JP2011208111A - Thermoplastic resin composition and molded product using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin thermoplastic resin composition having excellent light shielding property and well-balanced fluidity, shock resistance, and flame retardancy; and a molded product using the thermoplastic resin composition.SOLUTION: The thermoplastic resin composition comprises: 100 pts.mass of the total of 50-97 mass% of an aromatic polycarbonate resin and 50-3 mass% of an elastomer, 2-25 pts.mass of a phosphoric acid ester and/or phosphazene flame retardant; 1-15 pts.mass of a ZrO-SiO-HfOcomplex oxide with a mean diameter of 0.1-4 μm; and 0.001-1 pts.mass of a fluorine-containing resin. The molded product produced by molding the thermoplastic resin composition is also provided.

Description

  The present invention relates to a thermoplastic resin composition and a molded article using the same, and more specifically, a polycarbonate resin-based thermoplastic composition excellent in light shielding properties and excellent in balance between fluidity, impact resistance and flame retardancy, and It relates to a molded product comprising the same.

  Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used in, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. . In particular, the flame-retardant polycarbonate resin composition is suitably used as a member of OA / information equipment such as computers, notebook computers, mobile phones, printers, and copying machines.

As means for imparting flame retardancy to such 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, see Patent Document 1). Polycarbonate resin blended with phosphorus flame retardants has the effect of diluting the combustion gas in the gas phase, and the effect of blocking the combustion gas and air necessary for combustion by forming a heat insulating carbonized layer on the surface of the molded product during combustion. It is known that the effect of delaying and the like is 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 imparted with high flame retardancy while reducing its use amount as much as possible, has excellent impact resistance and fluidity, and has excellent light shielding properties.

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 a polycarbonate resin composition excellent in light-shielding properties and excellent in balance between fluidity, impact resistance and flame retardancy, and a polycarbonate molded article comprising the same, in view of the problems of the prior art. is there.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have obtained a resin composition in which an elastomer is blended with a polycarbonate resin, a phosphate ester flame retardant and / or a phosphazene flame retardant, and an average particle diameter. By blending a specific ratio of zirconium, silicon and hafnium composite oxides in a specific range and fluorine-containing resin, they have excellent light shielding properties and excellent balance between fluidity, impact resistance and flame retardancy. The inventors have found that a polycarbonate resin material can be obtained, and have completed the present invention.

That is, according to 1st invention of this invention, with respect to 100 mass parts of thermoplastic resins containing 50-97 mass% of aromatic polycarbonate resin (A-1) and elastomer (A-2) 50-3 mass%. ,
ZrO ₂ —SiO ₂ —HfO ₂ composite oxidation of _{2 to} 25 parts by mass of phosphoric acid ester flame retardant (B-1) and / or phosphazene flame retardant (B-2) and an average particle size of 0.1 to 4 μm A thermoplastic resin composition comprising 1 to 15 parts by mass of the product (C) and 0.001 to 1 part by mass of the fluororesin (D) 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、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, in the first invention, the phosphate ester flame retardant (B-1) is a phosphate ester flame retardant represented by the following general formula (1). A thermoplastic 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 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 invention of the present invention, in any one of the first to fourth inventions, the elastomer (A-2) is a core layer containing polybutadiene-containing rubber or (meth) acrylic acid ester rubber. A thermoplastic resin composition comprising a core / shell type graft copolymer is provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, the elastomer (A-2) is made of a (meth) acrylic acid ester-based polymer or an acrylonitrile / styrene copolymer. There is provided a thermoplastic resin composition characterized by being a core / shell type graft copolymer having an outermost shell layer.

According to the seventh invention of the present invention, in any one of the first to sixth inventions, the surface treating agent (E) is further added to a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) 100. 1-10 mass parts is contained with respect to a mass part, The thermoplastic resin composition characterized by the above-mentioned is provided.

  According to an eighth aspect of the present invention, in the seventh 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 ninth invention of the present invention, there is provided a molded product formed by molding the thermoplastic resin composition according to any one of the first to eighth inventions.

  According to the polycarbonate resin composition of the present invention, it is possible to obtain a polycarbonate resin composition having excellent light shielding properties and having both high flame retardancy and excellent impact resistance.

