JP2008280491A - Flame retardant aromatic polycarbonate resin composition for thin wall molding, and thin wall molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thin wall molding which has a good appearance and flame retardance combined, excellent impact resistance and fluidity, a heat stablity good enough to withstand high temperature molding processes, and exhibits superior overall properties. <P>SOLUTION: The flame retardant aromatic polycarbonate resin composition is composed of 3-20 pts.wt. of (B) a phosphorus-based flame retarder, 0.01-1 pt.wt. of (C) polyfluoroethylene, and 1-20 pts.wt. of (D) a graft copolymer containing polyorganosiloxane based on 100 pts.wt. of (A) of an aromatic polycarbonate resin. The graft copolymer containing the polyorganosiloxane (D) is obtained by polymerizing 0.5-10 pts.wt. of (Y) a first vinyl-based monomer and then 5-50 pts.wt. of (Z) a second vinyl-based monomer in the presence of 40-90 pts.wt. of (X) polyorganosiloxane particles. The first vinyl-based monomer (Y) is composed of 100-50 wt.% of (y-1) a multifunctional monomer and 0-50 wt.% of (y-2) another polymerizable monomer. The flame retardance of a 0.6 mm thick test piece molded from the aromatic polycarbonate resin composition according to the UL94 specification is V-0 or V-1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame-retardant aromatic polycarbonate resin composition for thin-wall molding (hereinafter sometimes simply referred to as “aromatic polycarbonate resin composition”), and more specifically, flame retardancy, impact resistance, and fluidity. The present invention also relates to a flame-retardant aromatic polycarbonate resin composition for thin-wall molding excellent in thermal stability and appearance, and a thin-wall molded article.

Aromatic polycarbonate resin is a general-purpose engineering plastic that excels in transparency, impact resistance, heat resistance, dimensional stability, etc., and because of its excellent characteristics, it can be used as a raw material in the automotive field, OA equipment field, electrical / electronic field, etc. Widely used.
On the other hand, there is a strong demand for flame retardant resin materials, mainly for applications such as OA equipment and home appliances. To meet these demands, aromatic polycarbonate resins are made of halogen compounds, phosphorus compounds, and siloxane compounds. A number of techniques for blending polyfluoroethylene and the like to make it flame retardant have been proposed. Recently, resin containers used for cell phone battery packs, storage medium covers, and the like have become thinner year by year for the purpose of miniaturization, weight reduction, high functionality, and the like. As a result, thin molded products using aromatic polycarbonate resins are required to have excellent flame retardancy, impact resistance, fluidity, and appearance as well as thermal stability that can withstand high temperature molding.

For example, Patent Document 1 discloses that a thin thickness is obtained by blending a composite rubber-based graft copolymer having a specific phosphate ester compound, a polyorganosiloxane component, and a polyalkyl (meth) acrylate rubber component with a polycarbonate resin. It is described that a resin composition excellent in impact resistance and flame retardancy can be obtained even if molded into a resin.
In Patent Document 2, a resin composition excellent in impact resistance and flame retardancy is obtained by blending a specific polyorganosiloxane-containing graft copolymer with an aromatic polycarbonate resin. It is described that an auxiliary agent can be blended.
Furthermore, Patent Document 3 discloses that a resin composition obtained by blending an aromatic polycarbonate resin with a phosphorus-based flame retardant, a polyfluoroethylene resin, and a specific multilayer structure polymer has flame retardancy, thermal stability, and impact resistance. It is described that it is useful as a large-sized molded product or a thin-walled molded product because it has excellent properties and has an appearance improving effect.

In Patent Document 4, materials having excellent impact resistance, moldability, and fluidity and suitable for battery packs include polycarbonate resin, composite rubber-based graft copolymer, halogen-free phosphate ester compound, and polytetrafluoroethylene ( A resin composition comprising no coating is described.
Patent Document 5 discloses a resin composition excellent in thin-wall fluidity, heat resistance, and low warpage, which is obtained by blending a liquid crystalline resin and a phosphate ester in a polycarbonate resin, and has a maximum projection surface thickness. A resin composition for a battery pack housing member of a portable device in which a portion having a thickness of 0.6 mm or less is 100 mm ² or more is described.

