples of the polyorganosiloxane represented by the general formula (2) include compounds represented by the following general formulas (2-1) to (2-9).

In said general formula (2-1)-(2-9), R < ³ > -R < ⁶ > and n are as the said definition, and a preferable thing is also the same. R ⁸ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group, c represents a positive integer, and is usually an integer of 1 to 6.
R ⁸ is preferably an alkyl group, an alkenyl group, an aryl group, or an aralkyl group.
Among these, the phenol-modified polyorganosiloxane represented by the general formula (2-1) is preferable from the viewpoint of ease of polymerization. In terms of availability, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, which is a kind of the compound represented by the general formula (2-2), Α, ω-bis [3- (4-hydroxy-3-methoxyphenyl) propyl] polydimethylsiloxane which is one of the compounds represented by (2-3) is preferred.

The phenol-modified polyorganosiloxane can be produced by a known method. As a manufacturing method, the method shown below is mentioned, for example.
First, cyclotrisiloxane and disiloxane are reacted in the presence of an acidic catalyst to synthesize α, ω-dihydrogenorganopolysiloxane. At this time, α, ω-dihydrogenorganopolysiloxane having a desired average repeating unit can be synthesized by changing the charging ratio of cyclotrisiloxane and disiloxane. Next, in the presence of a hydrosilylation reaction catalyst, the α, ω-dihydrogenorganopolysiloxane is subjected to an addition reaction with a phenol compound having an unsaturated aliphatic hydrocarbon group such as allylphenol or eugenol. A phenol-modified polyorganosiloxane having an average repeating unit can be produced.
Further, at this stage, since low molecular weight cyclic polyorganosiloxane and an excessive amount of the phenol compound remain as impurities, it is preferable to distill off these low molecular compounds by heating under reduced pressure.

Furthermore, the PC-POS copolymer (A-1) is composed of a dihydric phenol represented by the general formula (1), a polyorganosiloxane represented by the following general formula (3), phosgene, carbonate or chloro It may be produced by copolymerizing with formate. General formula (3) is a reaction product of general formula (2) and a diisocyanate compound.

In the general formula (3), R ^{3 to} R ⁶ , n, m, Y ′, and Z are as defined above, and preferred ones are also the same.
Β represents a divalent group derived from a diisocyanate compound, and examples thereof include divalent groups represented by the following general formulas (3-1) to (3-4).

<Polycarbonates other than (A-1) (A-2)>
As described above, the component (A) may contain a polycarbonate resin (A-2) other than the component (A-1) to the extent that the effects of the present invention are not impaired. The component (A-2) may be an aromatic polycarbonate resin obtained using an aromatic dihydric phenol compound, or an aliphatic polycarbonate obtained using an aliphatic dihydric phenol compound. It may be a resin, an aliphatic polycarbonate resin obtained by using an aliphatic divalent hydroxyl group-containing compound, or a combination of an aromatic dihydric phenol compound and an aliphatic dihydric phenol compound. An aromatic-aliphatic polycarbonate resin obtained in this manner may be used. The said (A-2) component can be used in order to adjust content of the repeating unit containing the structure represented by general formula (II) contained in the resin mixture (A).
Among these, as the component (A-2), an aromatic polycarbonate resin is preferable.
From the viewpoint of physical properties, the viscosity average molecular weight of the polycarbonate resin of component (A-2) is preferably 10,000 to 40,000, more preferably 13,200 to 26,700, still more preferably 15,500 to 23,200.

The aromatic polycarbonate resin does not have a repeating unit including the structure represented by the general formula (II), and the main chain is composed of a repeating unit represented by the following general formula (III) It is preferable that Such an aromatic polycarbonate resin is not particularly limited, and various known aromatic polycarbonate resins can be used.

[Wherein, R ⁹ and R ¹⁰ each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X ′ is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, —S—, —SO. -, - _SO 2 -, - indicating O- or -CO- a. c and d each independently represent an integer of 0 to 4. ]
Specific examples of R ⁹ and R ¹⁰ include the same as R ¹ and R ^2, and preferred ones are also the same. R ⁹ and R ¹⁰ 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 described above, and preferable examples are also the same. c and d are each independently preferably 0 to 2, more preferably 0 or 1.

