JP5281969B2 - Aromatic polycarbonate resin composition and molded article using the same - Google Patents

Description

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

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

As means for imparting flame retardancy to a polycarbonate resin, conventionally, a halogen-based flame retardant or a phosphorus-based flame retardant has been added to the polycarbonate resin. However, a polycarbonate resin composition containing a halogen-based flame retardant containing bromine or chlorine may lead to a decrease in thermal stability or corrosion of a molding machine screw or molding die during molding. there were. In addition, the polycarbonate resin composition containing a phosphorus-based flame retardant inhibits the high transparency that is characteristic of the polycarbonate resin and causes a decrease in impact resistance and heat resistance, so that its use is limited. was there.
In addition, these halogen-based flame retardants and phosphorus-based flame retardants may cause environmental pollution at the time of product disposal and recovery, and in recent years, these flame retardants can be made flame retardant without using these flame retardants. It is desired.

  On the other hand, in recent years, metal salt compounds represented by organic alkali metal salt compounds and organic alkaline earth metal salt compounds have been studied as useful flame retardants. Examples of the flame retardant technology of polycarbonate using such a metal salt compound include a method of imparting flame retardancy to an aromatic polycarbonate resin composition using, for example, an alkali metal salt of perfluoroalkyl sulfonic acid having 4 to 8 carbon atoms. (Refer patent document 1) For example, the method etc. (refer patent document 2) etc. which provide flame retardance to an aromatic polycarbonate resin composition using sodium aromatic sulfonate are mentioned.

  However, the flame retardant effect that such a metal salt compound imparts to an aromatic polycarbonate resin is limited, and it has not been possible to obtain a satisfactory level of flame retardant properties. Further, even if the blending amount is increased so as to obtain a higher flame retardant effect, there is a problem that the effect does not increase or the flame retardancy deteriorates.

  Therefore, attempts have been made to improve flame retardancy by further blending silicate compounds such as talc and mica into the aromatic polycarbonate resin blended with the metal salt compound as described above (Patent Documents 3 to 12). reference).

  Further, 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 13 to 17).

  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, development of an aromatic polycarbonate resin having excellent light shielding properties, high flame retardancy, and excellent impact resistance has been strongly desired.

Japanese Patent Publication No. 47-40445 JP 2000-169696 A JP 2002-294063 A JP 2003-82217 A JP 2003-268226 A JP 2004-2750 A JP 2004-10825 A JP 2005-68281 A JP-A-2005-105206 JP 2005-154582 A JP 2006-45282 A JP 2006-117860 A JP-A-6-279661 JP-A-6-279665 Japanese Patent Laid-Open No. 7-25154 JP-A-7-145265 JP-A-8-311315

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

  As a result of intensive investigations to achieve the above-mentioned problems, the present inventors have found that an aromatic polycarbonate resin contains a metal salt compound and a composite oxide of zirconium, silicon, and hafnium having an average particle diameter in a specific range. It has been found that an aromatic polycarbonate resin material having excellent light-shielding properties, high flame retardancy and excellent impact resistance can be obtained by blending each in a specific ratio, and the present invention has been completed.

That is, according to the first invention of the present invention, the fluorine-containing aliphatic sulfonic acid alkali metal salt or aromatic sulfonic acid alkali metal salt (B) 0. Aromatic polycarbonate resin comprising 001 to ₁ part by mass and 0.5 to 10 parts by mass of ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) having an average particle size of 0.1 to 4 μm A composition is provided.

According to the second invention of the present invention, in the first invention, the composition of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) is ZrO ₂ : 50 to 80% by mass, SiO ₂ : An aromatic polycarbonate resin composition characterized by being 25 to 45% by mass and HfO ₂ : 0.05 to 5% by mass (the total amount is 100% by mass) is provided.

According to the third invention of the present invention, in the first or second invention, the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) further comprises Fe ₂ O ₃ , ZrO ₂ , SiO ₂ . ₂ An aromatic polycarbonate resin composition characterized by containing 0.005 to 0.05% by mass with respect to a total of 100% by mass of HfO ₂ is provided.

