JP2011219620A - Thermoplastic resin composition and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition of a polycarbonate resin, being superior in light blocking property and balance of flowability, impact resistance, and flame retardancy, and a molding article using the same.SOLUTION: The thermoplastic resin composition contains 2 to 25 parts by mass of a phosphoric ester flame retardant (B), 1 to 10 parts by mass of a ZrO-SiO-HfOcomposite oxide (C) that has a mean particle size of 0.1 to 4 μm, and 0.001 to 1 parts by mass of a fluorine-containing resin (D) with respect to 100 parts by mass of a thermoplastic resin containing 50% by mass or more to less than 93% by mass of an aromatic polycarbonate resin and more than 7% by mass to less than 50% by mass of an aromatic vinyl-diene-vinyl cyanide copolymer. The molded article is obtained by molding the thermoplastic resin composition.

Description

  The present invention relates to a thermoplastic resin composition and a molded article using the same, and more specifically, an aromatic polycarbonate thermoplastic resin having excellent light shielding properties and excellent balance of fluidity, impact resistance and flame retardancy. The present invention relates to a composition and a molded article comprising the composition.

  Aromatic polycarbonate resin is a resin with excellent heat resistance, mechanical properties, and electrical characteristics. For example, it is widely used in automobile materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. ing. In particular, the flame-retardant aromatic polycarbonate resin composition is suitably used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin.
However, a polycarbonate resin composition containing a halogen-based flame retardant containing chlorine or bromine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding processing. there were.

  On the other hand, as a technique for imparting flame retardancy to a thermoplastic resin without using a halogen compound, a technique using a phosphoric acid flame retardant has been actively studied. (For example, refer to Patent Document 1) Polycarbonate resin blended with a phosphorus-based flame retardant is necessary for combustion gas and combustion due to the effect of diluting the combustion gas in the air layer and forming a heat insulating carbonized layer on the surface of the molded product during combustion. It is known that the effect of blocking air, the effect of delaying heat conduction, and the like are exhibited, and the flame retardancy is improved.

  However, if the amount of the phosphorus-based flame retardant is increased for the purpose of obtaining high flame retardancy or enhancing fluidity, the excellent heat resistance and excellent impact resistance of the polycarbonate resin tend to be remarkably reduced. It was in. In addition, when a polycarbonate resin composition containing an excessive amount of phosphorus-based flame retardant is used in the product, the phosphorus-based flame retardant bleeds out from the product at the time of disposal, which may cause environmental pollution. There are also dangers to the human body.

In addition, it has been reported that various properties of a resin are modified by adding zirconium oxide, zirconium silicate, or the like to various thermoplastic resins (see Patent Documents 2 to 6).
However, in the method of adding flame retardancy by adding specific inorganic particles to the aromatic polycarbonate as described above, the decomposition of the polycarbonate due to the addition of the inorganic particles cannot be sufficiently controlled, and the polycarbonate is used during molding processing. There was a problem that decomposition of the material occurred and the physical properties deteriorated.

In addition, when a plate-like or needle-like silicate compound such as mica or talc as described above is blended, the stress tends to concentrate when an impact is applied, and the excellent impact resistance of the aromatic polycarbonate resin is significantly reduced. Has a fatal drawback.
Further, when talc or mica is blended, the polycarbonate resin composition can be easily seen through, the concealability and the light shielding property are insufficient, and there is a drawback that the use of the molded product is limited.
Under such circumstances, there has been a strong demand for the development of a polycarbonate resin composition that is excellent in light-shielding properties and has a good balance of fluidity, impact resistance, and flame retardancy.

JP 59-202240 A JP-A-6-279661 JP-A-6-279665 Japanese Patent Laid-Open No. 7-25154 JP-A-7-145265 JP-A-8-311315

  An object of the present invention is to provide an aromatic polycarbonate resin composition having excellent light shielding properties and excellent balance of fluidity, impact resistance and flame retardancy, and a polycarbonate molded article comprising the same, in view of the above-mentioned problems of the prior art. There is.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a resin composition containing a specific amount of an aromatic polycarbonate resin and an ABS resin, and a metal salt compound and an average particle size within a specific range. By blending zirconium, silicon, and hafnium composite oxides in specific proportions, an aromatic polycarbonate resin-based material that has excellent light shielding properties and excellent balance of fluidity, impact resistance, and flame retardancy can be obtained. The inventors have found that the present invention can be obtained and have completed the present invention.

That is, according to the first invention of the present invention, the aromatic polycarbonate resin (A-1) is 50% by mass or more and less than 93% by mass and the aromatic vinyl-diene-vinyl cyanide copolymer (A-2). ) For 100 parts by mass of thermoplastic resin (A) containing 50% by mass or less and more than 7% by mass,
2 to 25 parts by mass of phosphate ester flame retardant (B), 1 to 10 parts by mass of ZrO ₂ —SiO ₂ —HfO ₂ complex oxide (C) having an average particle size of 0.1 to 4 μm, and fluorine-containing resin (D) The thermoplastic resin composition characterized by containing 0.001-1 mass part is provided.

（式中、Ｒ_１、Ｒ_２、Ｒ_３およびＲ_４は、各々独立して、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基、Ｘはアリーレン基を示し、ｐ、ｑ、ｒおよびｓは、それぞれ０または１であり、ｋは１から５の整数である。） According to the second invention of the present invention, the thermoplastic resin according to the first invention, wherein the phosphate ester flame retardant (B) is a compound represented by the following general formula (1): A resin composition is provided.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, X Represents an arylene group, p, q, r and s are each 0 or 1, and k is an integer of 1 to 5.)

According to the third invention of the present invention, in the first or second invention, the composition of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) is ZrO ₂ : 50 to 80% by mass, A thermoplastic resin composition characterized by SiO ₂ : 25 to 45 mass% and HfO ₂ : 0.05 to 5 mass% is provided.

