JP2019099671A - Polycarbonate resin composition - Google Patents

Abstract

To provide a resin composition having high specific gravity, high rigidity, high dimensional stability (low anisotropy) and excellent flame retardancy.SOLUTION: The present invention provides an aromatic polycarbonate resin composition containing, based on (A) aromatic polycarbonate resin (component A) 100 pts.wt., (B) barium sulfate (component B) 50-400 pts.wt., (C) phosphorous flame retardant (component C) 5-50 pts.wt. and (D) fluorine-containing drip inhibitor having a fibril-forming ability (component D) 0.1-3 pts.wt.SELECTED DRAWING: None

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition having high specific gravity, high rigidity, high dimensional accuracy and good flame retardancy by containing barium sulfate and a flame retardant.

  In recent years, the resin material used for the chassis of an apparatus having an optical system unit such as a laser beam printer, a copying machine and a projector apparatus (hereinafter sometimes simply referred to as "optical unit chassis") is often high. Stiffness, high dimensional accuracy (low anisotropy) and good flame retardancy are required. Many resin compositions suitable for these chassis have been proposed conventionally. For example, Patent Document 1 describes a resin composition comprising a polycarbonate resin, a flame retardant, an inorganic filler in which glass fibers and wollastonite are combined in a specific ratio, and a polytetrafluoroethylene having a fibril-forming ability. Are disclosed to have high rigidity, high dimensional accuracy and good flame retardancy. Patent Document 2 describes a resin composition comprising a polycarbonate resin, a styrene resin, mica, talc, a phosphorus-based flame retardant and a fluorine-containing antidrop agent, and the composition has high rigidity and high dimensional accuracy (low anisotropy It is disclosed that the resin composition is a flame retardant resin composition which satisfies all of the properties of good flame retardancy, hydrolysis resistance and self tap characteristics in a well-balanced manner.

  On the other hand, in the case of an optical unit chassis for high-speed processing equipment such as a production printer, vibration caused by a motor driven at high speed is an issue, and therefore, in addition to the characteristics required for the material for optical unit chassis Vibration is required. As means for imparting vibration resistance, it is possible to increase the weight of the member, that is, to increase the specific gravity of the material. As means for increasing the specific gravity of the material, for example, a high specific gravity resin composition obtained by adding barium sulfate to a resin composition consisting of a polycarbonate resin and a polybutylene terephthalate resin is disclosed (Patent Document 3). However, since polybutylene terephthalate resin is contained, there are problems in dimensional accuracy and flame retardancy, and it is unsuitable as a material for an optical unit chassis.

  As described above, a resin composition having high specific gravity, high rigidity, high dimensional stability (low anisotropy) and good flame retardancy applicable to an optical unit chassis such as a production printer has not been obtained. It is.

JP 2001-164105 A JP, 2006-36877, A Unexamined-Japanese-Patent No. 08-199049

  In view of the above, it is an object of the present invention to provide an aromatic polycarbonate resin composition having high specific gravity, high rigidity, high dimensional stability (low anisotropy) and good flame retardancy and a molded article made therefrom is there.

  As a result of intensive investigations conducted by the present inventor, the resin composition comprising an aromatic polycarbonate resin, barium sulfate, a phosphorus-based flame retardant and a fluorine-containing antidrop agent has high specific gravity, high rigidity, high dimensional accuracy (low anisotropy ) And good flame retardancy, and completed the present invention.

  According to the present invention, (B) 50 to 400 parts by weight of barium sulfate (component B) with respect to 100 parts by weight of (1) (A) aromatic polycarbonate resin (component A), (C) phosphorus-based flame retardant (C) An aromatic polycarbonate resin composition is provided which contains 5 to 50 parts by weight of component (D) and 0.1 to 3 parts by weight of a fluorine-containing anti-dropping agent (component D) having fibril-forming ability.

One of the preferable embodiments of the present invention is that the composition (1) contains 10 to 150 parts by weight of a plate-like filler (component E) other than the component (E) per 100 parts by weight of the component (2). It is an aromatic polycarbonate resin composition.
One of the preferred embodiments of the present invention is (3) the aromatic polycarbonate resin composition of the above-mentioned constitution (2) wherein the E component is mica.
One of the preferred embodiments of the present invention is any of the above-mentioned constitutions (1) to (3) containing 10 to 150 parts by weight of (F) glass fiber (component F) with respect to 100 parts by weight of (4) component A It is an aromatic polycarbonate resin composition.
One of the preferable embodiments of the present invention is (5) the aromatic polycarbonate resin composition according to any one of the above configurations (1) to (4) having a specific gravity of 1.8 or more.
One of the preferred embodiments of the present invention is (6) a molded article comprising the aromatic polycarbonate resin composition of any of the above-mentioned constitutions (1) to (5).

  Hereinafter, the details of the present invention will be described.

<About component A>
The resin composition of the present invention contains an aromatic polycarbonate resin as the component A. The aromatic polycarbonate resin used in the present invention may be any of various aromatic polycarbonate resins having high heat resistance or low water absorption, which is polymerized using other dihydric phenol in addition to commonly used bisphenol A polycarbonate. It may be The aromatic polycarbonate resin may be produced by any production method, and in the case of interfacial polycondensation, a monohydric phenol terminator is usually used. The aromatic polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols. The viscosity average molecular weight of the aromatic polycarbonate resin is preferably 1.3 × 10 ^{4 to} 4.0 × 10 ⁴ , more preferably 1.5 × 10 ^{4 to} 3.8 × 10 ⁴ . The viscosity average molecular weight (M) of the aromatic polycarbonate resin is obtained by inserting the specific viscosity (η _sp ) obtained at 20 ° C. from a solution of 0.7 g of the aromatic polycarbonate resin dissolved in 100 ml of methylene chloride into the following formula is there. The details of the aromatic polycarbonate resin are described in JP-A-2002-129003.
η _sp /c=[η]+0.45×[η] ² c (where [η] is the limiting viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  As specific examples of various polycarbonate resins having high heat resistance or low water absorption, which are polymerized using other dihydric phenols, the following are suitably exemplified.