According to the fourth aspect of the present invention, in any one of the first to third aspects, the fluorine-containing resin (D) is further added in an amount of 0.001 to 100 parts by mass of the aromatic polycarbonate resin (A). An aromatic polycarbonate resin composition containing ˜1 part by mass is provided.

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

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

Furthermore, according to the seventh invention of the present invention, there is provided a molded product formed by molding the aromatic polycarbonate resin composition according to any one of the first to sixth inventions.

  According to the aromatic polycarbonate resin composition of the present invention, it is possible to obtain an aromatic 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 aromatic polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (A), a metal salt compound (B), and a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) having a specific average particle size. It is contained in a specific amount.

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

In formula (1), 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;

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) used in the present invention is arbitrary and may be appropriately selected and determined. However, the viscosity average molecular weight [Mv] is preferably 10,000 to 40,000. When the viscosity average molecular weight is less than 10,000, the mechanical strength tends to be insufficient, and when the viscosity average molecular weight exceeds 40,000, the fluidity is poor and the moldability tends to be deteriorated. The viscosity average molecular weight is more preferably 16,000 to 40,000, still more preferably 18,000 to 30,000. 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 concerning 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) 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. Metal salt compound (B)]
The aromatic polycarbonate resin composition of the present invention contains 0.001 to 1 part by mass of the metal salt compound with respect to 100 parts by mass of the aromatic polycarbonate resin. Thus, the flame retardance of the aromatic polycarbonate resin composition of this invention can be improved by containing a metal salt compound.

  When the content of the metal salt compound is less than 0.001 part by mass, the resulting flame retardant property of the aromatic polycarbonate resin composition becomes insufficient. Conversely, when the content exceeds 1 part by mass, the thermal stability of the aromatic polycarbonate resin is reduced. As a result, the appearance of the molded product of the aromatic polycarbonate resin composition is deteriorated and the mechanical strength is lowered. The lower limit of the content is preferably 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, particularly preferably 0.05 parts by mass or more, and the upper limit is preferably 0.75 parts by mass or less. Preferably it is 0.5 mass part or less, Most preferably, it is 0.3 mass part or less.

  As a kind of metal which a metal salt compound has, it is preferable that they are an alkali metal or an alkaline-earth metal. The aromatic polycarbonate resin composition of the present invention can promote the formation of a carbonized layer at the time of combustion, can further enhance the flame retardancy, and has mechanical properties such as impact resistance, heat resistance, electrical properties, etc. possessed by the aromatic polycarbonate resin. This is because the properties such as the mechanical characteristics can be maintained well. Accordingly, the metal salt compound is preferably at least one metal salt compound selected from the group consisting of alkali metal salts and alkaline earth metal salts, and more preferably alkali metal salts.

Examples of the metal salt compound include an organic metal salt compound and an inorganic metal salt compound, and an organic metal salt compound is preferable from the viewpoint of good dispersibility in an aromatic polycarbonate resin.
Examples of the organic metal salt compound include organic sulfonic acid metal salts, organic sulfonamide metal salts, organic carboxylic acid metal salts, organic boric acid metal salts, and organic phosphoric acid metal salts. Among these, from the viewpoint of thermal stability when mixed with an aromatic polycarbonate resin, an organic sulfonic acid metal salt, an organic sulfonamide metal salt, and an organic phosphoric acid metal salt are preferable, and an organic sulfonic acid metal salt is particularly preferable.

  The metal of the metal salt compound includes alkali metals such as lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs); magnesium (Mg), calcium (Ca), strontium (Sr), alkaline earth metals such as barium (Ba); and aluminum (Al), titanium (Ti), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn ), Zirconium (Zr), molybdenum (Mo) and the like. Of these, alkali metals and alkaline earth metals are preferable, alkali metals are more preferable, and sodium, potassium, and cesium are most preferable.