  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 polycarbonate resin composition of the present invention comprises a polycarbonate resin, an elastomer, a phosphate ester flame retardant and / or a phosphazene flame retardant, a ZrO ₂ —SiO ₂ —HfO ₂ complex oxide having a specific average particle size, and a fluorine-containing compound. Each of the resins is characterized by containing a specific amount.

[2. Polycarbonate resin (A-1)]
The type of the aromatic polycarbonate resin (A-1) used in the thermoplastic resin composition of the present invention is not limited, and only one type may be used, and two or more types may be used in any combination and any type. You may use together by a ratio.
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.

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.

  The aromatic polycarbonate resin refers to a polycarbonate resin in which carbons directly bonded to carbonic acid bonds are aromatic carbons. 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 o-oxinebenzoic 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, the molecular weight of the aromatic polycarbonate resin obtained can also be adjusted by this operation.

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-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.
The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, in consideration of 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) is arbitrary and may be appropriately selected and determined, but is preferably 10,000 to 40,000 in terms of viscosity average molecular weight [Mv]. 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 [η _sp ] 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 1000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the aromatic polycarbonate resin composition of the present invention can be further improved. The lower limit is usually 10 ppm or more, preferably 30 ppm or more, and more preferably 40 ppm or more, particularly in the case of an aromatic polycarbonate resin produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the aromatic polycarbonate resin composition of this invention can be improved more.

  The unit of the terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm relative to the weight of the aromatic polycarbonate resin. The 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 mass 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. Elastomer (A-2)]
The thermoplastic resin composition of this invention contains 3-50 mass% of elastomer with respect to 100 mass% of total amounts with an 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 3% by mass, the impact resistance improvement effect by the elastomer will be insufficient, and if it exceeds 50% by mass, the appearance of molded products molded from the polycarbonate resin composition and the heat resistance will be reduced. Arise. The lower limit of the content is preferably 4% by mass or more, and the upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.

  Examples of the elastomer used in the present invention include methyl methacrylate-butadiene-styrene copolymer (MBS resin), styrene-butadiene triblock copolymer called SBS, SEBS, and hydrogenated products thereof, SPS, SEPS, Styrene-isoprene triblock copolymer and its hydrogenated product, olefinic thermoplastic elastomer called TPO, polyester elastomer, silicone rubber, acrylate rubber, silicone rubber and acrylate rubber Examples thereof include a composite rubber-based graft copolymer obtained by graft-polymerizing a vinyl monomer to a composite rubber composed of components.

  Of these, a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith is preferable. 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 the monomer component that can be graft copolymerized with the rubber component include aromatic vinyl compounds such as styrene, vinyl cyanide compounds such as acrylonitrile, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and glycidyl. Epoxy group-containing (meth) acrylic acid ester compounds such as (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acids such as maleic acid, phthalic acid and itaconic acid Examples thereof include acid compounds and anhydrides thereof (eg maleic anhydride). 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, a layer containing at least one rubber component selected from the above-mentioned polybutadiene-containing rubber, polyalkyl acrylate-containing rubber, and polyorganosiloxane / polyalkyl acrylate-containing rubber is used as a core layer, and its surroundings. A core / shell type graft copolymer comprising a shell layer formed by (co) polymerizing (meth) acrylic acid ester or acrylonitrile / styrene is particularly preferable. 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 applies 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.

[4. Phosphorus flame retardant]
The thermoplastic resin composition of the present invention comprises a phosphate ester flame retardant (B-1) and / or a phosphazene flame retardant (B-2), an aromatic polycarbonate resin (A-1) and an elastomer (A-2). 2) to 25 parts by mass with respect to 100 parts by mass in total. Thus, the flame retardance of the thermoplastic resin composition of this invention can be improved by containing a phosphorus flame retardant.

[4-1. Phosphate ester flame retardant (B-1)]
The phosphate ester flame retardant (B-1) in the present invention is a compound containing phosphorus in the molecule, and may be a low molecule, an oligomer, or a polymer. The phosphate ester compound represented by the general formula (1) or (2) is preferably exemplified, but the phosphate ester-based flame retardant represented by the general formula (1) is particularly preferable from the viewpoint of thermal stability.

（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、０または１であり、ｋは１から５の整数である。）

(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 0 or 1, and k is an integer of 1 to 5.)

The phosphate ester flame retardant represented by the general formula (1) is a condensed phosphate ester having k of 1 to 5, and for a mixture of condensed phosphate esters having different k, k is an average value of the mixture. Become. 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.

