JP2010059340A - Aromatic polycarbonate resin composition, and molded product and housing formed of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition exhibiting excellent flame retardancy and surface hardness, causing less yellowing, and having good appearance with high whiteness. <P>SOLUTION: The resin composition comprises 100 pts.wt. of an aromatic polycarbonate resin, 5-25 pts.wt. of titanium oxide, 0.01-1 pt.wt. of a metal salt compound, 0.01-1 pt.wt. of a fluoropolymer, and 0.1-5 pts.wt. of a silicone resin, wherein a unit represented by RSiO<SB>1.5</SB>(R is a 1-12C monovalent hydrocarbon group) is contained in an amount of 50 mol% or more for the whole siloxane units while an aromatic group content in the whole of contained hydrocarbon groups is 50 mol% or more and a silanol group content is 2.5-10 wt.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition from which a molded article having flame retardancy, surface hardness and a good white appearance can be obtained at the same time, and a molded body and a housing formed by molding the aromatic polycarbonate resin composition.

  Aromatic polycarbonate resins are resins having excellent heat resistance, mechanical properties, and electrical characteristics, and are widely used, for example, in automobile materials, electrical / electronic equipment materials, housing materials, and the like. In particular, the flame-retardant aromatic polycarbonate resin composition is used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

  In recent years, materials used for electrical and electronic equipment members such as computers, televisions, and printers, especially housings, have been required to have a high degree of flame resistance in consideration of home appliance fires. Therefore, aromatic polycarbonate resins imparted with flame retardancy are often used.

  On the other hand, from the viewpoint of environmental considerations and cost reductions in recent years, coating-less is desired, and accordingly, improvement of the surface hardness (scratch resistance) of the material itself is strongly desired. In addition, from the viewpoint of product design, a material having a good white appearance, specifically, low yellowness and high whiteness has been desired.

  However, the aromatic polycarbonate resin has a low surface hardness and tends to be easily damaged even when it is rubbed with a human nail or a hook, and cannot be used satisfactorily as a housing material. On the other hand, the present inventors improved the surface hardness and obtained a good whiteness, so that the titanium oxide used as a white pigment was highly filled, and in order to impart flame retardancy, a silicone resin was used. Attempted to blend.

As such a resin composition, for example, in Patent Document 1, a resin composition in which titanium oxide and a specific silicone compound are blended with an aromatic polycarbonate resin is proposed as a liquid crystal backlight material.
Patent Document 2 proposes a resin composition in which an aromatic polycarbonate resin, a white pigment, and an organopolysiloxane containing a specific organoxysilyl group are blended.

JP 2003-155405 A JP-A-6-200140

However, in the technique described in Patent Document 1, a molded product obtained by molding the above-described resin composition has a large degree of yellowing and tends to cause a decrease in whiteness. For this reason, it was not possible to obtain a molded article having a satisfactory white appearance.
Further, Patent Document 2 has no description or suggestion about flame retardancy, and does not mention the degree of yellowing.

  The present invention was devised in view of the above problems, and is an aromatic polycarbonate resin composition having an excellent appearance with excellent flame retardancy and surface hardness, low yellowing, and high whiteness, and An object of the present invention is to provide a molded body and a housing.

  In view of the above-mentioned problems, the present inventors have intensively studied the structures of aromatic polycarbonate resin, titanium oxide, and silicone resin, and the relationship between silanol group content, flame retardancy, surface hardness, and whiteness. did.

  As a result, it is high by blending an aromatic polycarbonate resin, titanium oxide, a metal salt compound, a fluoropolymer, and a silicone resin having a specific structure and containing a specific amount of silanol groups at a predetermined ratio. It has been found that an aromatic polycarbonate resin composition having flame retardancy and excellent surface hardness and satisfying the whiteness requirement can be obtained, and the present invention has been completed.

That is, the aromatic polycarbonate resin composition of the present invention comprises 100 parts by weight of an aromatic polycarbonate resin (A), 5 to 25 parts by weight of titanium oxide (B), and 0.01 to 1 part by weight of a metal salt compound (C). And 0.01 to 1 part by weight of fluoropolymer (D) and a unit represented by RSiO _1.5 (in the above formula, R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms). containing more than 50 mol% relative to the siloxane units _{(R 0~3 SiO 2.0~0.5),} and aromatic groups of all hydrocarbon group containing (R) occupies more than 50 mol%, further The gist is to contain 0.1 to 5 parts by weight of a silicone resin (E) having a silanol group content of 2.5 to 10% by weight.

At this time, the aromatic group of the silicone resin (E) is preferably a phenyl group.
The metal salt compound (C) is preferably an alkali metal salt and / or an alkaline earth metal salt of a fluorine-containing alkyl sulfonic acid and / or an aromatic sulfonic acid.
Furthermore, the aromatic polycarbonate resin composition of the present invention preferably contains 0.1 to 10 parts by weight of powdery silicone (F) in which polyorganosiloxane is supported on the surface of silica powder.

  The gist of the molded article of the present invention is that the aromatic polycarbonate resin composition of the present invention is molded.

  The gist of the housing of the present invention is that the aromatic polycarbonate resin composition of the present invention is molded.

  The aromatic polycarbonate resin composition, the molded product and the housing of the present invention are excellent in flame retardancy and surface hardness, have low yellowing, and have a good appearance with high whiteness.

Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Further, the “group” of various compounds in the present specification may have a substituent without departing from the gist of the present invention.

[1. Overview]
The aromatic polycarbonate resin composition of the present invention contains an aromatic polycarbonate resin (A), titanium oxide (B), a metal salt compound (C), a fluoropolymer (D), and a silicone resin (E). To do. Moreover, it is preferable that the aromatic polycarbonate resin composition of this invention contains powdery silicone (F) further. Furthermore, the aromatic polycarbonate resin composition of the present invention may contain other components in addition to these unless the effects of the present invention are significantly impaired.
In addition, the code | symbol with (A), (B), (C), (D), (E), and (F) attached | subjected to the end of the structural component of an aromatic polycarbonate resin composition clearly shows each structural component. It is the code | symbol attached | subjected for distinguishing.

[2. Aromatic polycarbonate resin (A)]
Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin used for this invention, For example, the aromatic polycarbonate polymer formed by making an aromatic dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the aromatic dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. The aromatic polycarbonate polymer may be linear or branched. Furthermore, the aromatic polycarbonate polymer may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. Usually, such an aromatic polycarbonate polymer becomes a thermoplastic resin.

  Examples of the aromatic dihydroxy compound among the monomers used as the raw material for the aromatic polycarbonate resin include 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), 2,2-bis (3,5). -Dibromo-4-hydroxyphenyl) propane (ie tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) ) Butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (3-butyl) Mo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxyphenyl)- 1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) -1, Bis (hydroxyaryl) alkanes such as 1,1,3,3,3-hexafluoropropane;

Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether;

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone;

Hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like can be mentioned.

Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A) is particularly preferable from the viewpoint of impact resistance.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Of the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters, haloformates and the like are used as examples of carbonate precursors. Specific examples include phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; and dihaloformates of dihydric phenols.
In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

-Manufacturing method of aromatic polycarbonate resin The manufacturing method of aromatic polycarbonate resin is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case of producing an aromatic polycarbonate resin by the interfacial polymerization method will be described. In the interfacial polymerization method, in the presence of an organic solvent inert to the reaction and an aqueous alkali solution, the pH is usually kept at 9 or higher, and an aromatic dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted and then polymerized. An aromatic polycarbonate resin is obtained by interfacial polymerization in the presence of a catalyst. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present if necessary, and an antioxidant may be present for preventing the oxidation of the aromatic dihydroxy compound.

  The aromatic dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

  Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. In addition, 1 type may be used for an alkali compound and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in the density | concentration of the alkali compound in aqueous alkali solution, Usually, in order to control pH in aqueous alkali solution of reaction to 10-12, it is used at 5 to 10 weight%. For example, when phosgene is blown, the molar ratio of the bisphenol compound and the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

  Examples of the polymerization catalyst include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride. Ammonium salts and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group. Specific examples include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The usage-amount of a molecular weight regulator is 0.5 mol or more normally with respect to 100 mol of aromatic dihydroxy compounds, Preferably it is 1 mol or more, and is 50 mol or less normally, Preferably it is 30 mol or less. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of an aromatic polycarbonate resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as the desired aromatic polycarbonate resin is obtained, and an appropriate order may be set arbitrarily. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is from the reaction (phosgenation) of the aromatic dihydroxy compound and phosgene to the start of the polymerization reaction. .
In addition, reaction temperature is 0-40 degreeC normally, and reaction time is normally several minutes (for example, 10 minutes)-several hours (for example, 6 hours).

-Melt transesterification method Next, the case where an aromatic polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound is performed.

The aromatic dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of the aromatic dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired aromatic polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the aromatic dihydroxy compound. More preferably, 0.01 mol or more is used. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

  In an aromatic polycarbonate resin, the amount of terminal hydroxyl groups tends to have a great influence on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the melt transesterification reaction, an aromatic polycarbonate resin in which the terminal hydroxyl group amount is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. . In addition, this operation can also adjust the molecular weight of the aromatic polycarbonate resin obtained normally.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

  When producing an aromatic polycarbonate resin by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among these, for example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

  The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, among them, the melt polycondensation reaction is preferably carried out in a continuous manner in consideration of the stability of the aromatic polycarbonate resin and the aromatic polycarbonate resin composition.

  In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

  The molecular weight of the aromatic polycarbonate resin according to the present invention is arbitrary and may be appropriately selected and determined. The viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more, preferably 16000 or more, more preferably It is 18000 or more, and is usually 40000 or less, preferably 30000 or less. By making the viscosity average molecular weight more than the lower limit of the above range, the mechanical strength of the aromatic polycarbonate resin composition of the present invention can be further improved, and more preferable when used for applications requiring high mechanical strength. Become. On the other hand, by making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity reduction of the aromatic polycarbonate resin composition of the present invention, so that the molding processability can be improved and the molding process can be easily performed. Become. Two or more kinds of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed and used. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above preferred range may be mixed. Good.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  Furthermore, when an aromatic polycarbonate resin having a branched structure is used as the aromatic polycarbonate resin (hereinafter referred to as “branched aromatic polycarbonate resin” as appropriate), the production method is not particularly limited, and any known production method should be used. Can do. Specific examples thereof include the methods described in JP-A-8-259687, JP-A-8-245782, and the like. In the methods described in these documents, when the aromatic dihydroxy compound and the carbonic acid diester are reacted by the melt transesterification method, the structural viscosity index is selected without using a branching agent by selecting the conditions of the catalyst or the production conditions. And an aromatic polycarbonate resin excellent in hydrolysis stability can be obtained.

  Further, as another method for producing a branched aromatic polycarbonate resin, a trifunctional or higher polyfunctional aromatic compound is used in addition to the aromatic dihydroxy compound and the carbonate precursor, which are the raw materials of the aromatic polycarbonate resin described above. These may be copolymerized by interfacial polymerization or melt stealth exchange.

  Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4, 6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) benzene, Polyhydroxy compounds such as 1,1,1-tri (4-hydroxyphenyl) ethane;

3,3-bis (4-hydroxyaryl) oxyindole (that is, isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.
In addition, a polyfunctional aromatic compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  A polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound. The amount of the polyfunctional aromatic compound used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and usually 10 mol% or less, preferably 3 mol, based on the aromatic dihydroxy compound. % Or less.

Examples of the branched structure contained in the aromatic polycarbonate resin obtained by the melt transesterification method include structures of the following formulas (1) to (4). In the following formulas (1) to (4), 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, or 5 carbon atoms. 15 cycloalkylidene group or,, -O -, - S - , - CO -, - SO -, - SO 2 - in showing what is selected from the group consisting of divalent groups represented.

-Other matters regarding aromatic polycarbonate resin Among the aromatic polycarbonate resin compositions according to the present invention, those having a structural viscosity index N of 1.2 or more are preferably used. Many aromatic polycarbonate resins having such a structural flammability index N have a branched structure. The branched aromatic polycarbonate resin that can be suitably used in the present invention has a structural viscosity index N of usually 1.2 or more, and the use of this branched aromatic polycarbonate resin has a dripping prevention effect (of a molten resin ignited during combustion). The effect of preventing dripping) is preferable. Here, the structural viscosity index N is a value described in, for example, a known document (Shigeharu Onoki, “Rheology for chemists”, pages 15 to 16).

  The terminal hydroxyl group concentration of the aromatic polycarbonate resin according to the present invention is arbitrary, and may be appropriately selected and determined, but is usually 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the aromatic polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the aromatic polycarbonate resin composition of this invention can be improved more.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The measurement method is colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by the titanium tetrachloride / acetic acid method.

  The aromatic polycarbonate resin according to the present invention is not limited to an aromatic polycarbonate resin alone (the aromatic polycarbonate resin alone is not limited to an embodiment containing only one type of aromatic polycarbonate resin. For example, a plurality of monomer compositions and molecular weights different from each other are used. It may be used in the meaning including an embodiment including a kind of aromatic polycarbonate resin.) Or an alloy (mixture) of an aromatic polycarbonate resin and another thermoplastic resin may be used in combination. Furthermore, for example, for the purpose of further increasing the flame retardancy, the aromatic polycarbonate resin may be configured as a copolymer mainly composed of an aromatic polycarbonate resin, such as a copolymer with an oligomer or polymer having a siloxane structure. Good.

  In addition, the aromatic polycarbonate resin may contain an aromatic polycarbonate oligomer in order to improve the appearance and fluidity of the molded product. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is usually 1500 or more, preferably 2000 or more, and usually 9500 or less, preferably 9000 or less. Furthermore, the aromatic polycarbonate ligomer contained is preferably 30% by weight or less of the aromatic polycarbonate resin (including the aromatic polycarbonate oligomer).