  Examples of organic sulfonic acid metal salts include organic sulfonic acid lithium (Li) salt, organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, organic sulfonic acid rubidium (Rb) salt, organic sulfonic acid Examples thereof include a cesium (Cs) salt, an organic magnesium sulfonate (Mg) salt, an organic calcium sulfonate (Ca) salt, an organic sulfonic acid strontium (Sr) salt, and an organic sulfonic acid barium (Ba) salt. Among these, organic sulfonic acid alkali metal salts such as organic sulfonic acid sodium (Na) salt, organic sulfonic acid potassium (K) salt, and organic sulfonic acid cesium (Cs) salt are particularly preferable.

  Among the metal salt compounds, preferred examples include metal salts of fluorine-containing aliphatic sulfonic acid or aromatic sulfonic acid, and metal salts of aromatic sulfonamide. Specific examples of preferable ones include potassium perfluorobutane sulfonate, lithium perfluorobutane sulfonate, sodium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, and the like. Alkali metal salt of fluorine-containing aliphatic sulfonic acid having a bond; magnesium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, barium perfluorobutanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, trifluoromethanesulfone A fluorine-containing aliphatic sulfonic acid metal salt of a fluorine-containing aliphatic sulfonic acid having at least one C—F bond in the molecule, such as barium acid;

  Diphenylsulfone-3,3′-disulfonate dipotassium, diphenylsulfone-3-sulfonate potassium, sodium benzenesulfonate, sodium (poly) styrenesulfonate, sodium paratoluenesulfonate, sodium (branched) dodecylbenzenesulfonate, tri Sodium chlorobenzenesulfonate, potassium benzenesulfonate, potassium styrenesulfonate, potassium (poly) styrenesulfonate, potassium paratoluenesulfonate, potassium (branched) dodecylbenzenesulfonate, potassium trichlorobenzenesulfonate, cesium benzenesulfonate, ( Poly) cesium styrene sulfonate, cesium p-toluenesulfonate, cesium (branched) dodecylbenzene sulfonate, cesium trichlorobenzene sulfonate An alkali metal salt of an aromatic sulfonic acid having at least one aromatic group in the molecule; magnesium paratoluenesulfonate, calcium paratoluenesulfonate, strontium paratoluenesulfonate, barium paratoluenesulfonate, (branched Aromatic sulfonic acid metal salts such as :) alkaline earth metal salts of aromatic sulfonic acids having at least one aromatic group in the molecule, such as magnesium dodecylbenzene sulfonate, calcium (branched) calcium dodecylbenzene sulfonate etc,

  Bis (trifluoromethane) sulfonylimide lithium, bis (trifluoromethane) sulfonylimide sodium, bis (trifluoromethane) sulfonylimide potassium, bis (nonafluorobutane) sulfonylimide lithium, bis (nonafluorobutane) sulfonylimide sodium, bis (nona Chain fluorinated fats such as potassium fluorobutane) sulfonylimide, potassium trifluoromethane (pentafluoroethane) sulfonylimide, sodium trifluoromethane (nonafluorobutane) sulfonylimide, potassium trifluoromethane (nonafluorobutane) sulfonylimide, trifluoromethane Alkali metal salts of aromatic sulfonamides; cyclo-hexafluoropropane-1,3-bis (sulfonyl) imidolithium, Alkaline metal salts of cyclic fluorinated aliphatic sulfonic imides such as sodium chloro-hexafluoropropane-1,3-bis (sulfonyl) imide, potassium cyclo-hexafluoropropane-1,3-bis (sulfonyl) imide; Of metal salt of fluorine-containing aliphatic sulfonic acid imide,

  Sodium salt of saccharin, potassium salt of N- (p-tolylsulfonyl) -p-toluenesulfimide, potassium salt of N- (N′-benzylaminocarbonyl) sulfanilimide, potassium of N- (phenylcarboxyl) -sulfanilimide Examples thereof include metal salts of aromatic sulfonic acid imides such as alkali metal salts of aromatic sulfonic acid imides having at least one aromatic group in the molecule, such as salts.

Among the above-described examples, alkali metal salts of fluorine-containing aliphatic sulfonic acids and alkali metal salts of aromatic sulfonic acids are more preferable, alkali metal salts of fluorine-containing aliphatic sulfonic acids are particularly preferable, and perfluoroalkanesulfonic acid. The alkali metal salt is more preferable, and specifically, potassium perfluorobutanesulfonate is preferable.
In addition, 1 type may be used for a metal salt compound, and it may use 2 or more types together by arbitrary combinations and a ratio.