Specifically, the aromatic polycarbonate resin is prepared by reacting with an aromatic dihydric phenol compound and phosgene in the presence of an organic solvent inert to the reaction, an aqueous alkaline solution, and then a tertiary amine or quaternary ammonium. Conventional methods such as the interfacial polymerization method in which a polymerization catalyst such as a salt is added and polymerized, and the pyridine method in which an aromatic dihydric phenol compound is dissolved in pyridine or a mixed solution of pyridine and an inert solvent and phosgene is directly introduced are used. What is obtained by the manufacturing method of an aromatic polycarbonate can be used.
In the above reaction, a molecular weight regulator (terminal terminator), a branching agent and the like are used as necessary.
In addition, as said aromatic dihydric phenol type compound, what is represented by the following general formula (III ') is mentioned.

[Wherein R ⁹ , R ¹⁰ and X ′ are as defined above, and preferred ones are also the same. ]
Specific examples of the aromatic dihydric phenol compound include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4- Bis (hydroxyphenyl) alkanes such as hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane Bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ketone and the like.
Among these, bis (hydroxyphenyl) alkane dihydric phenol is preferable, and bisphenol A is more preferable.

The said aromatic polycarbonate resin may be used individually by 1 type, and may use 2 or more types together.
The aliphatic polycarbonate resin can be produced by using an aliphatic dihydric hydroxyl group-containing compound or an aliphatic dihydric phenol compound instead of the aromatic dihydric phenol compound.
In addition, an aromatic-aliphatic polycarbonate resin can be manufactured by using together an aromatic dihydric phenol type compound and an aliphatic dihydric phenol type compound as above-mentioned.

<Ratio of (A-1) component and (A-2) component>
(A) The polycarbonate-type resin of a component is a ratio which consists of PC-POS copolymer (A-1) 10-100 mass% and polycarbonate (A-2) other than (A-1) 0-90 mass%. It needs to be. When the component (A-1) is less than 10% by mass, impact resistance, particularly impact resistance at low temperatures is lowered, which is not preferable. The content of the repeating unit represented by the general formula (II) in the component (A-1) with respect to 100% by mass of the total amount of the component (A-1) and the component (A-2) is 1.0 to The ratio of the component (A-1) and the component (A-2) can be arbitrarily adjusted at a ratio of 10.0% by mass. Preferably, it is desirable to mix and use the component (A-1) in the range of 30 to 100% by mass and the component (A-2) in the range of 0 to 70% by mass.

[(B) Additive]
In the polycarbonate resin composition of the present invention, the component (B) additive is blended with the component (A) polycarbonate resin. (B) As an additive of a component, if it is an additive mix | blended with polycarbonate-type resin, unless it impairs the transparency which polycarbonate-type resin has, it will not specifically limit, An ultraviolet absorber, antioxidant, Examples include flame retardants, flame retardant aids, light stabilizers, plasticizers, antistatic agents, antiblocking agents, antibacterial agents, compatibilizers, colorants (dyes, pigments) mold release agents, and lubricants.
(B) 0.01-5.0 mass parts with respect to 100 mass parts of polycarbonate-type resin of (A) component, Preferably it is desirable to mix | blend 0.03-3.0 mass parts.
(B) The ultraviolet absorber and antioxidant of a component are demonstrated below.

<Ultraviolet absorber>
Examples of the ultraviolet absorber include various compounds such as benzoxazinone, benzotriazole, salicylate, malonic ester, oxalyl alanide, triazine, benzophenone, and cyanoacrylate. These can be used alone or in combination of two or more.
Examples of the benzoxazinone compound include compounds represented by the following general formula (1).

[Wherein, R ₁ represents a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule. R ₂ represents hydrogen, a halogen group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. n represents an integer of 2 to 3, and m represents an integer of 1 to 4. ]

In general formula (1), R ₁ is a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule, such as a phenylene group, a biphenylene group, or a naphthylene group. An arylene group can be mentioned. Examples of the alkyl group having 1 to 8 carbon atoms as R ₂ include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, and examples of the alkoxy group having R ₂ as 1 to 8 carbon atoms include methoxy group. , An ethoxy group, a propoxy group, and a butoxy group. R ₂ is an alkenyloxy group having 2 to 8 carbon atoms, such as allyloxy group, 2-propenyloxy group, 2-butenyloxy group, and 2-methyl-3-propenyl. An oxy group etc. can be mentioned.