  Specific examples of the phosphate ester flame retardant represented by the general formula (1) include, when resorcinol is used as a dihydroxy compound, phenyl resorcin / 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 Resorcinol polyphosphate is preferred.

  As the phosphate ester flame retardant (B-1), a phosphorus flame retardant represented by the following general formula (2) can also be preferably used.

（式中、Ｒ^５、Ｒ^６及びＲ^７は、各々独立して、炭素数１〜６のアルキル基又はアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｈ、ｉ及びｊは、０又は１である。）

(Wherein R ⁵ , R ⁶ and R ⁷ 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, h, i and j are 0 or 1.)

  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. Preferred examples include diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

  The content of the phosphate ester flame retardant (B-1) is 2 parts by mass or more, preferably 5 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A-1) and the elastomer (A-2). More preferably, it is 8 parts by mass or more, 25 parts by mass or less, preferably 22.5 parts by mass or less, and more preferably 20 parts by mass or less. When the blending amount of the phosphoric ester-based flame retardant is less than 2 parts by mass, the flame retardancy is insufficient, and when it exceeds 25 parts by mass, it causes a significant decrease in heat resistance and mechanical properties, which is not preferable. .

[4-2. Phosphazene flame retardant (B-2)]
The phosphazene flame retardant (B-2) used in the present invention is an organic compound having a -P = N- bond in the molecule, preferably a cyclic phosphazene compound represented by the following general formula (3), The chain phosphazene compound represented by (4) and a crosslinked phosphazene compound obtained by crosslinking at least one phosphazene compound selected from the group consisting of the following general formula (3) and the following general formula (4) with a crosslinking group At least one flame retardant selected from the group consisting of: As the crosslinked phosphazene compound, those crosslinked by a crosslinking group represented by the following general formula (5) are preferable from the viewpoint of flame retardancy.

（式（３）中、ｍは３〜２５の整数であり、Ｒ^１１は、同一又は異なっていてもよく、アリール基又はアルキルアリール基を示す。）

(In Formula (3), m is an integer of 3 to 25, and R ¹¹ may be the same or different and represents an aryl group or an alkylaryl group.)

（式（４）中、ｎは３〜１０，０００の整数であり、Ｒ^１２は同一又は異なっていてもよく、アリール基又はアルキルアリール基を示し、Ｘは、−Ｎ＝Ｐ（ＯＲ^１２）_３基又は−Ｎ＝Ｐ（Ｏ）ＯＲ^１２基を示し、Ｙは、−Ｐ（ＯＲ^１２）_４基又は−Ｐ（Ｏ）（ＯＲ^１２）_２基を示す。）

(In Formula (4), n is an integer of 3 to 10,000, R ¹² may be the same or different, and represents an aryl group or an alkylaryl group, and X represents —N═P (OR ¹² ). _{3 represents a} group or —N═P (O) OR ¹² group, and Y represents a —P (OR ¹² ) ₄ group or —P (O) (OR ¹² ) ₂ group.

（式（５）中、Ａは−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−、又は−Ｏ−であり、ｌは０又は１である。）

(In the formula (5), A is _{-C (CH 3) 2 -,} - SO 2 -, - S-, or a -O-, l is 0 or 1.)

Examples of the cyclic and / or chain phenoxyphosphazene compounds represented by the general formulas (3) and (4) include, for example, phenoxyphosphazene, (poly) tolyloxyphosphazene (for example, o-tolyloxyphosphazene, m-tolyloxyphosphazene). P-tolyloxyphosphazene, o, m-tolyloxyphosphazene, o, p-tolyloxyphosphazene, m, p-tolyloxyphosphazene, o, m, p-tolyloxyphosphazene, etc.), (poly) xylyloxyphosphazene and cyclic and / or linear C _1-6 alkyl C _6-20 aryloxy phosphazene etc., (poly) phenoxy tolyloxy phosphazene (e.g., phenoxy o- tolyloxy phosphazene, a phenoxy m- tolyloxyethyl phosphazene, a phenoxy p- Toriruoki Phosphazenes, phenoxy o, m-tolyloxyphosphazenes, phenoxy o, p-tolyloxyphosphazenes, phenoxy m, p-tolyloxyphosphazenes, phenoxy o, m, p-tolyloxyphosphazenes), (poly) phenoxyxyloxyphosphazenes And cyclic and / or chain C _6-20 aryl C _1-10 alkyl C _6-20 aryloxy phosphazene such as (poly) phenoxytolyloxyxyloxyphosphazene, preferably cyclic and / or chain phenoxy Phosphazene, cyclic and / or chain C _1-3 alkyl C _6-20 aryloxyphosphazene, C _6-20 aryloxy C _1-3 alkyl C _6-20 aryloxyphosphazene (eg, cyclic and / or tolyloxyphosphazene, ring And / or a chain phenoxy tolyl phenoxyphosphazene like.