Furthermore, the aromatic polycarbonate resin according to the present invention may be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product (so-called material recycled aromatic polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the regenerated aromatic polycarbonate resin is preferably 80% by weight or less of the aromatic polycarbonate resin contained in the aromatic polycarbonate resin composition of the present invention, and more preferably 50% by weight or less. preferable. The regenerated aromatic polycarbonate resin is likely to have been subjected to deterioration such as heat deterioration and aging deterioration, so when such an aromatic polycarbonate resin is used more than the above range, the hue and mechanical properties are not improved. This is because there is a possibility of lowering.

[3. Titanium oxide (B)]
The aromatic polycarbonate resin composition of the present invention contains titanium oxide. By containing titanium oxide in this manner, the surface hardness of the aromatic polycarbonate resin composition of the present invention and the molded body formed by molding the same can be improved, and a white appearance can be imparted. As the titanium oxide, a suitable one may be arbitrarily selected from conventionally known ones, and the production method, crystal form, shape such as average particle diameter, and the like are not particularly limited.

  The particle diameter of titanium oxide is usually 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.15 μm or more, and usually 0.5 μm or less, preferably 0.35 μm or less. If the particle size is too small, the light shielding property tends to be inferior. On the other hand, if the particle size is too large, the white appearance or the surface appearance tends to deteriorate, or the impact strength tends to decrease.

  The production method of titanium oxide is arbitrary, and for example, those obtained by any method such as chlorine method and sulfuric acid method can be used. Among these, titanium oxide produced by the chlorine method is preferable because it is superior in terms of whiteness and the like as compared with titanium oxide produced by the sulfuric acid method. In addition, a titanium oxide may use only what was manufactured with the single manufacturing method, and may use together 2 or more types of titanium oxide manufactured with the different manufacturing method in arbitrary combinations and a ratio.

  The crystal form of titanium oxide may be, for example, either anatase type or rutile type. Of these, the rutile type is preferred because it is superior in whiteness, light reflectance, and weather resistance compared to the anatase type. Note that only one titanium oxide having a single crystal form may be used, or two or more titanium oxides having different crystal forms may be used in any combination and ratio.

  Moreover, you may use the titanium oxide surface-treated with the surface treating agent. In this case, one type of surface treatment agent may be used, or two or more types may be used in any combination and ratio. Moreover, you may use only 1 type of titanium oxide surface-treated with the same surface treating agent, and you may use together 2 or more types of titanium oxide surface-treated with a different surface treating agent in arbitrary combinations and ratios.

  Examples of the surface treatment agent include inorganic compounds other than titanium oxide. Examples of inorganic compounds used for the surface treatment include alumina, silica, zirconia and the like. These inorganic compounds other than titanium oxide are usually used when treating titanium oxide in the production process of titanium oxide for the purpose of improving the handling of titanium oxide.

  In titanium oxide, the content of inorganic compounds other than titanium oxide used for the surface treatment may be appropriately selected and determined, but is usually 2 to 5% by weight in titanium oxide. If the content of the inorganic compound is too large, the adsorbed water in the inorganic compound used for the surface treatment may cause poor appearance or dripping during combustion in the molded article of the present invention. In particular, when the amount of the silica component is too large among the inorganic compounds, the above-mentioned poor appearance and dripping become remarkable. Therefore, when the surface of titanium oxide is treated with an inorganic compound, it is preferably treated with alumina, zirconia or the like rather than silica.

  Furthermore, examples of the surface treatment agent include organic silicon compounds such as organic silane compounds and organic silicone compounds. The use of titanium oxide surface-treated with an organosilicon compound is preferable because the thermal stability is greatly improved. Further, prior to the surface treatment with the organosilicon compound, the titanium oxide surface may be surface treated with another surface treatment agent such as an inorganic compound. However, in this case, it is preferable that the amount of the inorganic compound used for the surface treatment is small, for example, 2% by weight or less with respect to titanium oxide.

  Further, the surface treatment with the organosilicon compound improves the uniform dispersibility of titanium oxide in the aromatic polycarbonate resin composition of the present invention, improves the stability of the dispersed state of titanium oxide, and the aromatic polycarbonate resin composition. It is also preferable from the viewpoint of improving the flame retardancy of the resin, and improving the affinity between the metal salt compound constituting the aromatic polycarbonate resin composition and the titanium oxide.

  Among the organosilicon compounds, for example, an organosilicon compound having an alkoxy group, an epoxy group, an amino group, or a Si—H bond is preferable, and among them, a silicone compound (hydrogen polysiloxane) having a Si—H bond is particularly preferable. More preferably, it is used. This is because the reactivity is high and the surface treatment effect tends to be high.

  The amount of the organosilicon compound used as the surface treatment agent is usually 1% by weight or more, preferably 1.5% by weight or more, and usually 5% by weight or less, preferably 3% by weight with respect to titanium oxide. % Or less. If the amount of the organosilicon compound is too small, the effect of the surface treatment may not be obtained. If the amount is too large, the amount of unreacted components increases, which may lead to the generation of gas and the deterioration of mechanical properties.

  The content of titanium oxide in the aromatic polycarbonate resin of the present invention is usually 5 parts by weight or more, preferably 7.5 parts by weight or more, more preferably 10 parts by weight or more with respect to 100 parts by weight of the aromatic polycarbonate resin described above. It is usually 25 parts by weight or less, preferably 20 parts by weight or less. If the amount of titanium oxide is too small, the surface hardness of the aromatic polycarbonate resin composition and the molded body of the present invention tends to be insufficient, and good whiteness is difficult to obtain. On the other hand, when there is too much titanium oxide, the impact resistance of the molded product of the present invention tends to be insufficient.

[4. Metal salt compound (C)]
The aromatic polycarbonate resin composition of the present invention contains a metal salt compound. Thus, the flame retardance of the aromatic polycarbonate resin composition of this invention can be improved by containing a metal salt compound.
As a kind of metal which a metal salt compound has, it is preferable that they are an alkali gold electrode or an alkaline-earth metal. The aromatic polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further enhance the flame retardancy, and has mechanical properties such as impact resistance, heat resistance, electrical properties, etc. possessed by the aromatic polycarbonate resin. This is because properties such as characteristics can be maintained satisfactorily. Accordingly, the metal salt compound according to the present invention is preferably at least one metal salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, and more preferably alkali metal salts.

Examples of the metal salt compound include an organic metal salt compound and an inorganic metal salt compound, and an organic metal salt compound is preferable from the viewpoint of good dispersibility in an aromatic polycarbonate resin.
Examples of the organic metal salt compound include an organic sulfonic acid metal salt compound, an organic carboxylic acid metal salt compound, an organic borate metal salt compound, and an organic phosphate metal salt compound. Of these, organic sulfonic acid metal salts are preferred from the viewpoint of thermal stability when mixed with an aromatic polycarbonate resin.