According to the fourth invention of the present invention, in any one of the first to third inventions, the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) further contains Fe ₂ O ₃ and ZrO _2. , SiO ₂ and HfO ₂ are provided in a thermoplastic resin composition characterized by containing 0.005 to 0.05% by mass with respect to 100% by mass in total.

According to the fifth aspect of the present invention, in any one of the first to fourth aspects, the surface treating agent (E) is further added to a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) 100. A thermoplastic resin composition containing 0.05 to 10 parts by mass with respect to parts by mass is provided.

  According to a sixth aspect of the present invention, in the fifth aspect, the surface treatment agent (E) is a SiH group-containing organosilicon polymer or a silane coupling agent. Things are provided.

  Furthermore, according to the 7th invention of this invention, the molded article formed by shape | molding the thermoplastic composition which concerns on either of the 1st-6th invention is provided.

  According to the thermoplastic resin composition of the present invention, it is possible to obtain an aromatic polycarbonate resin composition having excellent light shielding properties and excellent balance of fluidity, impact resistance and flame retardancy.

  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

[1. Overview]
The aromatic polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (A-1), an aromatic vinyl-diene-vinyl cyanide copolymer (A-2), and a metal salt compound (B). Each of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxides (C) having a specific average particle size is contained in a specific amount.

[2. Aromatic polycarbonate resin (A-1)]
The type of the aromatic polycarbonate resin used in the aromatic polycarbonate resin composition of the present invention is not limited, and only one type may be used, and two or more types are used in any combination and in any ratio. May be.
The aromatic polycarbonate resin in the present invention is a polymer having a basic structure having a carbonic acid bond represented by the following general formula.

（式中、Ｘ^１は、一般には炭化水素であるが、種々の特性付与のためヘテロ原子、ヘテロ結合の導入されたＸ^１を用いてもよい。）

(In the formula, X ¹ is generally a hydrocarbon, but for imparting various properties, X ¹ into which a hetero atom or a hetero bond is introduced may be used.)

  As the aromatic polycarbonate resin, a polycarbonate resin in which carbons directly bonded to carbonic acid bonds are aromatic carbons is used. Aromatic polycarbonate is excellent from the viewpoints of heat resistance, mechanical properties, electrical characteristics, etc., among various polycarbonates.

  Although there is no restriction | limiting in the specific kind of aromatic polycarbonate resin, For example, the aromatic polycarbonate polymer formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used. 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 may be a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. Normally, such an aromatic polycarbonate polymer is a thermoplastic resin.

Examples of the aromatic dihydroxy compound among the monomers used as the raw material for the aromatic polycarbonate resin are as follows.
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;

2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2′-dihydroxydiphenyl ether, 3,3′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxy diaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α′-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,10-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,4-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;
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;
And dihydroxydiaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone;

Of these, bis (hydroxyaryl) alkanes are preferable, and bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane is particularly preferable in terms of impact resistance and heat resistance. (Ie bisphenol A) is preferred.
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.

  Among the monomers used as the raw material for the aromatic polycarbonate resin, carbonyl halides, carbonate esters and the like are used as examples of the carbonate precursor. 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.

  Specific examples of carbonyl halides include phosgene; haloformates such as bischloroformate of dihydroxy compounds and monochloroformate of dihydroxy compounds.

  Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-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, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. An aromatic polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and the 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 compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate. Among them, sodium hydroxide and Potassium hydroxide 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 alkaline aqueous solution, Usually, in order to control pH in the alkaline aqueous solution of reaction to 10-12, it is used at 5-10 mass%. 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. In particular, it is preferably set to 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 aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine. Formula tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; 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 aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, and the like. Among them, aromatic phenols are preferable. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropanyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as 0-oxine benzoic acid and 2-methyl-6-hydroxyphenylacetic acid; 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 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 between the reaction (phosgenation) of the dihydroxy compound and phosgene and 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 a dihydroxy compound is performed.

The 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. Of these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is particularly 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 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 dihydroxy compound. It is more preferable to use the above. 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 the 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 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 pressure reduction 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 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 them, it is preferable to use, for example, 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 conditions while removing by-products such as aromatic hydroxy compounds.

  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 aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, considering the stability of the aromatic polycarbonate resin and the aromatic polycarbonate resin composition, the melt polycondensation reaction is preferably carried out continuously.

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 (A-1) used in the present invention is arbitrary and may be appropriately selected and determined. However, the viscosity average molecular weight [Mv] is preferably 10,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength tends to be insufficient, and when the viscosity average molecular weight exceeds 40,000, the fluidity is poor and the moldability tends to be deteriorated. The viscosity average molecular weight is more preferably 16,000 to 40,000, further preferably 18,000 to 30,000, particularly 13,500 to 20,500. The molecular weight can be adjusted to such a range by a known method such as controlling the amount of the molecular weight regulator as described later.

  Here, 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, Schnell's viscosity formula, That is, it means a value calculated from 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 [ηsp] at each solution concentration [C] (g / dl).

Other matters regarding aromatic polycarbonate resin The terminal hydroxyl group concentration of the aromatic polycarbonate resin is arbitrary and may be appropriately selected and determined, but is usually 1,000 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 measuring method is performed by colorimetric determination (method described in Macromol. Chem. 88 215 (1965)) by a titanium tetrachloride / acetic acid method.

  In addition, aromatic polycarbonate resin (A-1) is not limited to the aspect containing only 1 type of aromatic polycarbonate resin, 2 or more types of aromatic polycarbonate resin from which a monomer composition, molecular weight, terminal hydroxyl group concentration, etc. differ is mixed. May be used. Moreover, you may use combining as an alloy (mixture) which mixed another thermoplastic resin with aromatic polycarbonate resin.

  Further, for example, for the purpose of further improving flame retardancy and impact resistance, an aromatic polycarbonate resin is a copolymer with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy. Copolymer with monomer, oligomer or polymer having phosphorus atom; copolymer with monomer, oligomer or polymer having dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; polystyrene to improve optical properties A copolymer with an oligomer or polymer having an olefinic structure such as; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; May be.