  (1) 20 to 80 mol% (more preferable) of 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as “BPM”) component in 100 mol% of dihydric phenol components constituting the polycarbonate 40 to 75 mol%, more preferably 45 to 65 mol%), and the 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as “BCF”) component is Copolymerized polycarbonate which is 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  (2) 10 to 95 mol% (more preferably 50 to 90 mol%, still more preferably 60 to 85 mol%) of the bisphenol A component in 100 mol% of the dihydric phenol component constituting the polycarbonate, And a copolymerized polycarbonate wherein the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).

  (3) The BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%) Copolycarbonate. These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used with the bisphenol A type polycarbonate generally used. The production methods and properties of these special polycarbonates are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435 and JP-A-2002-117580. ing. It is also possible to use polycarbonate-polyorganosiloxane copolymers in which the polyorganosiloxane units are copolymerized.

  As the aromatic polycarbonate resin, not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product can be used. Examples of the used products include containers represented by water bottles, optical disks and automobile headlamps.

<About B component>
The resin composition of the present invention contains barium sulfate as the B component. By containing barium sulfate, high specific gravity can be achieved without impairing the flame retardancy of the resin composition.

  The barium sulfate of the present invention may be either naturally occurring or synthetically obtained. As naturally occurring ones, for example, crushed natural barite can be used. . In addition, barium sulfate synthesized by a known synthesis method can be used as one obtained by the synthesis.

  The shape of the barium sulfate of the present invention is not particularly limited, such as granular, spherical or plate-like. The particle diameter is also not particularly limited, but is preferably 0.5 to 50 μm, and more preferably 3 to 20 μm. As a commercial item of this barium sulfate, Takehara Chemical Industry Co., Ltd. W-6, W-10, A-200 etc. are mentioned.

  The content of the component B is 50 to 400 parts by weight, preferably 70 to 300 parts by weight, and more preferably 90 to 250 parts by weight with respect to 100 parts by weight of the component A. If the content of the component B is too large to exceed the above range, extrusion becomes difficult. Conversely, if the amount is too small, the desired specific gravity can not be obtained.

<About the C component>
The resin composition of the present invention contains a phosphorus-based flame retardant as the component C. As phosphorus-based flame retardants according to the invention, phosphate compounds, in particular aryl phosphate compounds, are suitable. Such phosphate compounds are effective in improving the flame retardancy, and since the phosphate compounds have a plasticizing effect, they have a decrease in heat resistance, but they are advantageous in that they can enhance the molding processability of the resin composition of the present invention. It is. As such phosphate compounds, various phosphate compounds conventionally known as flame retardants can be used, and more preferably, one or two or more phosphate compounds represented by the following general formula (1) can be mentioned.

(Wherein X represents hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis (4-hydroxyphenyl) ketone; It is a dihydric phenol residue derived from a dihydroxy compound selected from the group consisting of 4-hydroxyphenyl) sulfide, and n is an integer of 0 to 5 or, in the case of a mixture of different phosphoric acid esters, their averages R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently derived from an aryl group selected from the group consisting of independent phenol, cresol, xylenol, isopropylphenol, butylphenol and p-cumylphenol Price Pheno Residue))

The phosphate compound of the above general formula (1) may be a mixture of compounds having different n numbers, and in the case of such a mixture, the average n number is preferably 0.5 to 1.5, more preferably 0. The range is 8 to 1.2, more preferably 0.95 to 1.15, and particularly preferably 1 to 1.14. Preferable specific examples of the dihydric phenol which derives X of the above-mentioned general formula (1) are resorcinol, bisphenol A and dihydroxydiphenyl, and among them resorcinol and bisphenol A are preferable among them. Preferred specific examples of the monohydric phenol for deriving R ¹¹ , R ¹² , R ¹³ and R ¹⁴ of the above formula (1) are phenol, cresol, xylenol, 2,6-dimethylphenol, and among them, phenol is particularly preferable. And 2,6-dimethylphenol. Specific examples of the phosphate compound of the above general formula (1) are mainly based on monophosphate compounds such as triphenyl phosphate and tri (2,6-xylyl) phosphate and resorcinol bis (2,6-xylyl) phosphate). Phosphate oligomers, phosphate oligomers based on 4,4-dihydroxydiphenyl bis (diphenyl phosphate) and phosphoric acid ester oligomers based on bisphenol A bis (diphenyl phosphate) are preferred, among which resorcinol bis di (2, 6-xylyl) ) Phosphate oligomers based on (phosphate), Phosphate oligomers based on 4, 4-dihydroxydiphenyl bis (diphenyl phosphate) and bisphenol A bis (diphenyl phosphate) Phosphoric acid ester oligomer composed mainly of Feto) is particularly preferred. Moreover, a phosphazene compound is also mentioned as a suitable phosphorus flame retardant. The phosphazene compound is preferably a cyclic phenoxy phosphazene represented by the following general formula (2).