[4. ZrO ₂ —SiO ₂ —HfO ₂ Complex Oxide (C)]
The aromatic polycarbonate resin composition of the present invention comprises a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide having an average particle size of 0.1 to 4 μm in an amount of 0.5 to 100 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Contains 10 parts by weight. By containing a predetermined amount of the ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide having such a particle size, the light shielding property is improved, and the flame extinguishing effect during combustion and the dripping prevention property are improved. The flame retardancy of the composition can be increased.

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

When the content of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is less than 0.5 parts by mass, it is difficult to obtain a sufficient flame retardancy improving effect, and when it exceeds 10 parts by mass, the aromatic polycarbonate resin composition The impact resistance is reduced. The lower limit of the content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and the upper limit of the content is preferably 7.5 parts by mass or less, more preferably 6 parts by mass or less, particularly preferably. Is 4 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 tetraisoproposide (Zr (O-iPr) ₄ ), hafnium tetraisoproposide (Hf (O-iPr) ₄ ), starting from ethyl silicate and zirconium and hafnium alkoxides,
Zirconium silicon hafnium oxide obtained by sol-gel method, hydrothermal synthesis method using SiO ₂ sol, zirconium tetraisoproposide and hafnium tetraisoproposide, or
Sodium silicate _{(Na 2 O · nSiO 2 ·} xH 2 O: n = 2~4) and, zirconium oxychloride, _{ZrO 2} -SiO 2 -HfO 2 composite obtained by hydrolytic polycondensation of hafnium oxychloride An oxide is mentioned.

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

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 measured according to the JIS K 5101-17-2 method of 4 to 7.5. More preferably, it is 4 to 7.0. When the pH of the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide is less than 4, the heat and humidity stability of the aromatic polycarbonate resin tends to decrease, and when the pH exceeds 7.5, the aromatic polycarbonate This is not preferable because the decomposability of the resin is increased and the thermal stability and impact resistance are reduced, and the appearance is poor.

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

The ZrO ₂ component is preferably 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, the SiO ₂ component is preferably 25% by mass or more, more preferably 30% by mass or more, and 45% by mass or less, more preferably 40% by mass or less.
Further, the HfO ₂ component is preferably 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. In particular, it is 2% by mass or less.

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

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

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

  When the content of the fluorine-containing resin is less than 0.001 part by mass, the effect of improving the flame retardancy due to the fluorine-containing resin tends to be insufficient, and when it exceeds 1 part by mass, molding of an aromatic polycarbonate resin composition is performed. There is a tendency that the appearance defect of the product and the mechanical strength 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” manufactured by Daikin Chemical Industries, Ltd. "," 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 covering a fluoroolefin resin, those having a high affinity with an aromatic polycarbonate resin are preferable from the viewpoint of dispersibility when blended with an aromatic polycarbonate resin. An aromatic vinyl monomer, a (meth) acrylic acid ester monomer, and a vinyl cyanide monomer are more preferable.

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

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

[6. Surface treatment agent (E)]
The aromatic polycarbonate resin 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 aromatic polycarbonate resin is reduced, and the influence of decomposition or the like on the aromatic polycarbonate resin is reduced. The aromatic polycarbonate resin is improved in heat 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 formula (2) can be preferably used.

In the above formula (2), R ¹ represents a saturated or unsaturated hydrocarbon group or a hydrogen atom, preferably a hydrocarbon group having 1 to 10 carbon atoms. A functional group may be introduced into the hydrocarbon group. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, and R ¹ may have a substituent, such as a vinyl group, an epoxy group, a methacryl group. And an alkyl group having a group, an amino group, or a mercapto group.