  Further, in order to improve the appearance of the molded product and improve the fluidity, the polycarbonate resin may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by weight or less of the polycarbonate resin (including the polycarbonate oligomer).

Furthermore, the aromatic polycarbonate resin may be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product (a 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 mass or less, more preferably 50% by mass or less, among the aromatic polycarbonate resins contained in the aromatic polycarbonate resin composition of the present invention. More preferred. The regenerated aromatic polycarbonate resin is likely to have been subjected to deterioration such as heat deterioration and aging deterioration. Therefore, when such an aromatic polycarbonate resin is used more than the above range, hue and mechanical properties It is because there is a possibility of lowering.

[3. Aromatic vinyl-diene-vinyl cyanide copolymer (A-2)]
The copolymer (A-2) used in the present invention comprises an aromatic vinyl monomer and a diene, a vinyl cyanide monomer, and, if necessary, other copolymerizable monomers.
The diene is butadiene, isoprene or the like, preferably a prepolymerized diene rubber, such as polybutadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, etc. These can be mentioned, and these can be used alone or in combination of two or more. Particularly preferably, polybutadiene rubber and / or styrene-butadiene copolymer rubber is used.

Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, vinyltoluene, and the like, and styrene and / or α-methylstyrene is particularly preferable.

The copolymer composition ratio is not particularly limited, but 10 to 70 parts by weight of a diene rubber is preferable with respect to 100 parts by weight of the copolymer from the viewpoint of molding processability and impact resistance of the obtained resin composition. Similarly, the amount of vinyl cyanide monomer is preferably 8 to 40 parts by weight. The aromatic vinyl monomer is preferably in the range of 20 to 80 parts by weight.
The method for producing the copolymer is not particularly limited, and known methods such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or bulk / suspension polymerization are used.

  The content of the aromatic vinyl-diene-vinyl cyanide copolymer (A-2) is that of the polycarbonate resin (A-1) and the aromatic vinyl-diene-vinyl cyanide copolymer (A-2). It is more than 7 mass% and 50 mass% or less with respect to a total of 100 mass%. By containing the aromatic vinyl-diene-vinyl cyanide copolymer in this way, the impact resistance and fluidity of the polycarbonate resin composition of the present invention can be improved. A more preferable content is 10 to 30% by mass, particularly 12 to 25% by mass.

[4. Phosphate ester flame retardant (B)]
The thermoplastic resin composition of the present invention contains 2 to 25 parts by mass of the phosphate ester flame retardant with respect to 100 parts by mass of the thermoplastic resins (A-1) and (A-2). Thus, the flame retardance of the aromatic polycarbonate resin composition of this invention can be improved by containing a phosphate ester type flame retardant.

  The phosphate ester flame retardant in the present invention is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. For example, the following general formula (1 ) Or a phosphorus compound represented by (2), and the phosphorus flame retardant represented by the general formula (1) is particularly preferable from the viewpoint of thermal stability.

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group). X represents an arylene group, p, q, r and s are each 0 or 1, and k is an integer of 1 to 5.)

(Wherein R ₅ , R ₆ and R ₇ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, and h, i and j) Represents 0 or 1 respectively.)

The phosphorus compound represented by the general formula (1) is a condensed phosphate ester having k of 1 to 5. For a mixture of condensed phosphate esters having different k, k is an average value of the mixture. X represents an arylene group, for example, resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3′-dihydroxybiphenyl, 3, 4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1 , 7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and the like. Of these, residues from resorcinol or bisphenol A are particularly preferred.
Further, p, q, r and s in the general formula (1) are preferably 1.

  As a specific example of the phosphorus compound represented by the general formula (1), when resorcinol is used as a dihydroxy compound, phenyl resorcinol polyphosphate, cresyl resorcin polyphosphate, phenyl cresyl resorcin polyphosphate, Xylyl resorcin polyphosphate, phenyl-pt-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin polyphosphate Etc.

  The phosphorus compound represented by the general formula (2) can be produced from phosphorus oxychloride or the like by a known method. Specific examples of the phosphorus compound represented by the general formula (2) include triphenyl phosphate, tricresyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, and phenylphosphonic acid. Examples include diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

  Further, the phosphorus-based flame retardant in the present invention may be a phosphazene compound. Such a compound is at least one selected from a cyclic phenoxyphosphazene compound, a chain phenoxyphosphazene compound, and a crosslinked phenoxyphosphazene compound.

  The content of the phosphate ester flame retardant is 2 parts by mass or more, preferably 5 parts by mass or more, more preferably 8 parts by mass or more, and 25 parts by mass or less, preferably 22 with respect to 100 parts by mass of the thermoplastic resin. .5 parts by weight or less, more preferably 20 parts by weight or less. When the blending amount of the phosphorus-based flame retardant is less than 2 parts by mass, the flame retardancy is insufficient, and when it exceeds 25 parts by mass, a remarkable decrease in heat resistance and a decrease in mechanical properties are caused.

[5. ZrO ₂ —SiO ₂ —HfO ₂ Complex Oxide (C)]
The aromatic polycarbonate resin composition of the present invention comprises a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide having an average particle size of 0.1 to 4 μm with respect to 100 parts by mass of the thermoplastic resin (A). Contains 10 parts by weight. By containing a predetermined amount of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide having such a particle size, the light shielding property is improved, and the flame extinguishing effect during combustion and the dripping prevention property are improved. The flame retardancy of the composition can be increased.

In addition, compared to conventional plate-like silicate compounds such as talc and mica and needle-like silicate compounds such as wollastonite, the aromatic polycarbonate has excellent thermal properties and good mechanical properties and thermal characteristics. Even when the resin composition is obtained and the fluidity is improved, there is an advantage that the impact resistance is hardly lowered.
In addition, the aromatic polycarbonate resin composition satisfies the low light transmittance and whiteness, and exhibits an important performance in terms of application development of the polycarbonate material, which is excellent in light shielding properties.