As the cyclic phosphazene flame retardant represented by the general formula (3), cyclic phenoxyphosphazene in which R ¹¹ is a phenyl group is particularly preferable. As such a cyclic phenoxyphosphazene flame retardant, for example, from a mixture of cyclic and linear chlorophosphazene obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C., hexachlorocyclotriphosphazene, Compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as octachlorocyclotetraphosphazene and decachlorocyclopentaphosphazene and then substituting with a phenoxy group Can be mentioned. The cyclic phenoxyphosphazene compound is preferably a compound in which m in the general formula (3) is an integer of 3 to 8, and may be a mixture of compounds having different m. Among them, a mixture of compounds in which m = 3 is 50% by mass or more, m = 4 is 10 to 40% by mass, and m = 5 or more is 30% by mass or less is preferable.

As the chain phosphazene flame retardant represented by the general formula (4), chain phenoxyphosphazene in which R ¹² is a phenyl group is particularly preferable. Such a chain phenoxyphosphazene compound is obtained by, for example, subjecting hexachlorocyclotriphosphazene obtained by the above-described method to reverse polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichloromethane having a polymerization degree of 3 to 10,000. Examples thereof include compounds obtained by substituting phosphazene with a phenoxy group. N in the general formula (4) of the linear phenoxyphosphazene compound is preferably 3 to 1,000, more preferably 3 to 100, and still more preferably 3 to 25.

Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned.
Moreover, as the crosslinked phosphazene compound, a crosslinked phenoxyphosphazene compound obtained by crosslinking a cyclic phenoxyphosphazene compound in which R ¹¹ is a phenyl group in the general formula (3) with a crosslinking group represented by the general formula (5), or the above A crosslinked phenoxyphosphazene compound obtained by crosslinking a chain phenoxyphosphazene compound in which R ¹² is a phenyl group in the general formula (4) with a crosslinking group represented by the general formula (5) is preferable from the viewpoint of flame retardancy, and cyclic A crosslinked phenoxyphosphazene compound obtained by crosslinking a phenoxyphosphazene compound with a crosslinking group represented by the general formula (5) is more preferable.
The content of the phenylene group in the crosslinked phenoxyphosphazene compound is such that the cyclic phosphazene compound represented by the general formula (3) and / or the all phenyl groups in the chain phenoxyphosphazene compound represented by the general formula (4) and Based on the number of phenylene groups, it is usually 50 to 99.9%, preferably 70 to 90%. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  In the present invention, the phosphazene-based flame retardant (B-2) includes a cyclic phenoxyphosphazene-based flame retardant represented by the general formula (3) and a cyclic phenoxyphosphazene compound represented by the general formula (3). From the viewpoint of flame retardancy and mechanical properties, at least one selected from the group consisting of a crosslinked phenoxyphosphazene flame retardant crosslinked by a crosslinking group is preferable.

  The content of the phosphazene flame retardant (B-2) is 2 parts by mass or more, preferably 3 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A-1) and the elastomer (A-2). The amount is preferably 5 parts by mass or more, 25 parts by mass or less, preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. When the content of the phosphazene-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 mechanical properties are caused.

  Moreover, it is preferable that content in the case of using together both a phosphate ester type flame retardant (B-1) and a phosphazene type flame retardant (B-2) is 2-25 mass parts.

[5. ZrO ₂ —SiO ₂ —HfO ₂ Complex Oxide (C)]
The thermoplastic 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, the total of polycarbonate resin (A-1) and elastomer (A-2). 3-15 mass parts is contained with respect to 100 mass parts. 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, the flame extinguishing effect at the time of combustion, the dripping prevention property is improved, and the thermoplastic resin composition The flame retardancy of things can be increased.