In the above formula (2), R ² represents a saturated or unsaturated hydrocarbon group or a hydrogen atom, preferably a hydrocarbon group having 1 to 10 carbon atoms. Specific examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. R ² may be substituted with a halogen atom such as a chlorine atom.
Further, n 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 treatment agent (E) in the present invention is 0.1 parts by mass or more, more preferably 0.5 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 weight or less, more preferably 8 parts by weight or less, still more preferably 7.5 parts by weight or less, particularly preferably 6 parts by weight. 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.

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

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin (PET resin), polytrimethylene terephthalate (PTT resin), and polybutylene terephthalate resin (PBT resin);
Polystyrene resin (PS resin), high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA) Resin), styrene resin such as acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin);

Polyolefin resins such as polyethylene resin (PE resin), polypropylene resin (PP resin), cyclic cycloolefin resin (COP resin), cyclic cycloolefin copolymer (COP) resin;
Polyamide resin (PA resin); Polyimide resin (PI resin); Polyetherimide resin (PEI resin); Polyurethane resin (PU resin); Polyphenylene ether resin (PPE resin); Polyphenylene sulfide resin (PPS resin); Polysulfone resin (PSU) Resin); polymethacrylate resin (PMMA resin); and the like.
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

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

.. Heat stabilizer Examples of the heat stabilizer include phosphorus compounds. Any known phosphorous compound can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Examples thereof include phosphates of Group 1 or Group 10 metals such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds.

  Among them, triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl diphenyl phosphite, Dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) ) Organic phosphites such as octyl phosphite are preferred.

As such an organic phosphite compound, specifically, for example, “Adeka Stub 1178”, “Adeka Stub 2112”, “Adeka Stub HP-10”, manufactured by Adeka Co., Ltd., manufactured by Johoku Chemical Industry Co., Ltd. Examples thereof include “JP-351”, “JP-360”, “JP-3CP”, “Irgaphos 168” manufactured by Ciba Specialty Chemicals.
In addition, 1 type may contain the heat stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

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

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

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010” (registered trademark, the same shall apply hereinafter) manufactured by Ciba Specialty Chemicals, “Irganox 1076”, and “Adeka Stub” manufactured by Adeka. AO-50 "," ADK STAB AO-60 "and the like.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  The content of the antioxidant is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, and usually 1 part by mass or less, preferably 0.000 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. 5 parts by mass or less. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

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

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

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

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, and the like. Is mentioned.

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

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

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbon includes alicyclic hydrocarbons. Further, these hydrocarbons may be partially oxidized.

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

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

  The content of the release agent is usually 0.001 part by mass or more, preferably 0.01 part by mass or more, and usually 2 parts by mass or less, preferably 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate resin. Or less. When the content of the release agent is not more than the lower limit of the above range, the effect of releasability may not be sufficient, and when the content of the release agent exceeds the upper limit of the above range, hydrolysis resistance And mold contamination during injection molding may occur.

..Ultraviolet absorbers Examples of ultraviolet absorbers include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic acid ester compounds, Examples include organic ultraviolet absorbers such as hindered amine compounds. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the aromatic polycarbonate resin composition of the present invention are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others, 2- (2′- Hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] And 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is particularly preferable.

  Specific examples of such benzotriazole compounds include “Seesorb 701”, “Seesorb 702”, “Seesorb 703”, “Seesorb 704”, and “Seesorb 705” manufactured by Sipro Kasei Co., Ltd. (trade names, the same applies hereinafter). , “Seasorb 709”, “Biosorb 520”, “Biosorb 580”, “Biosorb 582”, “Biosorb 583” manufactured by Kyodo Yakuhin Co., Ltd. “UV5411”, “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, manufactured by Adeka Corporation, “Tinuvin P”, “Cinuvin 234” manufactured by Ciba Specialty Chemicals , "Tinubin 326", "Tinubin 327", "Tinubin 328 Etc. The.

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

-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.

Among these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, phthalocyanine-based dyes and the like are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio. In addition, dyes and pigments may be used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

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

[8. Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known aromatic polycarbonate resin composition can be employ | adopted widely.
Specific examples include aromatic polycarbonate resins and metal salt compounds, fluorine-containing resins, elastomers, ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxides according to the present invention, and other components blended as necessary. Are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc. Can be mentioned.