If the content of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is less than 1 part by mass, a sufficient effect of improving flame retardancy cannot be obtained, and if it exceeds 10 parts by mass, the resistance of the aromatic polycarbonate resin composition is increased. Impact resistance is reduced. The lower limit of the content is preferably 1.5 parts by mass or more, more preferably 2 parts by mass or more, and the upper limit of the content is preferably 8 parts by mass or less, more preferably 7 parts by mass or less.

The ZrO ₂ —SiO ₂ —HfO ₂ composite oxide used in the present invention is a composite oxide of zirconium (Zr), silicon (Si), and hafnium (Hf), and is a natural product produced from nature. Alternatively, a chemically synthesized product may be used, but a natural product is preferable from the viewpoint that the manufacturing process is easy, the manufacturing energy is small, and an industrially inexpensive product is obtained.

When the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide used in the present invention is a natural product, the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide produced from nature may be appropriately pulverized and used. At this time, purification may be performed, or drying or baking may be performed. Further, the pulverization method may be appropriately selected as long as it is a known method. Specifically, it may be a dry method or a wet method, but ZrO having a relatively fine particle size and high purity. _{In view of} obtaining a ₂ -SiO ₂ —HfO ₂ -based composite oxide, grinding by a wet method is more preferable.

Further, when the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is a synthetic product,
Ethyl silicate _{(Si (OC 2 H 5)} 4) and zirconium oxychloride (ZrOCl ₂ · _{8H 2} O) and hafnium oxychloride _{(HfOCl 2 · 8H 2 O)} ,
Zirconium tetraisopropoxide (Zr (O-iPr) ₄ ), hafnium tetraisopropoxide (Hf (O-iPr) ₄ ), starting from ethyl silicate and zirconium and hafnium alkoxides,
Sol-gel method using SiO ₂ sol, zirconium tetraisopropoxide and hafnium tetraisopropoxide, zirconium silicon hafnium oxide obtained by hydrothermal synthesis method, or
Sodium silicate _{(Na 2 O · nSiO 2 ·} xH 2 O: n = 2~4) and, zirconium oxychloride, _{ZrO 2} -SiO 2 -HfO 2 composite obtained by hydrolytic polycondensation of hafnium oxychloride An oxide is mentioned.

The average particle diameter of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide used in the present invention is 0.1 to 4 μm. When a particle having a particle size in this range is blended with a polycarbonate resin, the originally dark color becomes white and a beautiful color is easily exhibited. When the average particle size is out of the range of 0.1 to 4 μm, it becomes difficult to achieve an appropriate light transmittance and whiteness, resulting in poor light shielding properties. A preferable lower limit is 0.5 μm or more, and a preferable upper limit is 3.5 μm or less, and particularly preferably 3 μm or less. When the average particle size is less than 0.1 μm, the dispersibility in the aromatic polycarbonate resin is remarkably reduced. When the average particle size exceeds 4 μm, the appearance of the molded product is deteriorated, and the impact resistance is increased. This is not preferable because the properties also deteriorate.

Note that the average particle size of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide in the present invention is the integration in the particle size distribution obtained by measurement using a cedy graph (X-ray transmission type particle size distribution measuring device). The particle size at which the weight distribution is 50%. The Cedygraph is an apparatus that irradiates a suspension during sedimentation with an X-ray beam and measures the particle size distribution from the amount of X-ray transmission.

In addition, the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide used in the present invention preferably has a pH value of 4 to 7.5 measured according to the JIS K5101-17-2 method. More preferably, it is 4 to 7.0. When the pH of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is less than 4, the heat and humidity stability of the aromatic polycarbonate resin tends to decrease, and when the pH exceeds 7.5, the aromatic polycarbonate This is not preferable because the decomposability of the resin is increased and the thermal stability and impact resistance are reduced, and the appearance is poor.

_{ZrO 2} -SiO 2 -HfO 2 based composite oxide used in the present invention preferably has a composition of 50 to 80% by mass as ZrO _2, 25 to 45% by mass as SiO _2, 0.05 to 5 mass% HfO ₂ It is preferable that Here, the total amount of ZrO ₂ , SiO ₂ and HfO ₂ is 100% by mass.

The ZrO ₂ component is 50% by mass or more, more preferably 60% by mass or more, and usually 80% by mass or less, more preferably 70% by mass or less. Further, SiO ₂ component, 25 mass% or more, more preferably 30 mass% or more and 45 mass% or less, and more preferably not more than 40 wt%.
Further, the HfO ₂ component is 0.05% by mass or more, more preferably 0.5% by mass or more, particularly 1.5% by mass or more, and 5% by mass or less, more preferably 3% by mass or less, particularly 2%. It is below mass%.

Moreover, the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide of the present invention may contain an oxide of iron (Fe) in addition to the ZrO ₂ component, the SiO ₂ component, and the HfO ₂ component. The amount of iron oxide is preferably 0.005 to 0.05% by mass as Fe ₂ O ₃ with respect to 100% by mass in total of ZrO ₂ , SiO ₂ , and HfO ₂ . If it exceeds 0.05% by mass, the color tone of the molded product tends to be reddish, and when it is within this range, a molded product with a good color tone can be obtained.

Furthermore, the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide of the present invention includes metal oxides such as Al ₂ O ₃ and TiO ₂ in addition to the above ZrO ₂ component, SiO ₂ component, HfO ₂ component, and iron oxide. And heavy metals such as yttrium, thorium and uranium may be contained.
Among the above, the content of the metal oxide is preferably 3% by mass or less, and more preferably 1% by mass or less. When the content of the metal oxide exceeds 3% by mass, the thermal stability and wet heat stability of the aromatic polycarbonate resin composition may be lowered, which is not preferable.
The heavy metal content is preferably 1000 ppm or less, and more preferably 500 ppm or less. If the heavy metal content exceeds 1000 ppm, the aromatic polycarbonate resin is decomposed, resulting in a decrease in mechanical properties and further coloration, which is not preferable.