In addition, compared with conventionally used plate-like silicate compounds such as talc and mica and acicular silicate compounds such as wollastonite, thermoplastic resins having excellent mechanical properties and thermal properties are excellent in thermal stability. Even when the composition is obtained and the fluidity is improved, there is an advantage that there is little reduction in impact resistance.
Furthermore, it exhibits important performance in terms of application development of polycarbonate materials, which satisfies the low light transmittance and whiteness of polycarbonate resin and is excellent in light shielding properties.

If the content of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is less than 3 parts by mass, a sufficient effect of improving flame retardancy cannot be obtained, and if it exceeds 15 parts by mass, the impact resistance of the thermoplastic resin composition Sexual deterioration occurs. The lower limit of the content is preferably 4 parts by mass or more, more preferably 5 parts by mass or more, and the upper limit of the content is preferably 10 parts by mass or less, more preferably 7.5 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. In addition, when the average particle size is less than 0.1 μm, the dispersibility in the polycarbonate resin is remarkably reduced, and when the average particle size exceeds 4 μm, the appearance of the molded product is deteriorated and the impact resistance is also improved. Since it falls, it is not preferable.

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 wet heat stability of the polycarbonate resin tends to decrease, and when the pH exceeds 7.5, the decomposability of the polycarbonate resin Is unfavorable because it tends to cause a decrease in thermal stability, impact resistance and poor appearance.

_{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 with respect to the total of 100% by mass of ZrO ₂ , SiO ₂ and HfO ₂ as Fe ₂ O ₃ . 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 heat stability and wet heat stability of the polycarbonate resin composition may be lowered, which is not preferable.
The heavy metal content is preferably 1,000 ppm or less, and more preferably 500 ppm or less. When the content of heavy metal exceeds 1,000 ppm, the polycarbonate resin is decomposed, mechanical properties are deteriorated, and further coloring may be caused.

[6. Fluorine-containing resin (D)]
The thermoplastic resin composition of the present invention preferably contains the fluorine-containing resin in an amount of 0.001 to 1 part by mass with respect to a total of 100 parts by mass of the polycarbonate resin (A-1) and the elastomer (A-2). . By containing the fluorine-containing resin as described above, the melting characteristics of the thermoplastic resin composition can be improved, and specifically, the dripping prevention property during 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 There is a tendency for the appearance defect and mechanical strength to decrease. 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 0.5 parts by mass or less, and particularly preferably 0.45 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 a commercial item of the aqueous dispersion of fluoroolefin resin, for example, “Teflon (registered trademark) 30J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd., “Fluon (registered trademark) D-1” manufactured by Daikin Chemical Industries, Ltd. and the like can be mentioned. .

  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 that coats a fluoroolefin resin, those having high affinity with the polycarbonate resin are preferable from the viewpoint of dispersibility when blended with the polycarbonate resin, and aromatic monomers are preferable. A 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 or the like on the polycarbonate resin is reduced. The thermoplastic resin composition has improved thermal stability, moist heat stability, impact resistance, and hue, and a molded product having excellent surface appearance with few silver streaks or the like can be 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 general formula (6) can be preferably used.
R ²¹ _z Si (OR ²² ) _4-z (6)

In the general formula (6), R ²¹ is a saturated, unsaturated hydrocarbon group, a hydrogen atom, is preferably Among them 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 ²¹ 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 general formula (6), R ²² is a saturated, unsaturated hydrocarbon group, a hydrogen atom, is preferably Among them 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. R ²² may be substituted with a halogen atom such as a chlorine atom. Further, z represents 0 or an integer of 1 to 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.

[8. Other ingredients]
The thermoplastic resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate resins and various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

-Resin additives Examples of resin additives include heat stabilizers, antioxidants, mold release agents, UV absorbers, dyes and pigments, anti-dripping agents, antistatic agents, antifogging agents, lubricants, antiblocking agents, and fluids. Examples include property improvers, plasticizers, dispersants, and antibacterial agents. 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 thermoplastic 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 part by mass or more, preferably 0.01 part by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A-1) and the elastomer (A-2). Is 0.03 parts by mass or more, and is usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts 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.