  Examples of organic sulfonic acid metal salt compounds include organic lithium sulfonate (Li) salt compounds, organic sodium sulfonate (Na) salt compounds, organic potassium sulfonate (K) salt compounds, and organic sulfonic acids. Rubidium (Rb) salt compound, organic cesium sulfonate (Cs) salt compound, organic magnesium sulfonate (Mg) salt compound, organic calcium sulfonate (Ca) salt compound, organic strontium sulfonate (Sr) salt compound And organic barium sulfonate (Ba) salt compounds. Among these, an organic sodium sulfonate (Na) salt compound, an organic potassium sulfonate (K) salt compound, and an organic cesium (Cs) salt compound are particularly preferable.

  Specific examples of the metal salt compound include potassium perfluorobutanesulfonate, lithium perfluorobutanesulfonate, sodium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, and the like. An alkali metal salt of a fluorine-containing alkylsulfonic acid having

At least one CF in the molecule, such as magnesium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, barium perfluorobutane sulfonate, magnesium trifluoromethane sulfonate, calcium trifluoromethane sulfonate, barium trifluoromethane sulfonate, etc. An alkaline earth metal salt of a fluorine-containing alkylsulfonic acid having a bond;

Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate Etc., alkali metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule;

Magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, magnesium (branched) dodecylbenzenesulfonate, calcium (branched) calcium dodecylbenzenesulfonate in the molecule And an alkaline earth metal salt of an aromatic sulfonic acid having the following aromatic group.

Of these, potassium perfluorobutanesulfonate, dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium paratoluenesulfonate, and potassium paratoluenesulfonate are particularly preferable.
In addition, 1 type may be used for a metal salt compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The content of the metal salt compound in the aromatic polycarbonate resin of the present invention is usually 0.01 parts by weight or more, preferably 0.03 parts by weight or more, more preferably 0, relative to 100 parts by weight of the aromatic polycarbonate resin described above. 0.05 parts by weight or more, particularly preferably 0.075 parts by weight or more, usually 1 part by weight or less, preferably 0.7 parts by weight or less, more preferably 0.5 parts by weight or less, particularly preferably 0.3 parts by weight. Or less. If the content of the metal salt compound is too small, the flame retardancy of the resulting aromatic polycarbonate resin composition may be insufficient. Conversely, if the content is too large, the thermal stability of the aromatic polycarbonate resin is reduced, and There is a possibility that the appearance defect of the molded product and the mechanical strength are lowered.

[5. Fluoropolymer (D)]
The aromatic polycarbonate resin composition of the present invention contains a fluoropolymer. Thus, by containing a fluoropolymer, the flame retardancy of the aromatic polycarbonate resin composition of the present invention can be improved, and in particular, the dripping prevention effect can be effectively enhanced.
As this fluoropolymer, a known polymer having fluorine can be arbitrarily selected and used, and among these, a fluoroolefin resin is preferred.

As fluoroolefin resin, the polymer and copolymer containing a fluoroethylene structure are mentioned, for example. Specific examples thereof include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. As this fluoroethylene resin, a fluoroethylene resin having a fibril forming ability is preferable.
Examples of the fluoroethylene resin having a fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui / Dupont Fluorochemicals, Polyflon F201L, Polyflon F103 manufactured by Daikin Chemical Industries, and the like.

Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries, Ltd.
Furthermore, a fluoroethylene polymer having a multilayer structure formed by polymerizing vinyl monomers can also be used as the fluoropolymer. Specific examples thereof include METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  The content of the fluoropolymer in the aromatic polycarbonate resin of the present invention is usually 0.01 parts by weight or more, preferably 0.05 parts by weight or more, more preferably 0.1 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. Part or more, particularly preferably 0.15 part by weight or more, usually 1 part by weight or less, preferably 0.5 part by weight or less, more preferably 0.4 part by weight or less, particularly preferably 0.35 part by weight or less. is there. If the content of the fluoropolymer is too small, the flame retardant property of the aromatic polycarbonate resin composition of the present invention may be insufficient. Conversely, if the content is too large, the molded article of the present invention has poor appearance and mechanical strength. May be reduced.

  By the way, when the aromatic polycarbonate resin mentioned above has a fluorine, the said aromatic polycarbonate resin functions not only as an aromatic polycarbonate resin based on this invention but as a fluoropolymer. In this case, the aromatic polycarbonate resin having fluorine is handled as an aromatic polycarbonate resin and a fluoropolymer in the calculation of the content of the fluoropolymer described above.

[6. Silicone resin (E)]
The aromatic polycarbonate resin composition of the present invention contains a predetermined silicone resin. By containing this silicone resin simultaneously with the metal salt compound, it is possible to impart high flame retardancy to the aromatic polycarbonate resin composition of the present invention. Further, the silicone resin exerts a certain surface treatment effect on titanium oxide, thereby suppressing the decomposition activity on the aromatic polycarbonate resin by titanium oxide. As a result, the yellow color of the aromatic polycarbonate resin composition of the present invention is reduced. It is possible to suppress the change and the decrease in whiteness. With conventional surface treatment agents, it has been difficult to completely suppress the decomposition activity of titanium oxide with a normal use amount, and thus the effect of the present invention is very useful in practice.

  The surface treatment effect on the titanium oxide by the silicone resin is exhibited regardless of the order of mixing. That is, the surface treatment effect is exhibited both when the titanium oxide is pretreated with a surface treating agent and then mixed with an aromatic polycarbonate resin or when the surface treatment is not performed in advance. For example, even when an aromatic polycarbonate resin and titanium oxide are mixed and then a silicone resin is mixed, the decomposition activity due to titanium oxide can be suppressed. Therefore, the aromatic polycarbonate resin composition of the present invention is advantageous in that its production method is easy.

The silicone resin according to the present invention has a T unit represented by RSiO _1.5 as an essential component, and (i) the T unit is an entire siloxane unit (R _0-3 SiO _{2.0-0 .5} ) Containing more than a predetermined concentration, (ii) Of the total hydrocarbon groups (R), aromatic groups occupy more than a predetermined concentration, and (iii) Silanol group content falls within a predetermined range It is. In addition to the T unit, the silicone resin according to the present invention contains a D unit represented by R ₂ SiO and a Q unit represented by the formula SiO ₂ , which impairs the object of the present invention. There is no problem unless it is.
Hereinafter, the configuration of the silicone resin will be described in detail.

The silicone resin according to the present invention usually has a monofunctional M unit represented by R ₃ SiO _0.5 , a bifunctional D unit represented by R ₂ SiO _1.0 , and RSiO _1.5. in represented by 3 functional groups of the T unit, and is composed of one or more repeating units selected from the group consisting of tetrafunctional group of Q units represented by SiO _2.0. Here, R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms. Each R may be the same or different.

  R is at least one hydrocarbon group selected from the group consisting of an alkyl group having usually 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having usually 6 to 12 carbon atoms. It is preferable that Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, hexyl group, octyl group, dodecyl group, and the like. Particularly preferred. Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, butenyl group, allyl group and the like. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, a tolyl group and the like, and among them, a phenyl group is particularly preferable.