[6. Fluorine-containing resin (D)]
The thermoplastic composition of the present invention contains 0.001 to 1 part by mass of the fluorine-containing resin with respect to 100 parts by mass of the aromatic polycarbonate resin. Thus, by containing a fluorine-containing resin, the melting characteristics of the resin composition can be improved, and specifically, the dripping prevention property at the time of combustion can be improved.

  If the content of the fluorine-containing resin is less than 0.001 part by mass, the effect of improving the flame retardancy by the fluorine-containing resin tends to be insufficient, and if it exceeds 1 part by mass, a molded product obtained by molding a thermoplastic resin composition This causes poor appearance and reduced mechanical strength. The lower limit of the content is more preferably 0.05 parts by mass or more, still more preferably 0.075 parts by mass or more, particularly preferably 0.1 parts by mass or more, and the upper limit of the content is more preferably 0. .75 parts by mass or less, more preferably 0.6 parts by mass or less, and particularly preferably 0.5 parts by mass or less.

Of these, a fluoroolefin resin is preferable. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure, and specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, Of these, tetrafluoroethylene resin is preferred.
Moreover, as this fluorine-containing resin, what has a fibril formation ability is preferable, and specifically, the fluoro olefin resin which has a fibril formation ability is mentioned. Thus, it has the tendency to improve dripping prevention property at the time of combustion by having fibril formation ability.

  Examples of the fluoroolefin resin having a fibril-forming ability include “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Polyflon (registered trademark) F201L” and “Polyflon (registered trademark) F103 manufactured by Daikin Chemical Industries. "," Polyflon (registered trademark) FA500 "and the like. Furthermore, as commercially available products of aqueous dispersions of fluoroolefin resins, for example, “Teflon (registered trademark) 30J”, “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon ( Registered trademark) D-1 "and the like.

  Furthermore, an organic polymer-coated fluoroolefin resin can also be suitably used. By using the organic polymer-coated fluoroolefin resin, the dispersibility is improved, the surface appearance of the molded product is improved, and the surface foreign matter can be suppressed. The organic polymer-coated fluoroolefin resin can be produced by various known methods. For example, (1) a polyfluoroethylene particle aqueous dispersion and an organic polymer particle aqueous dispersion are mixed and powdered by coagulation or spray drying. (2) A method of polymerizing a monomer constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing or producing the powder by solidification or spray drying. 3) After emulsion polymerization of a monomer having an ethylenically unsaturated bond in a dispersion obtained by mixing an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles, a powder is obtained by coagulation or spray drying. And the like, and the like.

The organic polymer for coating the fluoroolefin resin is not particularly limited, and specific examples of monomers for producing such an organic polymer include styrene, α-methylstyrene, p. -Methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4- Aromatic vinyl monomers such as dimethylstyrene;
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, tridecyl acrylate, (Meth) acrylic acid ester monomers such as tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate;

Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile;
Α, β-unsaturated carboxylic acids such as maleic anhydride; maleimide monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide;
Glycidyl group-containing monomers such as glycidyl methacrylate;
Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; vinyl carboxylate monomers such as vinyl acetate and vinyl butyrate;
Olefinic monomers such as ethylene, propylene, isobutylene;
Examples thereof include diene monomers such as butadiene, isoprene and dimethylbutadiene. In addition, these monomers can be used individually or in mixture of 2 or more types.

  Among them, as a monomer for producing an organic polymer covering a fluoroolefin resin, those having a high affinity with an aromatic polycarbonate resin are preferable from the viewpoint of dispersibility when blended with an aromatic polycarbonate resin. An aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

  The content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and particularly preferably 45% by mass or more. Usually, it is 95 mass% or less, Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less, Most preferably, it is 75 mass% or less. It is preferable that the content ratio of the fluoroolefin resin in the organic polymer-coated fluoroolefin resin is in the above-described range because the balance between the flame retardancy and the appearance of the molded product tends to be excellent.

As such an organic polymer-coated fluoroolefin resin, specifically, “Metabrene (registered trademark) A-3800” manufactured by Mitsubishi Rayon Co., Ltd., “Blendex (registered trademark) 449” manufactured by GE Specialty Chemical Co., Ltd., PIC Company "Poly TS AD001" manufactured by the company etc. are mentioned.
In addition, 1 type may contain fluorine-containing resin and 2 or more types may contain it by arbitrary combinations and a ratio.

[7. Surface treatment agent (E)]
The thermoplastic resin composition of the present invention preferably contains a surface treatment agent. By containing the surface treatment agent, the surface activity of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide contained in the thermoplastic resin composition is reduced, and the influence of decomposition on the aromatic polycarbonate resin is reduced. The thermoplastic resin composition of the invention is improved in thermal stability, moist heat stability, impact resistance, and hue, and a molded product having excellent surface appearance with few silver streaks or the like is obtained. The surface treatment agent according to the present invention is not particularly limited as long as it is a known surface treatment agent, and a silicon-based surface treatment agent, a titanium-based surface treatment agent, an aluminum-based surface treatment agent, and an organic acid-based surface treatment agent. Among them, a silicon surface treatment agent and a titanium surface treatment agent are preferable, and a silicon surface treatment agent is more preferable.

  As the silicon-based surface treating agent, a reactive functional group-containing organosilicon compound having a reactive functional group that reacts with the surface of the inorganic compound particles is particularly preferable. Examples of reactive functional groups include Si-H groups, Si-OH groups, Si-NH groups, and Si-OR groups, but those having Si-H groups, Si-OH groups, and Si-OR groups. More preferred are SiH group-containing organosilicon compounds having Si—H groups.