〔式中ｍは３〜２５の整数を示す。Ｐｈはフェニル基を示す。〕

Wherein m represents an integer of 3 to 25. Ph represents a phenyl group. ]

  Representative examples of commercially available cyclic phenoxy phosphazene include FP-100 manufactured by Fushimi Pharmaceutical Co., Ltd., and the like.

  The content of the component C is 5 to 50 parts by weight, preferably 7 to 40 parts by weight, and more preferably 10 to 30 parts by weight with respect to 100 parts by weight of the component A. If the content of the C component is too large to exceed the above range, the heat resistance decreases, and conversely, if it is too small, desired flame retardancy can not be obtained.

<About D component>
The resin composition of the present invention contains, as component D, a fluorine-containing anti-dripping agent having a fibril-forming ability. By containing this fluorine-containing anti-dropping agent, good flame retardancy can be achieved without impairing the physical properties of the molded article. Examples of the fluorine-containing anti-dripping agent include fluorine-containing polymers having fibril-forming ability, and such polymers include polytetrafluoroethylene and tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer). And the like, partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, and the like. Among them, polytetrafluoroethylene (hereinafter sometimes referred to as PTFE) is preferable. The molecular weight of the fibril-forming PTFE has an extremely high molecular weight, and tends to bond the PTFE to form a fiber by an external action such as shear force. The molecular weight is preferably 1,000,000 to 10,000,000, more preferably 2,000,000 to 9,000,000 in terms of the number average molecular weight determined from the standard specific gravity. Such PTFE may be used in the form of an aqueous dispersion in addition to the solid form. It is also possible to use a PTFE mixture in the form of a mixture with other resins in order to improve the dispersibility in the resin and to obtain good flame retardancy and mechanical properties, as well as such fibril-forming PTFE. is there. As a commercial item of PTFE which has such fibril formation ability, Teflon (registered trademark) 6J of Mitsui-Dupont Fluorochemicals Co., Ltd., polyflon MPA FA500 and F-201L of Daikin Industries, Ltd., etc. can be mentioned. Commercially available products of the aqueous dispersion of PTFE include Fluon AD-1 and AD-936 manufactured by Asahi IC Eye Fluoropolymers Co., Ltd., Fluon D-1 and D-2 manufactured by Daikin Industries, Ltd., Mitsui Dupont Floro Representative examples thereof include Teflon (registered trademark) 30J manufactured by Chemical Co., Ltd. and the like. As the mixed form of PTFE, (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and coprecipitating to obtain a co-agglomerated mixture (Japanese Patent Application Laid-Open No. 60-258263; (2) a method of mixing an aqueous dispersion of PTFE and dried organic polymer particles (a method described in JP-A-4-272957); (3) A method of uniformly mixing an aqueous dispersion of PTFE and an organic polymer particle solution and simultaneously removing the respective media from the mixture (described in JP-A 06-220210, JP-A 08-188653, etc.) Method), (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (the method described in JP-A-9-95583), and (5) A method of uniformly mixing an aqueous dispersion of TFE and an organic polymer dispersion, and then polymerizing a vinyl monomer in the mixed dispersion, and thereafter obtaining a mixture (described in JP-A-11-29679, etc.) Method) can be used. As a commercial item of PTFE of these mixed forms, "Metabrene A3800" (brand name) of Mitsubishi Rayon Co., Ltd., and "BLENDEX B 449" (brand name) manufactured by GE Specialty Chemicals, etc. can be mentioned. The proportion of PTFE in the mixed form is preferably 1 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the PTFE mixture. If the proportion of PTFE is in such a range, good dispersibility of PTFE can be achieved. The proportion of the component D indicates the net amount of the fluorine-containing anti-dropping agent, and in the case of the mixed form of PTFE, the net amount of PTFE.

  Content of D component is 0.1-3 weight part with respect to 100 weight part of A component, Preferably it is 0.3-2 weight part. If the content of the component D is too large to exceed the above range, the cost of the resin composition will increase. If the content is too small, the flame retardancy will be insufficient.

<About E component>
The resin composition of the present invention preferably contains a plate-like filler other than the B component as the E component, and examples thereof include mica, talc, glass flakes, metal flakes, metal coated glass flakes, etc., among which mica is preferable. It is. As a pulverization method of mica, a dry pulverization method of pulverizing mica ore by a dry pulverizer and a coarse pulverization of mica ore by a dry pulverizer, and then adding a pulverization aid such as water and the like, a wet pulverization in a slurry state There is a wet grinding method in which the main grinding is performed by a machine, followed by dehydration and drying. The mica of the present invention may be produced by any of the grinding methods, but the dry grinding method is less expensive and more general. In addition, even in mica produced by the dry pulverization method, the proportion of iron-containing impurities is reduced by sufficiently performing magnetic force sorting (for example, sorting by a magnetic force sorter of 1000 mT or more), and mica having good characteristics is obtained. It is possible to get. The wet grinding method is effective for grinding mica thinner and finely, but it is costly. Mica may be surface-treated with various surface treatment agents such as silane coupling agents, higher fatty acid esters, and waxes, and further granulated with various resins, higher fatty acid esters, and bundling agents such as waxes to form granules. It may be done. The particle size of mica is not particularly limited, but one having a number average particle diameter of 30 to 300 μm, which is calculated by a total number of 1,000 extracted indiscriminately by observation with a scanning electron microscope, is preferable . As the thickness of mica, one having a thickness of 0.01 to 10 μm measured by electron microscope observation is preferable. The mica used is preferably muscovite mica, and its Mohs hardness is about 3. Muscovite mica can achieve higher rigidity and high strength compared to other micas such as phlogopite.