Among the compounds represented by the general formula (1), p-phenylenebis (1,3-benzoxazin-4-one) is particularly preferable. p-phenylenebis (1,3-benzoxazin-4-one) is a compound represented by the following formula.

  Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, and 2- (2′-hydroxy). -5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'- Di-amylphenyl) benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and the like. .

Examples of the salicylate compound include phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, and the like. Examples of malonic ester compounds include benzylidene bisdiethyl malonate and 4-methoxyphenyl-methylene-dimethyl ester. Examples of the oxalyl alanide compound include an oxalyl alanide compound having a hydrocarbon group having 1 to 12 carbon atoms. These ultraviolet absorbers are 0 with respect to 100 parts by mass of the polycarbonate resin as the component (A). 0.1 to 3.0 parts by mass, preferably 0.1 to 2.0 parts by mass is desirable. In particular, when molding an injection-molded body, it is preferably 0.1 to 0.5 parts by mass, and when molding a sheet-like molded body, it is preferably 0.2 to 3 parts by mass.

<Antioxidant>
Examples of the antioxidant include phenolic, phosphorus and sulfur antioxidants. The following antioxidant may be used independently and may be used in mixture of 2 or more types. In particular, it is known that the effect of an antioxidant can be sustained by using a phenolic antioxidant and a phosphorus antioxidant in combination.
Although there is no restriction | limiting in particular as a phenolic antioxidant, A hindered phenol type is used suitably. Representative examples include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4- Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis [(3,5-di-tert-butyl-4-hydroxy) -hydrocinnamamide], 2,2-thio- Diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n -Octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, 1,3,5-trimethyl-2,4,6-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and bis (3,5-di-tert-butyl-4- And ethyl hydroxybenzylphosphonate) calcium.
These antioxidants are desirably blended in an amount of 0.003 to 0.5 parts by weight, preferably 0.01 to 0.2 parts by weight, with respect to 100 parts by weight of the polycarbonate-based resin (A).

  There is no restriction | limiting in particular as phosphorus antioxidant. Typical examples include tris (nonylphenyl) phosphite, 2-ethylhexidiphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl Trialkyl phosphites such as phosphite, trioctadecyl phosphite, distearyl pentaerythryl diphosphite, tris (2-chloroethyl) phosphite, tris (2,3-dichloropropyl) phosphite, and tricyclohexyl phosphite Tricycloalkyl phosphite, triphenyl phosphite, tricresyl phosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite, tris (hydroxyphenyl) phosphite And triaryl phosphites such as tris (2,4-di-tert-butylphenyl) phosphite, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, trioctadecyl phosphate , Trialkyl phosphates such as distearyl pentaerythrityl diphosphate, tris (2-chloroethyl) phosphate, tris (2,3-dichloropropyl) phosphate, tricycloalkyl phosphates such as tricyclohexyl-1-phosphate, And triaryl phosphates such as triphenyl phosphate, tricresyl phosphate, tris (nonylphenyl) phosphate, 2-ethylphenyldiphenyl phosphate, and the like. Of these, triaryl phosphites and triaryl phosphates are preferably used.

<Other additives>
Other additives include hindered amine light stabilizers, aliphatic carboxylic acid esters, paraffins, silicone oil, polyethylene wax and other plasticizers, various antistatic agents, flame retardants, antiblocking agents, antibacterial agents, and compatibilizers. Agents, colorants (dyes, pigments), mold release agents and lubricants.

[Sodium content in polycarbonate resin composition]
The polycarbonate resin composition of the present invention requires that the sodium content is 0.5 ppm or less. When the content of sodium exceeds 0.5 ppm, the resulting polycarbonate resin composition and the molded product thereof become cloudy, the transparency is impaired, and the weather resistance is also lowered. The content of sodium is preferably 0.4 ppm or less, more preferably 0.1 ppm or less. In order to reduce the sodium content in the polycarbonate resin composition to 0.5 ppm or less, the polycarbonate resin of the component (A) having a low sodium content and the additive of the component (B) having a low sodium content are added. It is necessary to use it. The polycarbonate resin of component (A) having a low sodium content can be reduced to 0.1 ppm or less by removing impurities by washing with pure water or the like in the production process by the interface method. On the other hand, some additives of component (B) have a high sodium content, and in the present invention, it is necessary to use an additive having as low a sodium content as possible. The content of sodium in the component (B) varies depending on the blending amount, but preferably 40 ppm or less of each additive is used.
In the polycarbonate resin composition of the present invention, it is preferable that the magnesium content is 20 ppm or less, the aluminum content is 20 ppm or less, and the iron content is 20 ppm or less.