  The SiH group-containing organosilicon compound is not particularly limited as long as it is a known compound having a Si—H group in the molecule, and may be appropriately selected and used. Among them, poly (dihydrogensiloxane), poly ( Methylhydrogensiloxane), polycyclo (methylhydrogensiloxane), poly (ethylhydrogensiloxane), poly (phenylhydrogensiloxane), poly [(methylhydrogensiloxane) (dimethylsiloxane)] copolymer, poly [(methylhydro Gensiloxane) (ethylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (hexylmethylsiloxane)] copolymer, poly [(methyl Idrogensiloxane) (octylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethoxysiloxane)] copolymer, poly [(methylhydrogen) Siloxane) (dimethoxysiloxane)] copolymer, poly [(methylhydrogensiloxane) (3,3,3-trifluoropropylmethylsiloxane)] copolymer, poly [(dihydrogensiloxane) ((2-methoxyethoxy) methyl Polyorganohydrogensiloxanes such as siloxane)] copolymers and poly [(dihydrogensiloxane) (phenoxymethylsiloxane)] copolymers are preferred.

  Examples of the polyorganohydrogensiloxane that can be preferably used in the present invention include trade name “SH1107” manufactured by Toray Dow Corning and trade name “KF99” manufactured by Shin-Etsu Chemical Co., Ltd.

As the organosilicon compound having a Si—OH group and Si—OR, a silicon compound having a structure represented by the following formula (3) can be preferably used.
R ⁸ _n Si (OR ⁹ ) _4-n (3)
In the above formula (3), R ⁸ represents a saturated or unsaturated hydrocarbon group or a hydrogen atom, preferably a hydrocarbon group having 1 to 10 carbon atoms. A functional group may be introduced into the hydrocarbon group. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and R ⁸ may have a substituent, such as a vinyl group, an epoxy group, a methacryl group. And an alkyl group having a group, an amino group, or a mercapto group.

In the above formula (3), R ⁹ represents a saturated or unsaturated hydrocarbon group or a hydrogen atom, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. In the above formula (3), R ⁹ may be substituted with a halogen atom such as a chlorine atom.
Furthermore, in said formula (3), n represents the integer of 0 or 1-3.

As such a silane coupling agent, specifically,
Alkoxy-based silane coupling agents such as tetramethoxysilane, tetraethoxysilane, and bis (trimethoxysilyl) hexane;

  Methyltrimethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, methyltrichlorosilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane, trimethylmethoxysilane, trimethylchlorosilane, etc. Alkyl-based silane coupling agents;

Aryl-based silane coupling agents such as phenyltrimethoxysilane, diphenyldimethoxysilane, triphenylsilanol, dimethylphenylmethoxysilane;
Alkenyl silane coupling agents such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (methoxyethoxy) silane, vinyltrichlorosilane, allyltrimethoxysilane;
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid Epoxy-based silane coupling agents such as xylpropylmethyldimethoxysilane;

a styryl-based silane coupling agent such as p-styryltrimethoxysilane;
Methacryloxy-based silane couplings such as methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Agent;

An acryloxy-based silane coupling agent such as 3-acryloxypropyltriethoxysilane;
N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. Amino-based silane coupling agents;
Ureido silane coupling agents such as 3-ureidopropyltriethoxysilane;
Halogen-based silane coupling agents such as trifluoropropyltrimethoxysilane and 3-chloropropyltrimethoxysilane;

Sulfide-based silane coupling agents such as bis- (3- (triethoxysilyl) -propyl) -disulfide and bis- (3- (triethoxysilyl) -propyl) -tetrasulfide;
Mercapto silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane;
Examples of the isocyanate type include isocyanate type silane coupling agents such as 3-isocyanatopropyltriethoxysilane.

These silane coupling agents may be two or more polycondensates produced by hydrolysis and dehydration condensation of part of the bonds. Two or more types may be used in combination or polycondensed.
Among such silane coupling agents, an alkyl silane coupling agent and an aryl silane coupling agent are particularly preferable, and a phenyl silane coupling agent is more preferable.

The preferable content of the surface treating agent (E) in the present invention is 1 part by mass or more, particularly 2 parts by mass or more, with respect to 100 parts by mass of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 7.5 parts by mass or less, and particularly preferably 6 parts by mass or less. When the content of the surface treatment agent is less than the lower limit value of the range, there is a tendency that sufficient surface treatment effect cannot be exhibited, and when the content of the surface treatment agent exceeds the upper limit value of the range, the effect This is not preferable because there is a possibility that the gas at the time of molding will increase and the gas during molding will increase or the appearance of the molded product will be poor.

[9. Other ingredients]
The aromatic polycarbonate resin composition of the present invention may contain other components in addition to those described above as needed, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than aromatic polycarbonate resins, various resin additives, and the like. 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 (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer Styrenic resin such as coalescence (AES resin);

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA 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 anti-blocking agents. Agents, fluidity improvers, plasticizers, dispersants, antibacterial 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 Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred. As such an organic phosphite compound, specifically, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10”, manufactured by Adeka Co., Ltd., manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include “JP-351”, “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by Ciba Specialty Chemicals.
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 mass or more, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more with respect to 100 parts by mass of the aromatic polycarbonate resin. Usually, it is 1 part by mass or less, preferably 0.7 part by mass or less, more preferably 0.5 part by mass 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.

.. Antioxidants Examples of antioxidants 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.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010” (registered trademark, the same shall apply hereinafter) manufactured by Ciba Specialty Chemicals, “Irganox 1076”, and “Adeka Stub” manufactured by Adeka. AO-50 "," ADK STAB AO-60 "and the like.
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 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.000 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. 5 parts by mass or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

.. Release agent Examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane silicone oil, and the like. Can be mentioned.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monovalent, divalent or trivalent carboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic 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, mellicic acid, tetrariacontanoic acid, montanic acid, adipine Examples include acids and azelaic acid.