  Content of antioxidant is 0.001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (A-1) and an elastomer (A-2), Preferably it is 0.01 mass part or more, Moreover, it is 1 mass part or less normally, Preferably it is 0.5 mass part 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.
As for the release agent mentioned above, 1 type may contain and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of a mold release agent is 0.001 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (A-1) and an elastomer (A-2), Preferably it is 0.01 mass part or more, Moreover, it is 2 mass parts or less normally, Preferably it is 1 mass part 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 polycarbonate resin composition of the present invention has good transparency and mechanical properties.

  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 Corporation “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31” manufactured by Adeka Company, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals ”,“ Tinuvin 326 ”,“ Tinuvin 327 ”,“ Tinuvin 32 ” "And the like.

  Content of a ultraviolet absorber is 0.01 mass part or more normally with respect to a total of 100 mass parts of polycarbonate resin (A-1) and an elastomer (A-2), Preferably it is 0.1 mass part or more, Moreover, it is 3 mass parts or less normally, Preferably it is 1 mass part 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.

-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 in total of the polycarbonate resin (A-1) and the elastomer (A-2). It is. If the content of the dye / pigment is too large, the impact resistance may not be sufficient.

[9. Production method of thermoplastic 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 polycarbonate resin, elastomer, phosphate ester flame retardant and / or phosphazene flame retardant, ZrO ₂ —SiO ₂ —HfO ₂ composite oxide, fluorine-containing resin, and necessary according to the present invention. Other ingredients to be blended depending on the type are mixed in advance using various mixers such as tumblers and Henschel mixers, and then Banbury mixers, rolls, brabenders, single-screw kneading extruders, twin-screw kneading extruders, kneaders, etc. The method of melt-kneading with these mixers 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.

[10. 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 a 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 product of the present invention can be used as a practical molded product having high flame resistance and impact resistance without impairing the excellent properties of the 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]
The evaluation of the flame retardancy of each thermoplastic resin composition was carried out in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50% using a test piece for UL test (1.2 mm thickness and 1.6 mm thickness) obtained by the method described later. Was conditioned for 48 hours according to the UL94 test (combustion test of plastic materials for equipment parts) established by US Underwriters 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 continues 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 the postscript table | surface which shows an evaluation result, it describes with "flame retardance."

[Fluidity evaluation]
After drying the pellets obtained by the production method described later at 120 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 280 ° C. and a load of 160 kgf ( (Unit: × 10 ⁻² cc / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high. In Table 3, it is expressed as “fluidity”.

[Hue evaluation]
The evaluation of the hue of each resin composition is a SE2000 type spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7105, using a 3 mm-thick flat plate molded product described later. L, a, and b values were measured, and Hunter Lab whiteness W (Lab) was determined from the following definition formula.
W (%) = 100 − [(100−L) ² + (a ² + b ² )] ^0.5
In the formula, L, a, and b represent the lightness (L) and the perceptual chromaticity index (a, b) in Lab color coordinates, respectively.

[Impact resistance evaluation]
Using the obtained pellets, an ISO multipurpose test piece (with a cylinder temperature of 280 ° C. and a mold temperature of 110 ° C.) using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., Psycap M-2, clamping force 75T) 3 mm), and Charpy impact strength CI (measured with a notch by ISO 179) was measured.

2. Use material (A-1) component [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 [elastomer]
(A-2-1): Core / shell copolymer comprising butadiene rubber-like polymer (core) / alkyl acrylate-alkyl methacrylate polymer (shell) Trade name “Paraloid EXL2603” manufactured by Rohm and Haas Japan
(A-2-2): Core / shell copolymer composed of alkyl acrylate polymer (core) / alkyl methacrylate polymer (shell) Rohm and Haas Japan trade name “Paraloid EXL2315”
(A-2-3): Core / shell type copolymer consisting of polyorganosiloxane / alkyl methacrylate polymer (core) / acrylonitrile-styrene copolymer (shell), trade name “METABRENE SRK-200” manufactured by Mitsubishi Rayon Co., Ltd. "
(A-2-4): Core / shell type copolymer consisting of butadiene-styrene polymer (core) / alkyl acrylate-alkyl methacrylate polymer (shell), trade name “KCZ201” manufactured by Rohm and Haas Japan
(A-2-5): Core / shell type copolymer consisting of alkyl acrylate polymer (core) / acrylonitrile-styrene copolymer (shell), trade name “STAPHYLOID MG1011” manufactured by Ganz Kasei Co., Ltd.
(A-2-6): Core / shell type copolymer comprising two kinds of alkyl acrylate polymer rubber component (core) / alkyl methacrylate polymer (shell), trade name “METABBRENE W-450A” manufactured by Mitsubishi Rayon Co., Ltd. "
(A-2-7): Composite rubber (core) composed of dimethylsiloxane polymer and alkyl acrylate polymer / core / shell copolymer composed of alkyl methacrylate polymer (shell) Trade name “Mitsubishi Rayon Co., Ltd.” METABLEN S-2001 "
(A-2-8): Methyl methacrylate-butadiene-styrene copolymer, trade name “METABRENE E-901” manufactured by Mitsubishi Rayon Co., Ltd.