In particular, when an ultraviolet absorber is used as an additive for the component (B), there is a commercial product with a high sodium content. In such a case, the amount of the polycarbonate resin composition is reduced as much as possible. The content of sodium needs to be 0.5 ppm or less.
As an ultraviolet absorber having a sodium content of 40 ppm or less, there is p-phenylenebis (1,3-benzoxazin-4-one) manufactured by Cytech Technology Co., Ltd., and this ultraviolet absorber is in the manufacturing process. When sodium hydroxide is not used, the content of sodium is low, and an ultraviolet absorber is used as an additive of the component (B) of the present invention, it is a preferable ultraviolet absorber.

  As the component (B) of the present invention, the thermal stability of the composition can be improved by using the antioxidant together with the ultraviolet absorber in the preferable blending amount.

[Kneading / Molding]
The polycarbonate-based resin composition of the present invention can be obtained by kneading a predetermined amount of the components (A) and (B) and, if necessary, other components. The kneading method is not particularly limited, and examples thereof include a method using a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder, and the like. . Moreover, the heating temperature at the time of kneading | mixing is preferably 240-330 degreeC normally, More preferably, it is 250-320 degreeC.
The polycarbonate resin composition produced by the above method has an L ^* value of preferably 50 or more, more preferably 65 or more, even more preferably in the measurement of L ^* a ^* b ^* according to the CIE 1976 standard described in the Examples. Is 80 or more, most preferably 90 or more. In addition, although there is no upper limit in particular, 99 or less, 97 or less, and 96 or less can be illustrated from a viewpoint of manufacture ease.
As the molding method, conventionally known various molding methods can be used, for example, injection molding method, injection compression molding method, extrusion molding method, blow molding method, press molding method, vacuum molding method and foam molding method. It is done.
The components other than the polycarbonate-based resin can be melt-kneaded with the polycarbonate-based resin in advance, that is, added as a master batch.
The polycarbonate resin composition is preferably formed into an injection-molded product by injection molding after pelletizing. For injection molding, a general injection molding method or a general injection compression molding method, or a special molding method such as a gas assist molding method can be used, and a molded body can be produced in this way.
Furthermore, it is also preferable that the polycarbonate-based resin composition is formed into a sheet-like molded body after being pelletized and then extrusion-molded. In order to obtain a sheet-like molded body by extrusion molding, a sheet-like molded body can be produced using a known extruder such as a T-die extruder.

When the molded body of the present invention is used as an appearance member, a molding technique for improving the appearance of a heat cycle molding method, a high temperature mold, a heat insulation mold, or the like can be used.
In addition, when the component is required to be flame retardant, a molding technique such as laminate molding with a flame retardant resin material or two-color molding can be used.
In order to obtain a large-sized thin-walled injection molded body, injection compression molding or high-pressure or ultra-high pressure injection molding can be used. For molding a molded body having a partial thin-walled portion, partial compression molding or the like should be used. You can also.

  The molded body of the present invention includes, for example, copying machines, fax machines, televisions, radios, tape recorders, video decks, personal computers, printers, telephones, information terminals, refrigerators, microwave ovens, OA equipment, home appliances, Used in electronic equipment housings and various parts.