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

[9. Molding]
The aromatic polycarbonate 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 electrical and electronic equipment include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, mobile phones, and batteries. Packs, recording medium drives and readers, mice, numeric keys, CD players, MD players, portable radio / audio players, and the like.

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

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

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
The measurement / evaluation methods and materials used in Examples and Comparative Examples are as follows.

1. Measurement / Evaluation Method [Flame Retardancy Evaluation]
Flame retardant evaluation of each aromatic polycarbonate resin composition was performed by conditioning a test piece for UL test obtained by the method described below for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. The test was conducted in accordance with UL94 test (combustion test of plastic material for equipment parts) defined by Reiters Laboratories (UL). UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 1 below.

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

[Total light transmittance measurement evaluation]
Evaluation of the total light transmittance of each aromatic polycarbonate resin composition is based on JIS K7361-1, using a flat molded product having a length of 90 mm, a width of 50 mm, and a thickness of 3 mm obtained by the method described below. This was measured with a NDH-2000 type turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd. Smaller values indicate lower light transmittance and better light blocking properties.

[Whiteness measurement evaluation]
Evaluation of the total light transmittance of each aromatic polycarbonate resin composition was performed using a SE2000 type spectral color difference meter manufactured by Nippon Denshoku Industries Co., Ltd. according to JIS K-7105, using the above-mentioned 3 mm-thick flat plate-shaped molded product. The L, a, and b values were measured by the reflection method, and the 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.
In addition, if the value a is on the plus side, it indicates that the color is reddish, and if it is on the minus side, the color is green.

[Impact resistance evaluation]
In accordance with ASTM D256, an ASTM test piece (a 3.2 mm thick notched test piece) obtained by the method described later was used, and the Izod impact strength (unit: J / m) was measured at 23 ° C.

2. Materials used (A) component [aromatic polycarbonate resin]
Bisphenol A-type aromatic polycarbonate resin, trade name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd. Viscosity average molecular weight: 21,000

(B) Component [metal salt compound]
(B-1): Potassium perfluorobutanesulfonate, manufactured by LANXESS, trade name “Bayowet C4”
(B-2): Sodium paratoluenesulfonate, manufactured by Cambridge International, trade name “Chemguard-NATS”
Component (C) [ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide]
The following _ZrO 2 are shown in Table 2 -SiO ₂ -HfO ₂ composite oxide (C-1) was prepared ~ a (C-8).

[Silates other than ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxides]
[talc]
Product name “Micron White # 5000S” manufactured by Hayashi Kasei Co., Ltd.
Average particle size 2.8 μm
[Mica]
Product name “A-21” manufactured by Yamaguchi Mica Co., Ltd., average particle size 22 μm
[Titanium oxide]
Made by Ishihara Sangyo Co., Ltd., trade name “Taipeke PC-3”, average particle size 0.2 μm

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 siloxane Made by Toray Dow Corning, trade name “SH1107 FLUID”

In addition to the above components, the following stabilizers (component (F)) and two lubricants (component (G)) were blended in the following amounts in the examples and comparative examples.
(F) component [stabilizer]
(F-1) Tris (2,4-di-tert-butylphenyl) phosphite manufactured by ADEKA, trade name “ADK STAB 2112” 0.05% by mass
(F-2) Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals,
Product name "Irganox 1010" 0.1% by mass

(G) component [lubricant]
(G-1) Stearic acid manufactured by NOF Corporation, trade name “NAA180” 0.075% by mass
(G-2) Pentaerythritol stearate, Cognis Japan, trade name “Roxyol VPG861” 0.075 mass%

(Examples 1-8, Comparative Examples 1-8)
As said (A)-(E) component, after mix | blending the material shown in Table 3, Table 4 in the ratio (all mass%) described in Table 3, Table 4, and mixing for 20 minutes with a tumbler, Molten resin extruded into a strand after being fed to a twin-screw extruder (TEX30HSST) manufactured by Nippon Steel Works, equipped with one vent, kneaded under the conditions of a screw speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 290 ° C. The composition was quenched in a water bath and pelletized using a pelletizer to obtain an aromatic polycarbonate resin composition pellet.