Furthermore, in Patent Document 6, a molded article obtained from a resin composition in which a thermoplastic resin and a mixed powder containing polytetrafluoroethylene (with coating) are blended with a thermoplastic resin has improved impact strength. Is described.
Patent Document 7 describes that a resin composition comprising an aromatic polycarbonate resin and a fluorine-containing organometallic salt compound containing a specific amount of fluoride ions has an excellent anti-drip effect.

However, with the advance of technology, higher levels of flame retardancy, fluidity, impact resistance and appearance are required.
Here, in patent documents 1 to 3, the thickness of the test piece for flame retardancy evaluation in those examples is 1/16 inch (1.6 mm), and in the examples of patent documents 4 and 7, the thickness is 0.8 mm. However, in recent years, thinner molded products, specifically, thin-walled molded products having a thickness of 0.6 mm or less have been demanded.
Therefore, even when molded into a thin-walled container having a flat plate part of 0.6 mm or less in whole or in part, it is possible to achieve both good molded product appearance and flame retardancy, and further improve impact resistance and fluidity. Development of a resin composition having excellent thermal stability that can withstand high-temperature molding and having comprehensively good performance is desired.

Japanese Patent Application Laid-Open No. 08-259791 Japanese Patent Laid-Open No. 2003-238639 JP 2001-123056 A Japanese Patent Laid-Open No. 11-21441 JP 2002-348460 A JP 2000-226523 A JP 2005-112973 A

However, as a result of investigation by the present inventor, in a thin molded article using the resin composition as described in Patent Documents 1 to 3, a thin container having a flat plate portion of 0.6 mm or less in whole or in part. It was found that the flame retardancy and fluidity were not sufficient when molded into the shape.
In addition, when a thin-walled molded product is molded with the resin composition described in Patent Document 4, not only flame retardancy and impact resistance are insufficient, but a large number of white spot foreign matters are generated on the molded product surface, and only a molded product with a poor appearance is produced. I found out I couldn't get it.
Furthermore, even when the resin compositions described in Patent Documents 5 to 7 are used, the flame retardancy at a thickness of 0.6 mm is insufficient, and the impact resistance, thermal stability, and appearance of the molded product are the objects of the present invention. It was found that we could not satisfy all of the above in a balanced manner.
The object of the present invention is a thin-walled molded article having a flat plate portion of 0.6 mm or less in whole or in part, which can achieve both a good molded article appearance and flame retardancy, and also has impact resistance and An object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition for thin-wall molding and a thin-wall molded article having excellent fluidity, thermal stability that can withstand high-temperature molding, and having comprehensively good performance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have made an aromatic polycarbonate resin contain a phosphorus-based flame retardant, polyfluoroethylene, and a specific polyorganosiloxane-containing graft copolymer. Has found that a resin composition and a thin-walled molded article having excellent flame retardancy, molded article appearance, impact resistance, fluidity, and thermal stability that can withstand high-temperature molding can be obtained, and the present invention has been completed. It was.

That is, the first gist of the present invention is that (A) 3 to 20 parts by weight of a phosphorus-based flame retardant and (C) 0.01 to 1 polyfluoroethylene are added to 100 parts by weight of an aromatic polycarbonate resin. A flame-retardant aromatic polycarbonate resin composition for thin-wall molding, comprising 1 part by weight of (D) polyorganosiloxane-containing graft copolymer,
The (D) polyorganosiloxane-containing graft copolymer comprises (Y) 0.5 to 10 parts by weight of the first vinyl monomer in the presence of 40 to 90 parts by weight of the polyorganosiloxane particles. Polymerized, and further obtained by polymerizing (Z) 5 to 50 parts by weight of the second vinyl monomer,
The (Y) first vinyl monomer comprises (y-1) 100 to 50% by weight of a polyfunctional monomer and (y-2) 0 to 50% by weight of other copolymerizable monomers. A flame retardant according to UL94 standard of a 0.6 mm thickness test piece molded from the aromatic polycarbonate resin composition is V-0 or V-1 In the aromatic polycarbonate resin composition.
The second gist of the present invention resides in a thin molded product having a flat plate portion having a thickness of 0.6 mm or less formed by molding the above aromatic polycarbonate resin composition.
The third gist of the present invention includes a step of using the above aromatic polycarbonate resin composition, wherein the flame retardancy in the UL94 standard of the 0.6 mm thickness test piece is V-0 or V-1, and the wall thickness is 0. It exists in the manufacturing method of the thin molded article which has a flat plate part of 6 mm or less.
The thin molded product in the present invention is, for example, a molded product used for a battery pack (battery pack of a mobile phone or the like) or a container constituting an outer portion of a small auxiliary storage device. A molded product having a flat plate portion of 6 mm or less.