  The silicone resin according to the present invention is usually at least 50 mol%, preferably 60 mol, of the total hydrocarbon groups (that is, R) of each repeating unit such as M unit, D unit, T unit and Q unit described above. % Or more, more preferably 65 mol% or more, particularly preferably 100 mol% is occupied by the aromatic group. When the content of the aromatic group is less than the above range, the heat resistance of the silicone resin itself decreases, and not only the silicone resin itself is easily decomposed during melt-kneading in the production process of the aromatic polycarbonate resin composition. In addition, the decomposed silicone resin may induce the decomposition of the polycarbonate resin, and further, the compatibility between the aromatic polycarbonate resin and the silicone resin is lowered, so that the dispersibility is lowered and sufficient flame retardancy is obtained. It's hard to be done. Moreover, it is preferable that content of a phenyl group is contained in the said range among aromatic groups.

Further, silicone resin according to the present invention, the T-unit, with respect to the total siloxane units _{(R 0~3 SiO 2.0~0.5),} usually 50 mol% or more, preferably 60 mol% or more More preferably, it is 70 mol% or more, still more preferably 80 mol% or more, and 100 mol% is particularly preferable. This means that the proportion of the T unit in the M unit, D unit, T unit, and Q unit constituting the silicone resin is not less than a predetermined concentration. When the content of the T unit is less than the predetermined concentration, the heat resistance of the silicone resin itself is lowered, and not only is it easily decomposed during melt-kneading, but flame retardancy tends to be extremely lowered.

  Furthermore, the content of silanol groups in the silicone resin according to the present invention is usually 2.5% by weight or more, preferably 3% by weight or more, more preferably 4% by weight or more, and particularly preferably 5% by weight or more. It is 10% by weight or less, preferably 9% by weight or less, more preferably 8% by weight or less, and particularly preferably 7.5% by weight or less. By setting the content of the silanol group in the above range, an aromatic polycarbonate resin having a low whiteness and a high whiteness, and a molded body can be obtained. The reason why such an advantage is obtained is not clear, but the silanol group exerts a kind of surface treatment effect on titanium oxide, and as a result, the decomposition activity of titanium oxide on aromatic polycarbonate resin is suppressed. Presumed to be. If the silanol group content is too small, the surface treatment effect on titanium oxide is small, and the aromatic polycarbonate resin composition may cause yellowing or a decrease in whiteness. Moreover, when there is too much silanol group content, the thermal stability of an aromatic polycarbonate resin composition may fall remarkably.

The silicone resin may contain an alkoxy group in addition to the hydroxyl group, but the amount is preferably 10% by weight or less. This is because if the alkoxy group exceeds 10% by weight, gelation is likely to occur, and the mechanical properties of the aromatic polycarbonate resin composition may be deteriorated.
Moreover, 1 type may be used for a silicone resin and it may use 2 or more types together by arbitrary combinations and a ratio.

  The average molecular weight (weight average molecular weight) of the silicone resin according to the present invention is not particularly limited and may be appropriately selected and used, but is usually 450 or more, preferably 1000 or more, more preferably 1500 or more, and particularly preferably 1700 or more. It is usually 300,000 or less, preferably 100,000 or less, more preferably 20000 or less, and particularly preferably 15000 or less. When the weight average molecular weight is less than the lower limit of the above range, it is difficult to produce, and the heat resistance of the silicone resin may be extremely lowered. Moreover, when the weight average molecular weight exceeds the upper limit of the above range, the flame retardancy tends to decrease because of poor dispersibility, and the mechanical properties of the aromatic polycarbonate resin composition tend to decrease. The weight average molecular weight is usually measured by GPC (gel permeation chromatograph).

  The content of the silicone resin in the aromatic polycarbonate resin of the present invention is usually 0.1 parts by weight or more, preferably 0.2 parts by weight or more, more preferably 0.3 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. Part or more, particularly preferably 0.5 part by weight or more, and usually 5 parts by weight or less, preferably 4.5 parts by weight or less, more preferably 4 parts by weight or less, particularly preferably 3.5 parts by weight or less. If the content of the silicone resin is too small, the flame retardant property of the aromatic polycarbonate resin composition of the present invention may be insufficient. Conversely, if the content is too large, the molded article of the present invention may have poor appearance and mechanical strength. And thermal stability may be reduced.

[7. Powdered silicone (F)]
The aromatic polycarbonate resin composition of the present invention preferably contains powdered silicone in which polyorganosiloxane is supported on the surface of silica powder. By containing this powdery silicone, the aromatic polycarbonate resin composition of the present invention tends to provide stable flame retardancy. In addition, as the powdery silicone according to the present invention, the powdery silicone described in Japanese Patent No. 3524192 can be used.

Examples of the silica powder used for the powdered silicone having a polyorganosiloxane supported on the surface of the silica powder include fumed silica, a finely pulverized silica obtained from a precipitation method, or a mining form. The fumed silica and the silica obtained from the precipitation method (hereinafter referred to as “precipitated silica” as appropriate) preferably have a surface area in the range of 50 to 400 m ² / g. When the surface area is in this range, polyorganosiloxane is easily supported (for example, absorbed, adsorbed or retained) on the surface. On the other hand, when using silica obtained from the mining form (hereinafter, referred to as “mining silica” as appropriate), at least an equal weight of fumed silica or precipitated silica is combined, and the surface area of the mixture is 50 to 400 m ² / g. The range is preferable.

  The surface of the silica powder may be pretreated with a surface treatment agent other than polyorganosiloxane (hereinafter referred to as “pretreatment agent” as appropriate). Examples of the pretreatment agent include low molecular weight polyorganosiloxane, hexaorganodisiloxane, and hexaorganodisilazane having a hydroxy group or an alkoxy group as a terminal group. Among these, particularly preferred are polydimethylsiloxanes which are oligomers having an average degree of polymerization of 2 to 100 having a hydroxyl group as a terminal group and exhibiting a liquid or viscous oil at room temperature.

  The surface of the powdery silicone according to the present invention is further treated with polyorganosiloxane (which may be referred to as a “polyorganosiloxane polymer” as appropriate in order to clarify the difference from the pretreatment agent). . The polyorganosiloxane polymer preferably has an average degree of polymerization of 100 to 10,000, more preferably 100 to 5,000. Furthermore, the polyorganosiloxane polymer may be linear or branched, but a linear polydiorganosiloxane polymer is more preferable. The organic group (organo group) possessed by the polyorganosiloxane polymer is an alkyl group having 1 to 20 carbon atoms; a substituted alkyl group such as a halogenated hydrocarbon group; an alkenyl group such as a vinyl group and a 5-hexenyl group; a cyclohexyl group Preferred examples include cycloalkyl groups such as; aryl groups such as phenyl groups, tolyl groups, and benzyl groups; and aralkyl groups. Among them, a lower alkyl group having 1 to 4 carbon atoms, a phenyl group, and a halogen-substituted alkyl group such as 3,3,3-trifluoropropyl are more preferable, and a methyl group is more preferable. In addition, 1 type may be used for a polyorganosiloxane polymer, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The polyorganosiloxane polymer may have a functional group in the molecular chain. The functional group is preferably a methacryl group or an epoxy group. When it has a methacryl group or an epoxy group, a crosslinking reaction with the aromatic polycarbonate resin can be caused at the time of combustion, so that the flame retardancy of the aromatic polycarbonate resin composition can be further improved. The amount of the functional group in the polyorganosiloxane polymer molecular chain is preferably 0.01 mol% or more, more preferably 0.03 mol% or more, particularly preferably 0.05 mol% or more, and 1 mol% or less. Is preferable, 0.5 mol% or less is more preferable, and 0.3 mol% or less is particularly preferable.