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
The performance test of the resin composition obtained in each example was performed as follows.
(1) Sodium content It calculated | required by calculation from the residual amount quantified by the plasma emission spectroscopy (ICP method), and the compounding quantity to a composition.
(2) Viscosity Number Using a single-screw extruder “NVC-50” manufactured by Nakatani Machine Co., Ltd., the viscosity number was measured according to ISO 1628 using pellets granulated at a cylinder temperature of 280 ° C.
(3) L ^* a ^* b ^* value The resin composition was 2 mm thick at an injection molding machine “EC-40” manufactured by Toshiba Machine Co., Ltd. with a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 30 seconds. The molded product was prepared and measured by the transmission method using a C2 light source based on the color measurement method of CIE1976 (L ^* a ^* b ^* ). L ^* is an index indicating brightness, and a ^* and b ^* are color quality indexes. When a ^* becomes positive, it becomes reddish. When a ^* becomes negative, it becomes greenish. When b ^* is positive, it becomes yellowish. When b ^* becomes negative, it becomes bluish.
(4) Weather resistance test: change in L ^* value Black panel temperature 63 ° C., humidity 50%, rainfall cycle 12/60 minutes (rain time is 12 minutes among 60 minutes), irradiation intensity (300 to 400 nm) 78.5 W The test piece (size: 40 mm x 30 mm x 2 mm) is left on a sunshine weather meter (SUGA SUNSHINE SUPER LONG-LIFE WEATHER) set to / m ² and taken out after 2040 hours ^. The value was measured. The difference from the L ^* value in (3) above was designated as ΔL ^* . It shows the difference in the index indicating the brightness of the test piece before and after the weather resistance test.
(5) Izod impact value (IZOD): impact resistance Using a test piece having a thickness of 1/8 inch, an Izod impact test with a notch was conducted at 23 ° C. in accordance with ASTM D256.
(6) Light transmittance: total light transmittance, diffuse light transmittance, parallel light transmittance As a light transmittance, a 2 mm thick flat plate obtained by injection molding is used, and a transmittance measuring instrument (NDH-300A) based on ISO14782. , Manufactured by Nippon Denshoku Industries Co., Ltd.), total light transmittance, diffuse light transmittance and parallel light transmittance were measured. The parallel light transmittance is the light transmittance that is transmitted coaxially with the incident light, and the sum of the parallel light transmittance and the diffuse light transmittance is the total light transmittance.

Production Example 1
[Production of polycarbonate oligomer production]
2,000 ppm of sodium dithionite is added to 5.6 mass% sodium hydroxide aqueous solution to bisphenol A (BPA) which is later dissolved, and BPA is dissolved so that the BPA concentration becomes 13.5 mass%. A sodium hydroxide aqueous solution of BPA 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 liter / hr of sodium hydroxide aqueous solution of BPA and 15 liter / hr of methylene chloride.
The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
The reaction liquid exiting the tubular reactor was continuously introduced into a baffled tank reactor having an internal volume of 40 liters equipped with a receding blade, and further 2.8 liters / hr of sodium hydroxide aqueous solution of BPA, 25 The reaction was carried out by adding 0.07 liter / hr of a mass% aqueous sodium hydroxide solution, 17 liter / hr of water, and 0.64 liter / hr of a 1 mass% triethylamine aqueous solution. The reaction liquid overflowing from the tank reactor was continuously extracted 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 329 g / L and a chloroformate group concentration of 0.74 mol / L.

Production Example 2
[Production of Polycarbonate-Polydimethylsiloxane Copolymer-1 (PC-PDMS Copolymer-1)]
Allylphenol end-modified poly having a polycarbonate oligomer solution 15L, methylene chloride 9.0L, and a dimethylsiloxane unit repeating number 40 in a 50L tank reactor equipped with a baffle plate, a paddle type stirring blade and a cooling jacket 384 g of dimethylsiloxane (PDMS) and 8.8 mL of triethylamine were charged, and 1389 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto under stirring, and the reaction between the polycarbonate oligomer and the allylphenol terminal-modified PDMS was performed for 10 minutes.
To this polymerization liquid, methylene chloride solution of pt-butylphenol (PTBP) (PTBP 132 g dissolved in 2.0 L of methylene chloride), BPA sodium hydroxide aqueous solution (NaOH 577 g and sodium dithionite 2.0 g in water) A solution obtained by dissolving 1012 g of BPA in an aqueous solution dissolved in 8.4 L) was added, and a polymerization reaction was carried out for 50 minutes.
For dilution, 10 L of methylene chloride was added and stirred for 10 minutes. Then, the organic phase was separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was washed successively with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid with respect to the solution. Washing with pure water was repeated until the electrical conductivity in the aqueous phase became 0.01 μS / m or less.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
The PDMS block portion content determined by nuclear magnetic resonance (NMR) of the obtained polycarbonate-polydimethylsiloxane copolymer was 6.0% by mass, and the viscosity number measured according to ISO 1628-4 (1999) was 49. 5. Viscosity average molecular weight Mv = 18500.