  The content of component E is preferably 10 to 150 parts by weight, more preferably 20 to 130 parts by weight, and still more preferably 30 to 110 parts by weight with respect to 100 parts by weight of component A. If the content of the component E is too large to exceed the above range, extrusion may be difficult. On the other hand, when the amount is too small, the effect of imparting rigidity or reducing the linear expansion coefficient is small, and the effect of addition may not be obtained.

<About the F component>
The resin composition of the present invention preferably contains glass fiber as the F component. Although there is no restriction | limiting in particular regarding the fiber diameter of glass fiber, 5-20 micrometers is preferable, More preferably, it is 8-15 micrometers. The fiber length is also not particularly limited, but preferably 1 to 10 mm. The glass fiber does not particularly limit the glass composition of A glass, C glass, E glass and the like, and may optionally contain components such as TiO ₂ , SO ₂ and P ₂ O ₅ . However, more preferably, E glass (alkali-free glass) is preferable in that it does not adversely affect the aromatic polycarbonate resin. Glass fiber is obtained by quenching molten glass while drawing it by various methods and forming it into a predetermined fibrous form. The conditions for quenching and stretching in such a case are also not particularly limited. Further, the cross-sectional shape may be an irregular cross-sectional shape in which true-circular fibers are overlapped in parallel, in addition to a general perfect circular shape. Furthermore, it may be a mixed glass fiber of a true circular shape and an irregular cross sectional shape. Glass fiber can be subjected to a focusing treatment with various compounds such as epoxy, urethane and acrylic. The amount of the bundling agent is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, in 100% by weight of the bundling glass fiber. Further, those which have been surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like are preferable.

  The content of the F component is preferably 10 to 150 parts by weight, more preferably 15 to 120 parts by weight, and still more preferably 20 to 90 parts by weight with respect to 100 parts by weight of the component A. If the content of the F component is too large to exceed the above range, the dimension anisotropy may increase. On the other hand, when the amount is too small, the effect of addition of the agent may not be obtained because the effect of imparting rigidity is small.

<About other ingredients>
The resin composition of the present invention further includes phosphorus stabilizers, hindered phenol antioxidants, mold release agents, ultraviolet absorbers, antistatic agents, foaming agents, dyes and pigments (carbon black, titanium oxide, etc.), etc. Can also be blended.

(I) Phosphorus-Based Stabilizer It is preferable that various heat stabilizers be blended in the resin composition of the present invention. Phosphorus stabilizers are suitable as such heat stabilizers. Examples of the phosphorus-based stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphines. Such phosphorus stabilizers can be used alone or in combination of two or more. As the phosphite compound, for example, trialkyl phosphite such as tridecyl phosphite, dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, triphenyl phosphite And triaryl phosphites such as tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Pentaellises such as bis (2,4-dicumylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Methylol phosphite, as well as 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2'-methylenebis (4,6-di-tert-butylphenyl) (2,4-) An example is a cyclic phosphite such as di-tert-butylphenyl) phosphite. Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl mono orthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate, and the like. Triphenyl phosphate, trimethyl phosphate. Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite, and tetrakis (2,4-di-tert) More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenyl phosphonite. Such a phosphonite compound can be used in combination with a phosphite compound having an aryl group in which two or more of the above-mentioned alkyl groups are substituted, which is preferable. As the phosphonate compound, dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. As a tertiary phosphine, a triphenyl phosphine is illustrated, for example.

  The content of the phosphorus-based stabilizer is preferably 0.0001 to 1.5 parts by weight, more preferably 0.0005 to 1.0 parts by weight, and more preferably 0.002 to 0.8 with respect to 100 parts by weight of the component A. Parts by weight are more preferred.

(Ii) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds which are usually blended in a resin can be used. As such hindered phenol compounds, for example, α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene bis (3-methyl-6-tert -Butylphenol), triethylene glycol N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-Butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1- Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl) -6-tert-Butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'- Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodiethyl Bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- (3) 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocy Anurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl-) 4-hydroxyphenyl) propionate] methane, triethylene glycol N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol N-bis-3- (3- tert-Butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [ Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy- 5-methylbenzyl) benzene, and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate and the like are exemplified. Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8, 10-tetraoxaspiro [5, 5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The above hindered phenolic antioxidants can be used alone or in combination of two or more.

  The content of the hindered phenol-based antioxidant is preferably 0.0001 to 1.5 parts by weight, more preferably 0.0005 to 1.0 parts by weight, and more preferably 0.002 to 100 parts by weight of the component A. 0.8 parts by weight is more preferred.

(Iii) Release Agent It is preferable to further add a release agent to the polycarbonate resin composition of the present invention for the purpose of improving the productivity at the time of molding and reducing the distortion of the molded product. As such a release agent, known ones can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., those modified with functional group containing compounds such as acid modified can also be used), silicone compounds, fluorine compounds ( Fluorine oil represented by polyfluoroalkyl ether etc.), paraffin wax, beeswax etc. can be mentioned. Among them, fatty acid esters are mentioned as preferable release agents. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol having two or more valences. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, mannitol and the like. In the fatty acid ester of the present invention, polyhydric alcohols are more preferred. On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as eicosanoic acid and docosanoic acid and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid and cereic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Among them, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred. The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from animal fats and oils represented by beef tallow and pork fat and natural fats and oils such as vegetable fats and oils represented by palm oil and sunflower oil Thus, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Therefore, aliphatic carboxylic acids produced from such natural oils and fats and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid, are preferably used also in the production of the fatty acid ester of the present invention. The fatty acid ester may be either partial ester or whole ester (full ester). However, partial esters usually have a high hydroxyl value and easily cause decomposition of the resin at high temperatures, and so are preferably full esters. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value may be substantially zero. Moreover, as for the hydroxyl value of fatty acid ester, the range of 0.1-30 is more preferable. Furthermore, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These properties can be determined by the method defined in JIS K 0070.