  When the polyorganosiloxane polymer is supported on silica powder, an adhesion promoter may be further used. By using an adhesion promoter, the interface between the silica powder and the polyorganosiloxane polymer can be adhered more firmly. Examples of the adhesion promoter include alkoxysilane adhesion promoters.

The alkoxysilane adhesion promoter is preferably a compound represented by the following general formula (5).
R ⁰ -Si (OMe) ₃ (5)
(In the general formula (5), Me represents a methyl group, R ⁰ is an epoxy group, an acryloxy group, methacryloxy group, vinyl group, phenyl group or N-beta-(N-vinylbenzyl-amino) ethyl -Represents a γ-aminoalkyl monohydrogenhydro chloride group.)
Specifically, alkoxysilane adhesion promoters include γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropylpropyltrimethoxysilane, N-β- (N-vinyl). Pendylamino) ethyl-γ-aminopropyltrimethoxysilane monohydrogenhydro chloride, phenyltrimethoxysilane, vinyltrimethoxysilane and the like are preferable examples.
In addition, 1 type may be used for an alkoxysilane type adhesion promoter, and it may use 2 or more types together by arbitrary combinations and a ratio.

  The adhesion promoter is preferably blended in the range of 0.5 to 15 parts by weight with respect to 100 parts by weight of the silica powder. It is desirable that the timing of blending is the same as when the silica powder and the polyorganosiloxane polymer are mixed.

  In the powdery silicone according to the present invention, the viscosity of the polyorganosiloxane polymer supported on the surface of the silica powder is not particularly limited, but is usually 10 cSt or more, preferably 100 cSt or more, more preferably 1000 cSt or more, It is 1,000,000 cSt or less, preferably 500,000 cSt or less, more preferably 100,000 cSt or less. If the viscosity is too small, the flame retardancy tends to decrease, and it tends to bleed out from the resin molded product. Conversely, if the viscosity is too large, the mixing property between the polyorganosiloxane polymer and the silica powder decreases, As a result, the dispersibility in the aromatic polycarbonate resin may be significantly reduced.

  In the powdered silicone according to the present invention, the content of polyorganosiloxane is usually 10% by weight or more, preferably 25% by weight or more, more preferably 50% by weight or more, and usually 90% by weight or less, preferably 80% by weight. % Or less, more preferably 75% by weight or less. If the content is too small, the effect of improving flame retardancy may be reduced, while if too large, the dispersibility in the aromatic polycarbonate resin may be significantly reduced.

  The particle size of the powdery silicone according to the present invention is usually 0.5 μm or more, preferably 1 μm or more, more preferably 3 μm or more, and is usually 100 μm or less, preferably 50 μm or less, more preferably 30 μm or less. If the particle size is too small, the dispersibility of the powder in the powder may be reduced. As a result, the dispersibility in the aromatic polycarbonate resin may be significantly reduced. There is a possibility of degrading.

  The content of the powdery silicone in the aromatic polycarbonate resin of the present invention is usually 0.1 parts by weight or more, preferably 0.2 parts by weight or more, more preferably 0, per 100 parts by weight of the aromatic polycarbonate resin. .3 parts by weight or more, particularly preferably 0.5 parts by weight or more, usually 10 parts by weight or less, preferably 7.5 parts by weight or less, more preferably 5 parts by weight or less, particularly preferably 3 parts by weight or less. . If the content of the powdery silicone resin is too small, the effect of improving the flame retardancy of the aromatic polycarbonate resin composition of the present invention tends to be small, and conversely, if it is too large, the appearance of the molded article of the present invention is poor. And mechanical strength and thermal stability may be reduced.

[8. Other ingredients]
The aromatic polycarbonate resin composition of the present invention is not limited to those described above, if necessary, as long as the desired physical properties (for example, flame retardancy, transparency, hue, thermal stability, etc.) are not significantly impaired. It may contain components. Examples of other components include other resins of various aromatic polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), and acrylonitrile-styrene copolymer. Styrene such as (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) Polyolefin resin; Polyethylene resin; Polyimide resin; Polyetherimide resin; Polyurethane resin; Polyphenylene ether resin; Polyphenylene Examples include sulfide resin; polysulfone resin; polymethacrylate resin, polylactic acid (PLA), polybutylene succinate (PBS) resin, and the like. In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, lubricants and antiblocking agents. Agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, fluorescent whitening agents and the like. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the aromatic polycarbonate resin composition of this invention is demonstrated concretely.

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Among these, the organic phosphate compound represented by the following formula (6) and / or the organic phosphite compound represented by the following formula (7) are preferable.

O = P (OH) _m (OR) _3-m (6)
In the above formula (6), R represents an alkyl group or an aryl group. Among them, R is usually an alkyl group having 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, or an aryl group having usually 6 or more and usually 30 or less carbon atoms. Is more preferable. Furthermore, R is preferably an alkyl group rather than an aryl group. In addition, when two or more R exist, each R may be the same or different.
In the formula (6), m is usually 0 or more, preferably 1 or more, and usually represents an integer of 2 or less.

  In the formula (7), R ′ represents an alkyl group or an aryl group. Among them, R ′ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. R ′ may be the same or different.

Preferred specific examples of the organic phosphite compound represented by the formula (7) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the heat stabilizer is usually 0.001 parts by weight or more, preferably 0.01 parts by weight or more, more preferably 0.03 parts by weight or more with respect to 100 parts by weight of the aromatic polycarbonate resin. Usually, it is 1 part by weight or less, preferably 0.7 part by weight or less, more preferably 0.5 part by weight or less. If the amount of the heat stabilizer is too small, the heat stabilization effect may be insufficient. If the amount of the heat stabilizer is too large, the effect may reach a peak and may not be economical.

.. Antioxidant Examples of the antioxidant include hindered phenol antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesi Tylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

Of these, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are preferable. . These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 1 part by weight or less, preferably 0.5 part, based on 100 parts by weight of the aromatic polycarbonate resin. Less than parts by weight. If there are too few antioxidants, the effect as an antioxidant may become inadequate, and when there are too many antioxidants, an effect may reach | attain and it may become economical.

.. Release agent Examples of the release agent include, for example, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols (that is, aliphatic carboxylic acid esters), aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, Examples include polysiloxane silicone oil.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated, linear or cyclic, aliphatic monovalent, divalent, or trivalent carboxylic acid. Among these, preferable aliphatic carboxylic acids are monovalent or divalent carboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetrariacontanoic acid, montanic acid. , Adipic acid, azelaic acid and the like.