Production Example 3
[Production of Polycarbonate-Polydimethylsiloxane Copolymer-2 (PC-PDMS Copolymer-2)]
Allylphenol terminal-modified poly having a polycarbonate oligomer solution 15L, methylene chloride 9.0L, and a dimethylsiloxane unit repeating number 90 in a 50L tank reactor equipped with a baffle plate, a paddle type stirring blade and a cooling jacket 384 g of dimethylsiloxane (PDMS) and 8.8 mL of triethylamine were charged, and 1389 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto under stirring, and the reaction between the polycarbonate oligomer and the allylphenol terminal-modified PDMS was performed for 10 minutes.
To this polymerization liquid, methylene chloride solution of pt-butylphenol (PTBP) (PTBP 132 g dissolved in 2.0 L of methylene chloride), BPA sodium hydroxide aqueous solution (NaOH 577 g and sodium dithionite 2.0 g in water) A solution obtained by dissolving 1012 g of BPA in an aqueous solution dissolved in 8.4 L) was added, and a polymerization reaction was carried out for 50 minutes.
For dilution, 10 L of methylene chloride was added and stirred for 10 minutes. Then, the organic phase was separated into an organic phase containing a polycarbonate-polydimethylsiloxane copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer thus obtained was washed successively with 15% by volume of 0.03 mol / L NaOH aqueous solution and 0.2 mol / L hydrochloric acid with respect to the solution. Washing with pure water was repeated until the electrical conductivity in the aqueous phase became 0.01 μS / m or less.
The methylene chloride solution of the polycarbonate-polydimethylsiloxane copolymer obtained by washing was concentrated and pulverized, and the obtained flakes were dried at 120 ° C. under reduced pressure.
The PDMS block portion content determined by nuclear magnetic resonance (NMR) of the obtained polycarbonate-polydimethylsiloxane copolymer was 6.0% by mass, and the viscosity number measured according to ISO 1628-4 (1999) was 49. 5. Viscosity average molecular weight Mv = 18500.

Examples 1-10 and Comparative Examples 1-6
Each component is mixed in the ratio shown in Table 1 [(B) component is expressed in parts by mass with respect to 100 parts by mass of component (A). Moreover, (A-1) component and (A-2) component which are (A) components show the mass%. In addition, 0.02 parts by mass of tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS168, trade name, manufactured by Ciba Specialty Chemicals) as an antioxidant was mixed uniformly and vented. With a single screw extruder (manufactured by Nakatani Machine Co., Ltd., model name: NVC50), granulation was performed at a resin temperature of 280 ° C. to obtain pellets.
The obtained pellets were injection-molded using an injection molding machine under the molding conditions of a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. to obtain test pieces.
Using the obtained test pieces, the sodium content, viscosity number, L ^* value, weather resistance test, Izod impact value, and light transmittance were evaluated according to the above methods. The results are shown in Tables 1 and 2.

[Explanation of Notes in Table 1 and Table 2]
* 1: PC-PDMS copolymer-1 obtained in Production Example 2: Sodium content is below the lower detection limit, (A-1) component * 2: PC-PDMS copolymer-2 obtained in Production Example 3 : Sodium content is lower than detection limit, (A-1) component * 3: “Taflon FN1700A: Sodium content is lower than detection limit” (trade name, manufactured by Idemitsu Kosan Co., Ltd., bisphenol A having pt-butylphenol as a terminal group Type aromatic polycarbonate, viscosity average molecular weight 17,700), (A-2) component * 4: bisbenzoxazinone Takemoto Yushi Co., Ltd. “trade name, Pionine ZA-101, benzoxazinone UV absorber: Sodium content is 760ppm "(B) component * 5: Bisbenzoxazinone" Product name, UV-3638 "manufactured by Cytech Technology Corporation , Benzoxazinone-based UV absorber: 17 ppm containing sodium (B) component * 6: Tris (2,4-di-t-butylphenyl) phosphite manufactured by Ciba Specialty Chemicals, Inc., “trade name, Irgaphos 168 , Phosphorus antioxidant: sodium content is below detection limit ”(B) component * 7: full ester of pentaerythritol and stearic acid and full ester of pentaerythritol and palmitic acid and mixture (mixing ratio is C16: C18 = 1: 1.1) “EW440A, mold release agent, sodium content is 20 ppm” manufactured by Riken Vitamin Co., Ltd.
In this measurement method, the lower limit of detection of sodium is 100 ppb.