  The content of the releasing agent is preferably 0.01 to 4.0 parts by weight, more preferably 0.05 to 3.0 parts by weight, still more preferably 0.1 to 2 parts by weight per 100 parts by weight of the component A. .5 parts by weight.

(Iv) Ultraviolet Absorbent The polycarbonate resin composition of the present invention can contain an ultraviolet absorbent. In the benzophenone series, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4-methoxy- 5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydrate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) ) Methane, 2-hydroxy -4-n-dodecyloxy bensophenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone and the like are exemplified. In the benzotriazole system, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,3) 5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2'-methylenebis [4- (1,1,3) , 3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2- Hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-) Di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2- (2-hydroxy-5-tert-butylphenyl) benzotriazole) 2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p-phenylenebis (1,3-benzoxazine-4) -One), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-hydroxy-5-methacryloxy) A copolymer of ethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with the monomer, or -A heavy chain having a 2-hydroxyphenyl-2H-benzotriazole skeleton such as a copolymer of-(2'-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole and a vinyl monomer copolymerizable with said monomer A combination etc. are illustrated. In the hydroxyphenyl triazine series, for example, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol, 2- (4,6-diphenyl-1,3,5) -Triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxyphenol, 2- (4,6-diphenyl) -1,3,5-Triazin-2-yl) -5-propyloxyphenol and 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-butyloxyphenol It is illustrated. Furthermore, the phenyl group of the above exemplified compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl The compound which became a phenyl group is illustrated. In cyclic imino ester systems, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) bis (3,1-benzoxazine) -4-one), and 2,2 '-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  In the cyanoacrylate system, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2-cyano-3,3-diphenylacryloyl) oxy Examples include methyl) propane, 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene and the like.

  Furthermore, the above-mentioned ultraviolet absorber takes such a structure of a monomer compound capable of radical polymerization, whereby such a UV-absorbing monomer and / or a light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate The ultraviolet absorber of the polymer type which copolymerized with monomers, such as, may be sufficient. Preferred examples of the UV absorbing monomer include compounds having a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. Ru.

  Among the above, benzotriazole-based and hydroxyphenyltriazine-based ones are preferable in view of ultraviolet light absorbing ability, and cyclic imino ester-based ones and cyanoacrylate-based ones are preferable in view of heat resistance and hue (transparency). The UV absorbers may be used alone or in combination of two or more.

  The content of the ultraviolet absorber is preferably 0.01 to 2.0 parts by weight, more preferably 0.02 to 1.5 parts by weight, and still more preferably 0.03 to 1 part by weight per 100 parts by weight of component A. .0 parts by weight.

(V) Other Heat Stabilizers The polycarbonate resin composition of the present invention may also be blended with other heat stabilizers other than the above-mentioned phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers The details of are preferably exemplified in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and the compound can be used. Furthermore, stabilizers obtained by mixing the compounds with various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. Such premixed stabilizers can also be utilized in the present invention. The amount of the lactone stabilizer blended is preferably 0.0005 to 0.1 parts by weight, more preferably 0.001 to 0.05 parts by weight, per 100 parts by weight of the component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. It is illustrated. Such stabilizers are particularly effective when the resin composition is applied to rotomolding. The compounding amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight with respect to 100 parts by weight of the component A.

(Vi) Other Fillers In the aromatic polycarbonate resin composition of the present invention, various fillers other than the B component, the E component, and the F component may be blended as a reinforcing filler in the range where the effects of the present invention are exhibited. it can. For example, calcium carbonate, glass beads, glass balloons, glass milled fibers, carbon fibers, carbon beads, carbon milled fibers, graphite, vapor grown ultrafine carbon fibers (fiber diameter is less than 0.1 μm), carbon nanotubes (fiber diameter is Less than 0.1 μm, hollow), fullerene, metal fiber, metal coated glass fiber, metal coated carbon fiber, silica, metal oxide particle, metal oxide fiber, metal oxide balloon, and various whiskers (potassium titanate) Examples include whiskers, aluminum borate whiskers, and basic magnesium sulfate). These reinforcing fillers may be used alone or in combination of two or more. The content of these fillers is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the component A.

(Vii) Other Resins and Elastomers In the resin composition of the present invention, a small proportion of other resins and elastomers can be used as long as the effects of the present invention are exhibited. Such other resins include, for example, polyester resin, AS resin, ABS resin, AES resin, polyamide resin, polyamide resin, polyimide resin, polyetherimide resin, polyurethane resin, silicone resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyethylene, Examples thereof include polyolefin resins such as polypropylene, resins such as polymethacrylate resins, phenol resins and epoxy resins. Examples of the elastomer include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, polyamide elastomers, and the like.