  As aliphatic carboxylic acid in aliphatic carboxylic acid ester, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol moiety of the ester include saturated or unsaturated, linear or cyclic, monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and saturated aliphatic monovalent or polyhydric alcohols having 30 or less carbon atoms are more preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaol. Examples include erythritol.

  The aliphatic carboxylic acid ester may contain an aliphatic carboxylic acid and / or an alcohol as an impurity. The aliphatic carboxylic acid ester may be a pure substance or a mixture of a plurality of aliphatic carboxylic acid esters. Furthermore, the aliphatic carboxylic acid and alcohol which combine and comprise one aliphatic carboxylic acid ester may each use 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  Specific examples of the aliphatic carboxylic acid ester include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin di Examples thereof include stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Moreover, these hydrocarbon compounds may be partially oxidized.

Among these aliphatic hydrocarbons, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
Further, the number average molecular weight of the aliphatic hydrocarbon is preferably 200 or more, and more preferably 5000 or less.
The aliphatic hydrocarbon may be a single substance or a mixture of various constituent components and molecular weights as long as the main component is within the above range.

  Examples of the polysiloxane silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

  In addition, 1 type may contain the mold release agent mentioned above, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the release agent is usually 0.001 part by weight or more, preferably 0.01 part by weight or more, and usually 2 parts by weight or less, preferably 1 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. Or less. If the content of the release agent is too small, the release effect may not be sufficient. If the content is too high, the hydrolysis resistance of the aromatic polycarbonate resin composition may deteriorate, and mold contamination may occur during injection molding. There is sex.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. Of these, organic ultraviolet absorbers are preferred. A benzotriazole compound is particularly preferable.

  Specific examples of the benzotriazole compound include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl. ] -Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methyl) Phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′-hydroxy-3 ′, 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2 ' -Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like. Among them, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazole) 2-yl) phenol] is preferred, and 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferred. Specific examples of such benzotriazole compounds include “Seasorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704” and “Seesorb 704” manufactured by Sipro Kasei Co., Ltd. Seasorb 709, “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. "LA-32", "LA-38", "LA-36", "LA-34", "LA-31" manufactured by Adeka Company, "Chinubin P", "Tinubin 234" manufactured by Ciba Specialty Chemicals, "Tinubin 326", "Tinubin 327", "Tinubin 328" And the like.

  Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4 Examples include '-dimethoxybenzophenone. Specific examples of such benzophenone compounds include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102” and “Seesorb 103” manufactured by Sipro Kasei Co., Ltd. “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 ", Ade Company Ltd. "ADK STAB 1413", and "ADEKA STAB LA-51" and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such salicylate compounds include “Seasorb 201” and “Seasorb 202” manufactured by Sipro Kasei Co., Ltd., “Chemisorb 21” and “Chemisorb 22” manufactured by Chempro Corporation. .

  Specific examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Examples of such cyanoacrylate compounds include, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., BASF Corporation. “Ubinurur N-35”, “Ubinurur N-539” and the like can be mentioned.

  Specific examples of the oxanilide compound include 2-ethoxy-2'-ethyloxalinic acid bis-arinide and the like. Specific examples of such oxalinide compounds include “Sanduboa VSU” manufactured by Clariant.

  Examples of the malonic acid ester compound include 2- (alkylidene) malonic acid esters, particularly 2- (1-arylalkylidene) malonic acid esters, particularly those represented by the following formula (8). preferable.

（式（８）中、Ｘ^１は、水素原子、置換基を有していてもよい、炭素数１〜８の、アルキル基若しくはアルコキシ基、または、炭素数２〜１０のアルケニル基を示し、Ｒ^１及びＲ^２はそれぞれ独立に炭素数１〜６のアルキル基を表わす。）

(In Formula (8), X ¹ represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent, R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms.)

In Formula (8), X ¹ represents a hydrogen atom, an alkyl group or an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, which may have a substituent.
The carbon number of the alkyl group and the alkoxy group in X ¹ is usually 1 or more, usually 8 or less, preferably 6 or less, more preferably 4 or less. Moreover, the alkyl group in an alkyl group or an alkoxy group may be linear or branched. Examples of this alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like.
Further, among X ¹ , the alkenyl group preferably has an ester group as a substituent. The carbon number of the alkenyl group including the carbon number of the substituent is usually 2 or more, preferably 3 or more, more preferably 4 or more, and usually 10 or less, preferably 8 or less. Among them, X ¹ itself is preferably a 2- (alkylidene) malonic acid ester which is a malonic acid ester moiety of the above formula (8), and among them, the same malon with the benzene ring of the formula (8) as the center. Those having acid ester residues are more preferred, and those having a para-position are particularly preferred.

In the formula (8), R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms. Among them, the number of carbon atoms in ^{R 1} and ^{R 2} are 1-4 preferred. In addition, the alkyl groups represented by R ¹ and R ² may each be linear or branched. Specific examples of R ¹ and R ² include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group and the like. Of these, a methyl group is more preferred. R ¹ and R ² may be the same or different.

  Specific examples of such malonic ester UV absorbers include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

  The content of the ultraviolet absorber is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and usually 3 parts by weight or less, preferably 1 part by weight or less with respect to 100 parts by weight of the base resin. It is. If the content of the ultraviolet absorber is too small, the effect of improving the weather resistance may be insufficient, and if it is too large, mold deposits and the like may occur. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the dye / pigment is usually 5 parts by weight or less, preferably 3 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

..Fluorescent whitening agent Examples of the fluorescent whitening agent include coumarins, naphthotriazolyl stilbenes, benzoxazoles, benzimidazoles, diaminostilbene disulfonates, and the like. Specific examples of the optical brightener include 3-phenyl-7- (2H-naphtho (1,2-d) -triazol-2-yl) coumarin (manufactured by Hackol Chemical Co., trade name: Hackol PSR), 2,5-thiophenediyl (5-tert-butyl-1,3-benzoxazole) (manufactured by Ciba, trade name: UVITEX OB), 4,4′-bis (benzoxazol-2-yl) stilbene (Ciba (Trade name: UVITEX OB-ONE).
In addition, 1 type of fluorescent whitening agents may be contained and 2 or more types may be contained by arbitrary combinations and ratios.

[9. Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include the above-described titanium oxide (B), metal salt compound (C), fluoropolymer (D) and silicone resin (E), and the aromatic polycarbonate resin (A) according to the present invention. The powdered silicone (F) and other components to be blended accordingly are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then Banbury mixer, roll, brabender, single-screw kneading extruder, twin screw A method of melt-kneading with a mixer such as a kneading extruder or kneader can be mentioned.