(B-1) Component [Phosphate ester flame retardant]
Resorcinol bis-2,6-xylenyl phosphate, manufactured by Daihachi Chemical Industry Co., Ltd., trade name “PX-200”
(B-2) component [phosphazene flame retardant]
Cyclic phenoxyphosphazene Fushimi Pharmaceutical Co., Ltd., trade name “FP-110”

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 .

Component (D) [fluorinated resin]
Polytetrafluoroethylene with ability to form fibrils, trade name “Teflon (registered trademark) 6J” manufactured by Mitsui DuPont Fluorochemicals, Inc.

(E) component [surface treatment agent]
SiH group-containing organosilicon polymer Methyl hydrogen polysiloxane, trade name “SH1107 FLUID” manufactured by Toray Dow Corning

(F) component [stabilizer]
(F-1) Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA, trade name “ADK STAB 2112”
(F-2) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals,
Product name "Irganox 1010"

(G) Component [talc]
Product name “Micron White # 5000S” manufactured by Hayashi Kasei Co., Ltd.
Average particle size 2.8 μm
(H) component [release agent]
Behenyl behenate NOF Corporation, trade name "M-2222SL"

(Examples 1-6, Comparative Examples 1-6)
Using the materials shown in Tables 3 and 4 as the components (A) to (G), the components were blended in the proportions (all mass%) shown in Tables 3 and 4, and mixed for 20 minutes with a tumbler. After that, it was supplied to a twin-screw extruder (TEX30HSST) manufactured by Nippon Steel Works, equipped with one vent, kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 280 ° C., and extruded into a strand shape. The molten resin composition was quenched in a water tank and pelletized using a pelletizer to obtain a polycarbonate resin composition pellet.

  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 270 ° C. and the mold temperature is 60 ° C. The plate-shaped test piece (90 mm × 50 mm × 3 mm thickness) was molded by injection molding under the following conditions.

Similarly, after drying the pellets obtained by the above-mentioned production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature is 270 ° C. and the mold temperature is 70 ° C. The test piece for UL test of length 125mm, width 13mm, thickness 1.2mm, and thickness 1.6mm was shape | molded on these conditions.
The evaluation results for the obtained test pieces are shown in Tables 3 and 4.

As can be seen by comparing Examples 1 to 6 and Comparative Examples 1 to 6, it can be seen that it exhibits high whiteness and excellent light shielding properties, has high flame retardancy, and is excellent in impact resistance and fluidity. .
That is, in Examples 1 to 3, the content of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide was changed, but all of them have high flame retardancy as V-1 and good whiteness. In Example 4, a surface treating agent was further used, and the same high flame retardance and good whiteness as in Examples 1 to 3 were exhibited. Example 5 is an example in which the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide has the same particle size but a high Fe ₂ O ₃ content, but the whiteness was slightly lowered. In Example 6, the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide having a small particle diameter was used, but the whiteness was slightly lowered, but the flame retardancy achieved V-0.

On the other hand, in Comparative Example 1 not including the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide, the flame retardancy was bad with V-2 and the whiteness was also deteriorated. In Comparative Example 2 in which the amount of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide is insufficient to the amount of the present invention, the flame retardancy is as bad as V-2. In Comparative Examples 3 and 4 using the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide that does not satisfy the particle size of the present invention, the impact resistance improving effect is hardly exhibited, and the whiteness is not sufficient. In Comparative Example 5 using talc, flame retardancy and whiteness are poor and impact resistance is low, and in Comparative Example 6 containing no elastomer, whiteness is not good, and flame retardancy and impact resistance are poor. I understand that.