  As aliphatic carboxylic acid in ester of aliphatic carboxylic acid and alcohol, the same thing as the said aliphatic carboxylic acid can be used, for example. On the other hand, examples of the alcohol include saturated or unsaturated 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 aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. In addition, an aliphatic includes an alicyclic compound here.

  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, dipentaerythritol, and the like. Is mentioned.

  In addition, said ester may contain aliphatic carboxylic acid and / or alcohol as an impurity. Moreover, although said ester may be a pure substance, it may be a mixture of a plurality of compounds. Furthermore, the aliphatic carboxylic acid and alcohol which combine to form one ester may be used alone or in combination of two or more in any combination and ratio.

  Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate Examples thereof include rate, glycerol distearate, glycerol 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 15,000 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. Further, these hydrocarbons may be partially oxidized.
Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.

The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.
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 mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

..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. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the aromatic polycarbonate resin composition of the present invention are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 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 ′) -Methylphenyl) -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 others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb” manufactured by Cytec Industries “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin” manufactured by Ciba Specialty Chemicals 234 "," Tinubin 326 "," Tinubin 327 "," Tinubin 3 8 ", and the like.

  The content of the ultraviolet absorber is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Or less. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination. In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

.. Elastomer The elastomer is preferably a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The production method of the graft copolymer may be any production method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and the copolymerization method may be single-stage graft or multi-stage graft.

  The rubber component usually has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) type composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in terms of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable. .

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to.

  The graft copolymer obtained by copolymerizing the rubber component is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. Among them, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing (meth) acrylic acid ester is particularly preferred. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such a core / shell type graft copolymer include “Paraloid (registered trademark, hereinafter the same) EXL2602”, “Paraloid EXL2603”, “Paraloid EXL2655”, “Paraloid” manufactured by Rohm and Haas Japan. “EXL2311”, “Paraloid EXL2313”, “Paraloid EXL2315”, “Paraloid KM330”, “Paraloid KM336P”, “Paraloid KCZ201”, “Metabrene (registered trademark, the same shall apply hereinafter) C-223A”, “Metabrene E” manufactured by Mitsubishi Rayon Co., Ltd. -901 "," Metabrene S-2001 "," Metabrene SRK-200 "," Kaneace (registered trademark, the same applies hereinafter) M-511 "," Kaneace M-600 "," Kaneace M-400 "manufactured by Kaneka Corporation "Kane Ace M-580 , "Kane Ace MR-01", and the like.

The content of the elastomer is preferably 1 to 12 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Thus, the impact resistance of a thermoplastic resin composition can be improved by containing an elastomer.
If the elastomer content is less than 1 part by mass, the impact resistance improvement effect by the elastomer tends to be insufficient, and if it exceeds 12 parts by mass, the appearance of molded products molded from the thermoplastic resin composition and the heat resistance are poor. Decline is likely to occur. The lower limit of the content is preferably 2 parts by mass or more, and the upper limit of the content is preferably 7.5 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

-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; quinoline, 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. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

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

[8. Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include the aromatic polycarbonate resin, ABS resin, metal salt compound, fluorine-containing resin, elastomer, ZrO ₂ —SiO ₂ —HfO ₂ composite oxide according to the present invention, and blended as necessary. Other ingredients are mixed in advance using various mixers such as tumblers and Henschel mixers, and then melted in a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. The method of kneading is mentioned.

In addition, for example, the thermoplastic resin composition of the present invention is manufactured without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. You can also
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, this master batch is again mixed with the remaining components and melt-kneaded. The thermoplastic resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

[9. Molding]
The thermoplastic resin composition of the present invention is usually molded into an arbitrary shape and used as a molded product (resin composition molded product). There are no restrictions on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  Examples of molded products include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and particularly suitable for use in parts of electrical and electronic equipment.

  Examples of the electric and electronic devices 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, and mobile phones. Battery pack, recording medium drive and reader, mouse, numeric keypad, CD player, MD player, portable radio / audio player, and the like.

  The manufacturing method of a molded article is not particularly limited, and a molding method generally adopted for the aromatic polycarbonate resin composition can be arbitrarily adopted. 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.

  The obtained molded article of the present invention can be used as a practical molded article having high flame resistance and impact resistance without impairing the excellent properties of the aromatic polycarbonate resin as described above.

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.
The measurement / evaluation methods and materials used in the examples and comparative examples are as follows.

1. Measurement / Evaluation Method [Flame Retardancy Evaluation]
Evaluation of flame retardancy of each aromatic polycarbonate resin composition was performed by conditioning a test piece for UL test obtained by the method described below for 48 hours in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%. It was performed in accordance with UL94 test (combustion test of plastic materials for parts of equipment) defined by LS Laboratories (UL). 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. In addition, in Tables 3-4, it describes with "flame retardance."

[Fluidity evaluation (MVR)]
The pellets obtained by the above-described production method were dried at 80 ° C. for 4 hours or more, and then measured under the conditions of a measurement temperature of 260 ° C. and a measurement load of 2.16 kgf according to ISO1133.
In addition, in Tables 3-4, it describes with "fluidity."

[Impact resistance evaluation]
Using the obtained pellets, an ISO multipurpose test piece was prepared under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., Psycap M-2, clamping force 75T). Manufactured and measured Charpy impact strength CI (measured with notch by ISO 179). In Tables 3 to 4, “Charpy” is used.

2. Use material (A-1) component [aromatic polycarbonate resin]
-Bisphenol A type aromatic polycarbonate resin (A-1-1)
Product name "Iupilon (registered trademark)" manufactured by Mitsubishi Engineering Plastics
S-3000 "Viscosity average molecular weight: 22,000
-Bisphenol A type aromatic polycarbonate resin (A-1-2)
Product name "Iupilon (registered trademark)" manufactured by Mitsubishi Engineering Plastics
H-4000 "Viscosity average molecular weight: 15,000
(A-2) Component [ABS resin]
・ Nippon A &L's product name "Santac AT-08" bulk polymer (A-2-1)
・ Product name “Techno ABS DP-611” manufactured by Techno Polymer Co., Ltd. (A-2-2)

(B) component [phosphate ester flame retardant]
Resorcinol bis-2,6-xylenyl phosphate, trade name “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.