  Next, after drying the pellet obtained by the above-mentioned manufacturing method at 120 ° C. for 5 hours, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, the cylinder temperature is 280 ° C. and the mold temperature is 80 ° C. The specimens were injection molded under the conditions described above to form flat test pieces (90 mm × 50 mm × 3 mm thickness) and ASTM test pieces (3.2 mm thickness). The ASTM test piece was further notched using an SA-1002 auto-notching machine manufactured by Tester Sangyo Co., Ltd.

Similarly, after the pellets obtained by the above-described production method were dried at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel, the cylinder temperature was 280 ° C. and the mold temperature was 80 A test piece for UL test having a length of 125 mm, a width of 13 mm, and a thickness of 1.2 mm was molded by injection molding under the condition of ° C.
The evaluation results for the obtained test pieces are shown in Table 3 (Examples) and Table 4 (Comparative Examples).

When Examples 1-8 and Comparative Examples 1-8 are contrasted, the ZrO ₂ —SiO ₂ —HfO ₂ composite oxide having a specific particle size of the present invention is mixed with a predetermined amount in an aromatic polycarbonate together with a metal salt. It can be seen that it exhibits whiteness, improves light shielding properties, has a flame retardancy evaluation of V-0, has high flame retardancy, and is excellent in impact resistance.
On the other hand, Comparative Example 1 that does not include a ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide and Comparative Example 2 that has a low content thereof are poor in flame retardancy and poor in light shielding properties and whiteness. Moreover, in Comparative Examples 3, 4, and 5 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 improvement effect is hardly exhibited, and the whiteness is not sufficient. The a value is getting higher. In Comparative Examples 6 and 7 using talc and mica, although the flame retardancy effect is high, the light shielding property and whiteness are poor and the impact resistance is low. In Comparative Example 8 using titanium oxide, the light shielding property and whiteness are good. However, it turns out that flame retardance and impact resistance are bad.

The composition of the present invention has low light transmittance, high whiteness, little redness, and its level is in contrast to the low light-shielding properties and whiteness of talc and mica of Comparative Examples 6 and 7, It turns out that the aromatic polycarbonate resin composition of this invention shows the light-shielding property and whiteness which are close to titanium white. In addition, although the thing of Example 8 with many iron oxide components is reddish, light-shielding property and whiteness are enough.
Therefore, from the above examples and comparative examples, the effect of obtaining an excellent light-shielding property, high whiteness, flame retardancy and impact resistance can be obtained for the first time by the configuration of the present invention. It was confirmed that there was.

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

Claims (7)

With respect to 100 parts by mass of the aromatic polycarbonate resin (A), 0.001 to 1 part by mass of an alkali metal salt of a fluorine-containing aliphatic sulfonic acid or an alkali metal salt of an aromatic sulfonic acid (B) and an average particle size of 0. An aromatic polycarbonate resin composition comprising 0.5 to 10 parts by mass of 1 to 4 μm of ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C). 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 (total amount) Is 100 mass%), the aromatic polycarbonate resin composition according to claim 1. ZrO ₂ —SiO ₂ —HfO ₂ -based composite oxide (C) further contains Fe ₂ 0 ₃ in an amount of 0.005 to 0.05% by mass with respect to 100% by mass of ZrO ₂ , SiO ₂ and HfO ₂ in total. The aromatic polycarbonate resin composition according to claim 1, wherein: Furthermore, 0.001-1 mass part is contained for fluororesin (D) with respect to 100 mass parts of aromatic polycarbonate resin (A), The fragrance in any one of Claims 1-3 characterized by the above-mentioned. Group polycarbonate resin composition. Further, a surface treatment agent _{(E), ZrO 2 -SiO 2} -HfO 2 composite oxide (C) relative to 100 parts by weight, more of claims 1-4, characterized in that it contains 1 to 10 parts by weight An aromatic polycarbonate resin composition according to claim 1. 6. The aromatic polycarbonate resin composition according to claim 5 , wherein the surface treatment agent (E) is a SiH group-containing organosilicon polymer or a silane coupling agent. An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 6 .