The aromatic polycarbonate resin composition used in the present invention exhibits good flame retardancy and appearance even when it is molded into a thin molded product having a flat plate portion of 0.6 mm or less entirely or partially. In addition, since the fluidity and heat stability are good and the productivity is excellent, the thin molded product obtained has excellent impact resistance and a comprehensively balanced performance.
That is, according to the present invention, it is possible to provide a thin molded article suitable as a container constituting the outer portion of a small auxiliary storage device such as a battery pack, a memory card, an SD card, etc. It became.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified. Further, in the case of a group having a limited number of carbons, the number of carbons means a number including the number of carbons that the substituent has.

(A) Aromatic polycarbonate resin (A) Aromatic polycarbonate resin used in the present invention is a thermoplastic heavy resin obtained by reacting an aromatic dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. It is a coalescence. The (A) aromatic polycarbonate resin may be branched or a copolymer. The method for producing the (A) aromatic polycarbonate resin is not particularly limited, and can be produced by a conventionally known phosgene method (interfacial polymerization method) or a melting method (transesterification method). Moreover, when using the aromatic polycarbonate resin obtained by a melting method, you may adjust and use the amount of OH groups of a terminal group.
(A) As an aromatic dihydroxy compound used as a raw material for the aromatic polycarbonate resin, 2,2-bis (4-hydroxyphenyl) propane (that is, bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl)- Examples include p-diisopropylbenzene, hydroquinone, resorcinol, 4,4-dihydroxydiphenyl, and bisphenol A is preferable. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

 In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with a branching agent such as phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene- 2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3 Polyhydroxy compounds such as 5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (ie, isatin) Bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like may be substituted. The amount of the compound to be substituted is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the aromatic dihydroxy compound.

 (A) As aromatic polycarbonate resin, among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other Polycarbonate copolymers derived from aromatic dihydroxy compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure. Furthermore, you may mix and use 2 or more types of the aromatic polycarbonate resin mentioned above.

 (A) The molecular weight of the aromatic polycarbonate resin is preferably 16,000 to 30,000, preferably 18,000 to 28, as the viscosity average molecular weight converted from the solution viscosity measured at 25 ° C. using methylene chloride as a solvent. 1,000 is more preferable. When the viscosity average molecular weight is 30,000 or less, the fluidity tends to be good, and when it is 16,000 or more, the impact strength tends to be good.

 In order to adjust the molecular weight of the aromatic polycarbonate resin, for example, m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol, etc. Valent aromatic hydroxy compounds can be used.

(B) Phosphorus flame retardant In the present invention, (A) an aromatic polycarbonate resin is blended with (B) a phosphorus flame retardant. The (B) phosphorus flame retardant used in the present invention may be a compound containing phosphorus in the molecule, and specifically, phosphazene compounds such as cyclic phenoxy phosphazene compounds, chain phenoxy phosphazene compounds and cross-linked phenoxy phosphazene compounds. A compound represented by the following general formula (1) and a compound represented by the following general formula (2) are preferable.

General formula (1)

(In the general formula (1), R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. , H, i and j each independently represent 0 or 1.)
R ¹ , R ² and R ³ are preferably each independently an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group.
The compound represented by the general formula (1) can be produced from phosphorus oxychloride and the like by a known method. Specific examples of the phosphorus compound represented by the general formula (1) include triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, methylphosphonic acid diphenyl ester, phenylphosphone. Examples include acid diethyl ester, diphenyl cresyl phosphate, and tributyl phosphate.

（一般式（２）中、Ｒ⁴、Ｒ⁵、Ｒ⁶およびＲ⁷は、各々独立に、炭素数１〜６のアルキル基またはアルキル基で置換されていてもよい炭素数６〜２０のアリール基を示し、ｐ、ｑ、ｒおよびｓは、各々独立に０または１であり、ｔは、１〜５の整数であり、Ｘは、アリーレン基を示す。ｔが２以上のとき、ｔ個の繰り返し単位は、各々同一であってもよいし、異なっていてもよい。） General formula (2)

(In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl having 6 to 20 carbon atoms which may be substituted with an alkyl group. P, q, r and s are each independently 0 or 1, t is an integer of 1 to 5, and X is an arylene group, t is t when t is 2 or more. The repeating units may be the same or different.