Component (C) [ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide]
C-1 to C-5 shown in Table 2 below were prepared as ZrO ₂ —SiO ₂ —HfO ₂ composite oxides. In Table 2, the content of Fe ₂ O ₃ is mass% with respect to a total of 100 mass% of ZrO ₂ , SiO _2, and HfO ₂ .

(Silicates other than ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide)
[talc]
Trade name “Micron White # 5000S” manufactured by Hayashi Kasei
Average particle size 2.8 μm

Component (D) [fluorinated resin]
Polytetrafluoroethylene with fibril forming ability "Teflon (registered trademark) 6J" manufactured by Mitsui DuPont Fluorochemicals
(E) component [surface treatment agent]
SiH group-containing organosilicon polymer Methylhydrogensiloxane Product name “SH1107 FLUID” manufactured by Toray Dow Corning

In addition to the above components, the following stabilizers (component (G)) were all blended in the examples and comparative examples.
(F) component [stabilizer]
(F-1) Tris (2,4-di-tert-butylphenyl) phosphite Product name “ADK STAB 2112” manufactured by ADEKA
(F-2) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Product name “Irganox 1010” manufactured by Ciba Specialty Chemicals
(G) component [release agent]
Stearyl stearate manufactured by NOF Corporation, trade name: UNISTAR M9766

(Examples 1-6, Comparative Examples 1-6)
The components shown in Table 3 and Table 4 were blended in the proportions (all mass%) shown in Table 3 and Table 4, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works, Ltd., equipped with 1 vent. Supplied to a shaft extruder (TEX30HSST), kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 250 ° C., the molten resin composition extruded in a strand shape is quenched in a water tank, and a pelletizer And pelletized using an aromatic polycarbonate resin composition.

  Next, after drying the pellet obtained by the above-mentioned manufacturing method at 80 ° C. for 5 hours, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature is 250 ° C. and the mold temperature is 70 ° C. The plate-shaped test piece (90 mm × 50 mm × 3 mm thickness) was molded by injection molding under the following conditions.

Similarly, after the pellets obtained by the above-described production method were dried at 80 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature was 250 ° C. and the mold temperature was 70 ° C. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.0 mm was molded by injection molding under the following conditions.
The evaluation results for the obtained test pieces are shown in Table 3 (Examples) and Table 4 (Comparative Examples).

As can be seen from Examples 1 to 6, the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide having a specific particle size according to the present invention is mixed with a phosphoric ester and a fluorine-containing resin together with an aromatic polycarbonate and an aromatic vinyl-diene-cyan. It can be seen that by adding a predetermined amount to the vinyl fluoride copolymer, the flame retardancy evaluation is also high flame resistance at V-0, and the impact resistance is also excellent.
On the other hand, Comparative Example 3 which does not contain a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide has poor flame retardancy as V-2, and in Comparative Example 1 and Comparative Example 2 in which a compound having a large particle size is blended, it is difficult. In Comparative Examples 4 to 6 using a talc instead of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide, the flame retardancy is poor with V-2 or the flame retardancy is poor. It can be seen that the balance between resistance and impact resistance is poor.

  Therefore, from the above examples and comparative examples, it has been confirmed that the effect of obtaining an excellent light-shielding property and simultaneously improving flame retardancy and impact resistance is obtained only by the configuration of the present invention. It was.

  According to the aromatic polycarbonate resin composition of the present invention, an aromatic polycarbonate resin molding material having excellent light shielding properties, high flame retardancy and high impact resistance can be obtained. It can be used in a wide range of fields such as equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building components, various containers, leisure goods / miscellaneous goods, lighting equipment, etc., and its industrial applicability is very high.

Claims (7)

The aromatic polycarbonate resin (A-1) is 50% by mass or more and less than 93% by mass and the aromatic vinyl-diene-vinyl cyanide copolymer (A-2) is 50% by mass or less and contains more than 7% by mass. For 100 parts by mass of the thermoplastic resin (A),
2 to 25 parts by mass of phosphate ester flame retardant (B), 1 to 10 parts by mass of ZrO ₂ —SiO ₂ —HfO ₂ complex oxide (C) having an average particle size of 0.1 to 4 μm, and fluorine-containing resin (D) A thermoplastic resin composition containing 0.001 to 1 part by mass. The thermoplastic resin composition according to claim 1, wherein the phosphate ester flame retardant (B) is a compound represented by the following general formula (1).

(Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, X Represents an arylene group, p, q, r and s are each 0 or 1, and k is an integer of 1 to 5.) The composition of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide (C) is ZrO ₂ : 50 to 80% by mass, SiO ₂ : 25 to 45% by mass, HfO ₂ : 0.05 to 5% by mass. The thermoplastic resin composition according to claim 1 or 2. ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) further contains Fe ₂ O ₃ in an amount of 0.005 to 0.05% by mass with respect to 100% by mass of ZrO ₂ , SiO ₂ and HfO ₂ in total. The thermoplastic resin composition according to any one of claims 1 to 3, wherein: Further, a surface treatment agent _(E), claim to ZrO ₂ -SiO ₂ -HfO ₂ composite oxide (C) 100 parts by weight, characterized in that it contains 0.05 to 10 parts by weight 1-4 The thermoplastic resin composition according to any one of the above.   The thermoplastic resin composition according to claim 5, wherein the surface treatment agent (E) is a SiH group-containing organosilicon polymer or a silane coupling agent.   A molded article formed by molding the thermoplastic composition according to claim 1.