(Viii) Adhesion Improver An adhesion improver can be added to the resin composition of the present invention. The adhesion improver is a compound that improves the adhesion between the aromatic polycarbonate resin as the component A, a plate-like filler other than the component B as the component B, barium sulfate as the component B, and the glass fiber as the component F. . Among them, organic compounds having at least one functional group selected from the group consisting of an epoxy group, a carboxylic acid group and an acid anhydride group in one molecule are preferably used. The epoxy group-containing compound is not particularly limited as long as it is an epoxy group-containing organic compound, and phenoxy resin and epoxy resin can be mentioned.

  As a phenoxy resin, the phenoxy resin etc. which are represented by following General formula (3) are mentioned, for example.

（式中、Ｘは下記一般式（４）で表される基からなる群より選ばれる少なくとも一つの基、Ｙは水素原子又は水酸基と反応する化合物の残基、ｎは０以上の整数である。）

(Wherein X is at least one group selected from the group consisting of groups represented by the following general formula (4), Y is a residue of a compound that reacts with a hydrogen atom or a hydroxyl group, n is an integer of 0 or more) .)

（式中、Ｐｈはフェニル基を示す。）

(In the formula, Ph represents a phenyl group.)

  As an epoxy resin, the epoxy resin etc. which are represented by following General formula (5) are mentioned, for example.

（式中、Ｘ及びｎは一般式（３）と同じである。）

(Wherein, X and n are the same as in the general formula (3))

  Examples of the compound which reacts with a hydroxyl group in the above general formula (3) include a compound having an ester, a carbonate, an epoxy group, etc., a compound having a carboxylic acid anhydride, an acid halide, an isocyanate group etc. Particularly preferred is an intramolecular ester, such as caprolactone. In the phenoxy resin represented by the above general formula (3), a compound in which Y is a hydrogen atom can be easily produced from dihydric phenols and epichlorohydrin. In addition, a compound in which Y is a residue of a compound that reacts with a hydroxyl group can be easily prepared by mixing a phenoxy resin prepared from a divalent phenol and epichlorohydrin with a compound that reacts with the hydroxyl group under heating. Can.

  The epoxy resin represented by the above general formula (5) can be easily produced from dihydric phenols and epichlorohydrin. As dihydric phenols, bisphenol A-type epoxy resins such as 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane or 4,4'-dihydroxy Biphenyl etc. are used. A commercial item can also be used as a phenoxy resin and an epoxy resin. Commercially available products of phenoxy resin (bisphenol A type) include PKHB (InChem, Mw = 13,700), PKHH (InChem, Mw = 29,000), and PKFE (InChem, Mw = 36,800). And YP-50 (made by Tohto Kasei Co., Ltd., Mw = 43, 500) and the like. Moreover, as a commercial item of an epoxy resin (bisphenol A type), EPICLON HM-101 (made by Dainippon Ink & Chemicals, Inc., Mw = 48,000), jER1256 (made by Mitsubishi Chemical Corporation, Mw = 26, 600), etc. Can be mentioned. The weight average molecular weight of the phenoxy resin and the epoxy resin is not particularly limited, but is usually 5,000 to 100,000, preferably 8,000 to 80,000, and more preferably 10,000 to 50,000. is there. When the weight average molecular weight is in the range of 5,000 to 100,000, mechanical properties are particularly good. Moreover, the polymer of a glycidyl group containing vinyl-type unit is mentioned as an organic compound containing an epoxy group. Specific examples of the glycidyl group-containing vinyl-based unit include glycidyl methacrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl ether, 4-glycidyl styrene and the like, and they have impact resistance, weld strength and elongation. Glycidyl methacrylate is most preferably used from the viewpoint that the degree improvement effect is large.

  The carboxylic acid group-containing compound is not particularly limited as long as it is an organic compound containing a carboxylic acid group, but from the viewpoints of resistance to flame retardants, heat resistance and compatibility with component A, polybutylene terephthalate, polyethylene terephthalate and An aromatic polyester resin such as polyarylate is preferable, and polybutylene terephthalate is most preferably used in terms of excellent impact resistance and fluidity. Among the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin, an aromatic polyester resin in which 70 mol% or more of 100 mol% of the dicarboxylic acid component among the dicarboxylic acid component and the diol component forming the polyester is an aromatic dicarboxylic acid The aromatic polyester resin is preferably an aromatic dicarboxylic acid, more preferably 90 mol% or more, and most preferably 99 mol% or more. Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid Acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4, 4- Diphenoxy ethane dicarboxylic acid, 5-Na sulfo isophthalic acid, ethylene-bis-p-benzoic acid and the like can be mentioned. These dicarboxylic acids can be used alone or in combination of two or more. The aromatic polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30% by mole in addition to the above-mentioned aromatic dicarboxylic acid. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like. Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,2. 4,4-Tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and the like can be mentioned. Even if these are individual, they can be used in mixture of 2 or more types. In addition, it is preferable that the dihydric phenol in a diol component is 30 mol% or less. The process for producing the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin used in the present invention is carried out according to a conventional method, while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony etc. It is carried out by polymerizing the component and the diol component and discharging the by-produced water or lower alcohol out of the system. For example, examples of the germanium-based polymerization catalyst include oxides, hydroxides, halides, alcoholates, phenolates and the like of germanium, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium etc. Can be illustrated. In the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in transesterification reaction prior to polycondensation known in the prior art, can be used together, and phosphoric acid or phosphorous after completion of transesterification reaction. It is also possible to deactivate such a catalyst and carry out polycondensation with a compound of an acid or the like. Furthermore, as a method for producing the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin, any method of batch type and continuous polymerization type can be adopted. The molecular weight of the aromatic polybutylene terephthalate resin and the aromatic polyethylene terephthalate resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.5. Preferably, it is preferably 0.5 to 1.2. The terminal carboxyl group content of the aromatic polybutylene terephthalate resin and aromatic polyethylene terephthalate resin used in the present invention is preferably 5 to 75 eq / ton, more preferably 5 to 70 eq / ton, and still more preferably 7 to 65 eq / ton. It is.