From Tables 1 and 2, the polycarbonate resin composition of the present invention has a sodium content of 0.5 ppm or less, so there is little decrease in viscosity number, low decrease in L ^* value immediately after molding, and weather resistance test. It can be seen that there is little change in the L ^* value at. Moreover, it turns out that the polycarbonate-type resin composition of this invention has few fall of impact resistance, and is excellent in transparency. On the other hand, from Comparative Examples 1-6, in the case of the resin composition which does not use the (A-1) component, it turns out that impact resistance is falling. Further, even when the component (A-1) is used, when the sodium content in the composition exceeds 0.5 ppm, the L ^* value decreases immediately after molding and the transparency is impaired. You can see that Therefore, it is difficult to determine the change in L ^* value in the weather resistance test. Or it turns out that impact resistance may fall.

  The polycarbonate-based resin composition of the present invention is excellent in transparency, weather resistance, and impact resistance. Therefore, the fields require these characteristics, for example, electronic / electric equipment, information / communication equipment, home appliances, OA equipment. In addition, it can be suitably used in the automobile field, the building material field, and the like.

Claims (11)

(A) The main chain includes a repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II) (where n = 10 to 500), and is represented by the general formula (II) Polycarbonate-polyorganosiloxane copolymer (A-1) having a repeating unit content of 1.0 to 10.0% by mass, 10 to 100% by mass, and a polycarbonate other than (A-1) (A-2) A polycarbonate resin composition obtained by blending (B) an additive with 0 to 90% by mass of a polycarbonate resin, wherein the component (B) contains an ultraviolet absorber, and the polycarbonate resin composition The polycarbonate-type resin composition whose sodium contained in is 0.5 ppm or less.

[Wherein, R ¹ and R ² each independently represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a fluorenediyl group, a carbon arylalkyl group having 7 to 15, aryl alkylidene group having 7 to 15 carbon atoms, -S -, - SO -, - SO 2 -, - indicating O- or -CO- a. a and b each independently represent an integer of 0 to 4.
R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n is the average number of repetitions. ]   The polycarbonate-type resin composition of Claim 1 whose compounding quantity of the said (B) component is 0.01-5 mass parts with respect to 100 mass parts of polycarbonate-type resin.   The polycarbonate-type resin composition of Claim 1 or 2 in which the said (B) component contains sodium. CIE 1976 (L) measured using a flat plate test piece having a cylinder temperature of 280 ° C., a mold temperature of 80 ° C. and a molding cycle of 30 seconds to form a flat plate test piece having a thickness of 2 mm. ^* , A ^* , b ^* ) The polycarbonate resin composition according to any one of claims 1 to 3, wherein an L ^* value in a color space is 50 or more. The polycarbonate-type resin composition in any one of Claims 1-4 whose said ultraviolet absorber is a compound represented by following General formula (1), and whose sodium content is 40 ppm or less.

[Wherein, R ₁ represents a residue obtained by removing n hydrogen atoms from a hydrocarbon compound having one or two aromatic rings in the molecule. R ₂ represents hydrogen, a halogen group, a nitro group, an alkyl group having 1 to 8 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. n represents an integer of 2 to 3, and m represents an integer of 1 to 4. ]   The polycarbonate-type resin composition in any one of Claims 1-5 whose said ultraviolet absorber is p-phenylenebis (1,3-benzoxazin-4-one).   The polycarbonate-type resin composition in any one of Claims 1-6 whose compounding quantity of the said ultraviolet absorber is 0.05-0.5 mass part with respect to 100 mass parts of polycarbonate-type resin.   The polycarbonate-type resin composition in any one of Claims 1-6 whose compounding quantity of the said ultraviolet absorber is 0.2-3 mass parts with respect to 100 mass parts of polycarbonate-type resin.   The molded object formed by shape | molding the polycarbonate-type resin composition in any one of Claims 1-8.   An injection-molded article obtained by injection-molding the polycarbonate resin composition according to claim 7.   The sheet-like molded object formed by extrusion molding the polycarbonate-type resin composition of Claim 8.