(Examples 7-14, Comparative Examples 7-11)
The types of elastomers listed in Table 5 and Table 6 below were used, and the same procedure as in Examples / Comparative Examples 1 to 6 was performed.
The results are shown in Tables 5 and 6.

  In Examples 7-14, the type of elastomer was changed in the formulation of Example 2, but as with the previous examples, it showed high whiteness, excellent light blocking properties, and high flame retardancy. It can be seen that there is no decrease in strength.

(Example 15, Comparative Examples 12-15)
[Production of resin pellets]
Each component described above was blended in the proportions (mass ratio) shown in Table 7, mixed for 20 minutes with a tumbler, and then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200 rpm The molten resin kneaded under conditions of a discharge rate of 15 kg / hour and a barrel temperature of 270 ° C. was rapidly cooled in a water tank and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition.

[Preparation of test piece]
After the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, the cylinder temperature was 280 ° C. and the mold temperature was 80 T using a Saicap M-2 manufactured by Sumitomo Heavy Industries, Ltd. and a clamping force of 75T. Injection molding was performed under the condition of ° C. to form an ISO multipurpose test piece (3 mm) and an ISO multipurpose test piece (4 mm).
Similarly, after drying the pellets obtained by the above-described production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. The test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was molded under the conditions described above.

[Moist heat stability evaluation]
Using the ISO multipurpose test piece (4 mm) obtained by the above-described method, the tensile fracture strain (unit:%) was measured according to the ISO527 standard. Next, the test piece was treated for 640 h under the conditions of a temperature of 75 ° C. and a relative humidity of 85%, and the tensile fracture strain (unit:%) was measured by the same method as described above. In Table 7, “strain” and “strain (after wet heat test)” are described.

Therefore, from the above Examples 1 to 15 and Comparative Examples 1 to 15, the effect of obtaining a good balance of fluidity, impact resistance, whiteness and flame retardancy, and Example 15 and Comparative Examples 12, the effect of obtaining an excellent impact resistance, flame retardancy, and moist heat resistance is obtained by using the phosphate ester flame retardant and / or phosphazene flame retardant and ZrO ₂ having a specific particle diameter according to the configuration of the present invention. It was confirmed that it was obtained for the first time by blending a predetermined amount of each of —SiO ₂ —HfO ₂ -based composite oxide and fluorine-containing resin into polycarbonate and elastomer.

  According to the polycarbonate resin composition of the present invention, a polycarbonate resin molding material having excellent light shielding properties and excellent balance of fluidity, impact resistance and flame retardancy can be obtained. For example, electrical and electronic equipment and components thereof, OA 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 (9)

For 100 parts by mass of the thermoplastic resin containing 50 to 97% by mass of the aromatic polycarbonate resin (A-1) and 50 to 3% by mass of the elastomer (A-2),
ZrO ₂ —SiO ₂ —HfO ₂ composite oxidation of _{2 to} 25 parts by mass of phosphoric acid ester flame retardant (B-1) and / or phosphazene flame retardant (B-2) and an average particle size of 0.1 to 4 μm A thermoplastic resin composition comprising 1 to 15 parts by mass of the product (C) and 0.001 to 1 part by mass of the fluororesin (D). The thermoplastic resin composition according to claim 1, wherein the phosphate ester flame retardant (B-1) is a phosphate ester flame retardant 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 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. It contains, The thermoplastic resin composition in any one of Claims 1-3 characterized by the above-mentioned.   The elastomer (A-2) is a core / shell type graft copolymer having a core layer containing a polybutadiene-containing rubber or a (meth) acrylic acid ester-based rubber. The thermoplastic resin composition according to claim 1.   The elastomer (A-2) is a core / shell type graft copolymer having an outermost shell layer made of a (meth) acrylic acid ester polymer or an acrylonitrile / styrene copolymer. The thermoplastic resin composition in any one of 1-5. Further, a surface treatment agent _(E), with respect to ZrO ₂ -SiO ₂ -HfO ₂ composite oxide (C) 100 parts by weight, any of the preceding claims, characterized in that it contains 1 to 10 parts by weight The thermoplastic resin composition according to claim 1.   The thermoplastic resin composition according to claim 7, wherein the surface treatment agent (E) is a SiH group-containing organosilicon polymer or a silane coupling agent.   A molded product formed by molding the thermoplastic resin composition according to claim 1.