  The aromatic polyarylate resin is obtained from an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof. As an aromatic dicarboxylic acid used for preparation of polyarylate, any may be used as long as it reacts with dihydric phenol to give a satisfactory polymer, and one kind or a combination of two or more kinds may be used. Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. Moreover, these mixtures may be sufficient. Specific examples of the dihydric phenol component include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane and 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenylmethane, 2,2'-bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4, 4'-dihydroxy diphenyl, hydroquinone etc. are mentioned. Although these dihydric phenol components are para-substituted, other isomers may be used, and furthermore, ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol components. Among the above-mentioned preferred polyarylate resins, those having an aromatic dicarboxylic acid component consisting of terephthalic acid and isophthalic acid and consisting of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) as a dihydric phenol component are mentioned. Be The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 1/9 (molar ratio), and particularly preferably 7/3 to 3/7 in view of melt processability and performance balance. Other representative polyarylate resins include those in which the aromatic dicarboxylic acid component comprises terephthalic acid and the dihydric phenol component comprises bisphenol A and hydroquinone. The ratio of bisphenol A to hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. . The viscosity average molecular weight of the polyarylate resin is preferably in the range of about 7,000 to 100,000 from the viewpoint of physical properties and extrusion processability. Further, as the polyarylate resin, any polymerization method of interfacial polycondensation method and transesterification method can be selected.

As the acid anhydride group-containing compound, as maleic acid resins, Marquide series (maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), Alastor series (styrene-maleic acid resin, manufactured by Arakawa Chemical Co., Ltd.), isoban series (Isobutylene-maleic anhydride block copolymer, manufactured by Kuraray Co., Ltd.) and the like, and from the viewpoint of heat resistance and compatibility with the component A, a styrene-maleic acid resin is most preferably used.
The content of the adhesion improver is preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the component A. If the content of the adhesion improver exceeds the above range and is too large, the flame retardancy may be deteriorated. On the other hand, if the amount is too small, the effect of improving adhesion may be small and the effect of addition may not be exhibited.

<Production of Resin Composition>
The resin composition of the present invention can be produced by mixing the above-mentioned components simultaneously or in any order by means of a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, extruder or the like. . Preferably, melt-kneading using a twin-screw extruder is preferable, and if necessary, optional components are preferably fed into the other components melt-mixed from the second feed port using a side feeder or the like. The resin extruded as described above is directly cut and pelletized or, after forming the strands, such strands are cut and pelletized with a pelletizer. When it is necessary to reduce the influence of external dust and the like at the time of pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellet may be a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 4 mm.

<On a Molded Article Made of the Resin Composition of the Present Invention>
The resin composition in the present invention can usually be produced by injection molding the pellets obtained by the above-mentioned method to produce various products. In such injection molding, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection of a supercritical fluid), insert molding, as well as ordinary molding methods according to the purpose as appropriate. Molded articles can be obtained using injection molding methods such as in-mold coating molding, insulation mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra high speed injection molding. The advantages of these various molding methods are already widely known. In addition, either cold runner method or hot runner method can be selected. Specific examples of molded articles in which the resin composition of the present invention is used include a chassis of an apparatus having an optical system unit, such as a laser beam printer, a copying machine, and a projector apparatus.

  Since the resin composition of the present invention has high specific gravity, high rigidity, high dimensional stability (low anisotropy) and good flame retardancy, it is suitable for optical unit chassis molded articles including production printers, Its industrial effects are exceptional.

  The form of the present invention which the present inventor considers to be the best is an aggregation of the preferred ranges of the above-mentioned respective requirements, and for example, representative examples thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In addition, as evaluation, it implemented about the following items.

(I) Specific gravity The specific gravity was measured using the ISO bending test piece obtained by the following method. For measurement, an electronic densimeter MD-200S manufactured by MIRAGE was used. The resin composition of the present invention needs to have a specific gravity of 1.8 or more.

(Ii) Flexural modulus The flexural modulus was measured according to ISO 178 using an ISO flexural test piece obtained by the following method.

(Iii) Deflection temperature under load The deflection temperature under load (load 1.80 MPa) was measured according to ISO 75-1 and ISO 75-2 using ISO bending test pieces obtained by the following method. The resin composition of the present invention needs to have a deflection temperature under load of 70 ° C. or higher.

(Iv) Linear Expansion Coefficient A sample of 5 mm × 5 mm × 4 mmt was cut from the central part of an ISO dumbbell test piece obtained by the following method, and the linear expansion coefficient in the range of 40 ° C. to 80 ° C. was measured. Further, the linear expansion coefficient ratio was calculated by the following equation. The anisotropy is smaller as the linear expansion coefficient ratio is closer to 1.0, and the resin composition of the present invention needs to have a linear expansion coefficient ratio in the range of 0.5 to 2.0.
Linear expansion coefficient ratio = linear expansion coefficient in the flow direction / linear expansion coefficient in the vertical direction (v) Flame retardancy The combustion test was carried out according to UL Standard 94 V, using a 2.4 mm-thick test piece obtained by the following method .
The resin composition of the present invention needs to be V-0 or V-1.