Also, for example, without mixing each component in advance, or only a part of the components are mixed in advance, and fed to an extruder using a feeder and melt-kneaded to obtain the aromatic polycarbonate resin composition of the present invention. It can also be manufactured.
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, the master batch is again mixed with other components and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced. In this case, the metal salt compound (C) and the silicone resin (E) are mixed with a resin component such as the aromatic polycarbonate resin (A) in advance to prepare a master batch, and then mixed with other components and melt-kneaded. It is preferable because an aromatic polycarbonate resin composition having excellent dispersibility and extruding workability can be obtained. Further, from the viewpoint of improving the dispersibility of the metal salt compound (C) described above, the metal salt compound (C) can be previously dissolved in a solvent such as water or an organic solvent and then kneaded.

[10. Main advantages]
The aromatic polycarbonate resin composition of the present invention is excellent in flame retardancy and surface hardness, has a small degree of yellowing, and has a good appearance with high whiteness. In addition, when the dye or pigment is contained, the aromatic polycarbonate resin composition of the present invention is not white, but even in that case, the yellowing can be suppressed unintentionally because the yellowing can be suppressed. The color of the aromatic polycarbonate resin of the present invention can be easily set to the color as intended.
In addition, the aromatic polycarbonate resin composition of the present invention usually has the above-mentioned flame retardancy, surface hardness, and without impairing the excellent mechanical properties, thermal properties, and electrical properties of the aromatic polycarbonate resin. A white appearance can be achieved.
Furthermore, the aromatic polycarbonate resin composition of the present invention usually has an advantage of being excellent in heat resistance, impact resistance, moldability and colorability.

[11. Molded body]
The above-described aromatic polycarbonate resin composition of the present invention is usually molded into some shape and used as a molded body (aromatic polycarbonate resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of molded articles include electric / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, lighting equipment, and the like. . Among these, it is particularly suitable for use in electrical / electronic equipment, OA equipment, information terminal equipment, housings for home appliances, cover members, vehicle exterior / skin parts, and interior parts.

  Examples of the electrical / electronic devices, OA devices, information terminal devices, housings for home appliances, and cover members include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks, and PDAs. , Electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, battery packs, drive and readers for recording media, mice, numeric keys, CD players, MD players, portable radio / audio player housings, covers, keyboards , Buttons, switch members, and the like.

  In addition, since the molded product of the present invention can be expected to improve light shielding properties and light reflectivity, for example, electrical / electronic devices using liquid crystal backlights, lighting devices such as advertising lights, automobile devices such as meter panels, etc. Also, it can be suitably used. Furthermore, it can be used for vehicle equipment other than automobiles, such as two-wheeled vehicles, agricultural vehicles, special vehicles for civil engineering and construction, and railway vehicles.

  The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by weight” based on the weight basis unless otherwise specified.

[Production of resin pellets]
Each component described in Table 2 to be described later is blended at a ratio (weight ratio) described in Table 3, mixed for 20 minutes with a tumbler, and then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent. The molten resin kneaded under the conditions of a screw rotational speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C., rapidly cooled in a water tank, pelletized using a pelletizer, and an aromatic polycarbonate resin composition Pellets were obtained.

[Preparation of UL test specimen]
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., a molding cycle of 30 using a J50-EP type injection molding machine manufactured by Nippon Steel. A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.58 mm was formed by injection molding under the conditions of seconds. The obtained molded body was evaluated for flame retardancy as a UL test sample in the manner described below.

[Preparation of flat molded body]
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, a cylinder temperature of 290 ° C., a mold temperature of 80 ° C., a molding cycle of 30 using a J50-EP type injection molding machine manufactured by Nippon Steel. A test piece having a length of 90 mm, a width of 50 mm, and a thickness of 3 mm was molded under injection conditions. The obtained molded body was evaluated as whiteness, yellowing degree and surface hardness as a test sample for whiteness, yellowing degree and surface hardness as described later.

[Flame retardance evaluation]
The flame retardant evaluation of each aromatic polycarbonate resin composition was carried out by conditioning a test specimen for UL test for 48 hours in a temperature-controlled room with a temperature of 23 ° C. and a humidity of 50%. US Underwriters Laboratory (UL) UL In accordance with the UL94 test (combustion test of plastic materials for equipment parts). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

  Here, the after-flame time is the length of time for which the flammable combustion of the test piece is continued after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. Further, when any one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

[Whiteness]
According to JIS K-7105, the above-mentioned flat molded body (3 mm thickness) was used as a test piece, and the SE, 2000 type spectral colorimeter manufactured by Nippon Denshoku Industries Co., Ltd. Measured, and Hunter Lab whiteness W (Lab) was obtained from the following definition formula.
W (%) = 100 − [(100−L) ² + (a ² + b ² )] ^0.5
In the above formula, L, a, and b represent the lightness (L) and the perceptual chromaticity index (a, b) in Lab color coordinates, respectively.

[Yellowness]
According to JIS K-7105, the above-mentioned flat molded body (thickness 3 mm) was used as a test piece, and a Y2000 (Yellow Index) value was obtained by a reflection method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. It was measured. A smaller YI value indicates a lower degree of yellowing and is preferred.

[surface hardness]
In accordance with JIS K-5400, the above-mentioned flat molded body (thickness 3 mm) was used as a test piece, a pencil hardness test was performed, and the surface hardness (scratch resistance) was evaluated.

  From Table 3, the present invention includes aromatic polycarbonate resin (A), titanium oxide (B), metal salt compound (C), fluoropolymer (D), and silicone resin (E) in predetermined amounts. It can be seen that the aromatic polycarbonate resin composition is excellent in flame retardancy and surface hardness, has low yellowing, and has a good whiteness.

  The present invention can be used in a wide range of industrial fields. For example, electric / electronic devices and parts thereof, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure It is suitable for use in the fields of goods, miscellaneous goods, lighting equipment and the like.

Claims (6)

100 parts by weight of aromatic polycarbonate resin (A),
5 to 25 parts by weight of titanium oxide (B),
0.01 to 1 part by weight of a metal salt compound (C),
0.01-1 part by weight of fluoropolymer (D),
The unit represented by RSiO _1.5 (wherein R represents a monovalent hydrocarbon group having 1 to 12 carbon atoms) is the entire siloxane unit (R _0-3 SiO _2.0-0.5 ). And 50 mol% or more of the total hydrocarbon group (R), the aromatic group occupies 50 mol% or more, and the silanol group content is 2.5 to 10 wt%. An aromatic polycarbonate resin composition comprising 0.1 to 5 parts by weight of a resin (E).   The aromatic polycarbonate resin composition according to claim 1, wherein the aromatic group of the silicone resin (E) is a phenyl group.   The metal salt compound (C) is an alkali metal salt and / or an alkaline earth metal salt of a fluorine-containing alkyl sulfonic acid and / or an aromatic sulfonic acid, according to claim 1 or 2. Aromatic polycarbonate resin composition.   The aromatic polycarbonate resin according to any one of claims 1 to 3, comprising 0.1 to 10 parts by weight of powdery silicone (F) having a polyorganosiloxane supported on the surface of silica powder. Composition.   A molded article obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 4.   A housing formed by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 4.