[Examples 1 to 16, Comparative Examples 1 to 6]
Among the components listed in Table 1 and Table 2, components A, B and D excluding the components (eg mica, glass fiber) which can be stably supplied or can be stably supplied by supplying independently are V The mixture was made by mixing in a mold blender. Using a vent type twin screw extruder with a screw diameter of 30 mm (manufactured by Japan Steel Works Co., Ltd. TEX30α-38.5BW-3V), the mixture mixed in a V-type blender is measured from the last first supply port using a measuring device The mixture was supplied to a predetermined ratio, and melt extruded and pelletized at a cylinder temperature of 270 ° C. under a vacuum of 3 kPa using a vacuum pump. For the E component and the F component, a side feeder was used and supplied from the second supply port. With regard to the D component, it is prescribed from the middle of the cylinder (between the first supply port and the second supply port) using a liquid injection apparatus (HYM-JS-08 manufactured by Fuji Techno Kogyo Co., Ltd.) while heated to 80 ° C. It fed to the extruder so that it became the ratio of. The obtained pellets are dried in a hot air circulating dryer at 90 to 100 ° C. for 6 hours, and then an ISO bending test piece for evaluation is performed using an injection molding machine (cylinder temperature 280 ° C., mold temperature 60 ° C.) , ISO dumbbell specimens (according to ISO 527-1 and ISO 527-2) and 2.4 mm specimens (according to UL 94).

In addition, the following were used as a raw material.
(A component)
A-1: aromatic polycarbonate resin (manufactured by Teijin Ltd .: Panlite L-1250WP (trade name), aromatic polycarbonate resin powder having a viscosity average molecular weight of 23, 900, which is produced from bisphenol A and phosgene by a conventional method)
(B component)
B-1: Barium sulfate [manufactured by Takehara Chemical Industry Co., Ltd .: W-10 (trade name), average particle size about 10 μm]
B-2: Barium sulfate [manufactured by Takehara Chemical Industry Co., Ltd .: W-6 (trade name), average particle size about 4.5 μm]
B-3: Ferrite [manufactured by Dowa Eftec Co., Ltd .: SF-D630 (trade name)]
(C ingredient)
C-1: phosphoric acid ester having bisphenol A bis (diphenyl phosphate) as a main component [Daihachi Chemical Industry Co., Ltd. product: CR-741 (trade name)]
C-2: phosphazene compound [Fushimi Pharmaceutical Co., Ltd .: FP 110 (trade name)]
(D component)
D-1: Polytetrafluoroethylene having a fibril-forming ability (manufactured by Daikin Industries, Ltd .: Polyflon MPA FA 500 (trade name))
(E ingredient)
E-1: mica (manufactured by Kinseimatic Co., Ltd .: MT200B (trade name), average particle diameter about 35 μm)
E-2: mica (manufactured by Kinseimatic Co., Ltd .: MT60B (trade name), average particle diameter about 200 μm)
(F ingredient)
F-1: Glass fiber [manufactured by Nitto Boseki Co., Ltd .: CS-3PE-455FB]
(Other ingredients)
G-1: Phosphorus-based stabilizer [Daihachi Chemical Industry Co., Ltd. product: TMP trimethyl phosphate]
G-2: mold release agent [manufactured by Clariant Japan Ltd .: Licowax E (trade name)]
G-3: Talc [manufactured by Shokoyama Mining Co., Ltd .: Victor Trilight TK-RC (trade name)]
G-4: Acrylonitrile-Styrene Copolymer ("Wyack-A BS-218" (trade name) manufactured by Nippon A & L Co., Ltd., weight average molecular weight in terms of standard polystyrene by GPC measurement: 78,000, acrylonitrile component content: 26 wt%, styrene content: 74 wt%)
G-5: bisphenol A type epoxy resin [Mitsubishi Chemical Corporation: jER1256 (trade name), Mw = 26,600]
G-6: Carbon black [made by Koshigaya Kasei Kogyo Co., Ltd .: ROYAL BLACK RB 90003 S (trade name)]

  From the above table, high specific gravity, high rigidity, high dimensional accuracy (low anisotropy) can be obtained by adding a predetermined amount of barium sulfate, a phosphorus-based flame retardant and a fluorine-containing anti-dropping agent having fibril forming ability to an aromatic polycarbonate resin. And it turns out that the resin composition which has a favorable flame retardance is obtained.

Claims (6)

  (B) 50 to 400 parts by weight of barium sulfate (B), (C) 5 to 50 parts by weight of phosphorus based flame retardant (C), and 100 parts by weight of the aromatic polycarbonate resin (A) D) An aromatic polycarbonate resin composition containing 0.1 to 3 parts by weight of a fluorine-containing anti-dripping agent (component D) having fibril-forming ability.   The aromatic polycarbonate resin composition according to claim 1, which comprises 10 to 150 parts by weight of a plate-like filler (component E) other than the component (E) B with respect to 100 parts by weight of the component A.   The aromatic polycarbonate resin composition according to claim 2, wherein the component E is mica.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, which comprises 10 to 150 parts by weight of (F) glass fiber (component F) with respect to 100 parts by weight of the component A.   The aromatic polycarbonate resin composition according to any one of claims 1 to 4, which has a specific gravity of 1.8 or more. The molded article which consists of an aromatic polycarbonate resin composition of any one of Claims 1-5.