The compound represented by the general formula (2) is a condensed phosphate ester having t of 1 to 5. However, in the case of a mixture of a plurality of types of condensed phosphate esters having different t, t is a mixture of those compounds. Calculate as an average value.
X is preferably a divalent group derived from a dihydroxy compound such as resorcinol, hydroquinone or bisphenol A.
R ⁴ , R ⁵ , R ⁶ and R ⁷ are preferably each independently derived from phenol, cresol or xylenol.

Among the above-mentioned (B) phosphorus-based flame retardants, in the present invention, the compound represented by the general formula (2) is excellent in terms of workability and thermal stability and a small amount of gas generated during molding. More preferred. Particularly preferably, in the general formula (2), X is derived from resorcinol or bisphenol A, p, q, r and s are each 1, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are Are derived from cresol or xylenol, respectively. Specific examples include cresyl-resorcin polyphosphate and xylyl-resorcin polyphosphate.

(B) The compounding quantity of a phosphorus flame retardant is 3-20 weight part with respect to 100 weight part of (A) aromatic polycarbonate resin, Furthermore, 4-18 weight part, Especially 5-15 weight part is preferable. . If the amount of the phosphorus-based flame retardant exceeds 20 parts by weight, the mechanical properties may decrease, and if it is less than 3 parts by weight, the flame retardancy and fluidity may decrease.
In addition, in this invention, (B) phosphorus flame retardant may use 2 or more types together. When using 2 or more types, the total amount becomes the said compounding quantity.

(C) Polyfluoroethylene (C) Polyfluoroethylene used in the present invention has, for example, a fibril-forming ability, and is easily dispersed in a polymer and bonded to each other to form a fibrous material. To help. In order to improve the appearance of a thin molded product obtained by melt-molding a resin composition containing polyfluoroethylene, a specific coated polyfluoroethylene coated with an organic polymer (hereinafter abbreviated as “coated polyfluoroethylene”). It may be preferable to contain. The coated polyfluoroethylene preferably employed in the present invention has a polyfluoroethylene content in the coated polyfluoroethylene in the range of 40 to 95% by weight, of which 43 to 80% by weight, and more particularly 45 It is preferable to be -70 wt%, particularly 47-60 wt%.
By setting the polyfluoroethylene content in the coated polyfluoroethylene to 40% by weight or more, flame retardancy tends to be improved, and by setting it to 95% by weight or less, white spot foreign matter tends to be further suppressed. Yes, it is preferable.
Moreover, as polyfluoroethylene coat | covered with an organic type polymer, polytetrafluoroethylene (PTFE) is preferable, and what has a fibril formation ability is especially preferable. Such PTFE tends to disperse easily in the polymer and bind the polymers together to form a fibrous material.
By blending such a coated polyfluoroethylene, generation of white spot foreign matter on the surface of the thin molded article can be further suppressed while maintaining good flame retardancy.

 The coated polyfluoroethylene can be produced by various known methods. For example, (1) an aqueous dispersion of polyfluoroethylene particles and an aqueous dispersion of organic polymer particles are mixed and powdered by coagulation or spray drying. (2) A method for producing a polymer by polymerizing monomers constituting an organic polymer in the presence of an aqueous dispersion of polyfluoroethylene particles, and then pulverizing the product by coagulation or spray drying; (3) Poly Manufactured by emulsion polymerization of monomers with ethylenically unsaturated bonds in a dispersion obtained by mixing an aqueous dispersion of fluoroethylene particles and an aqueous dispersion of organic polymer particles, followed by pulverization or spray drying. And the like.

 The organic polymer coating polyfluoroethylene is not particularly limited, but is preferably a polymer having high affinity with an aromatic polycarbonate resin from the viewpoint of dispersibility when blended with the resin.

 Specific examples of the monomer for producing the organic polymer include styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, tert-butylstyrene, o-ethylstyrene, p-chlorostyrene, Aromatic vinyl monomers such as o-chlorostyrene, 2,4-dichlorostyrene, p-methoxystyrene, o-methoxystyrene, 2,4-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, tridecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, Acrylic acid cyclohex (Meth) acrylic acid ester monomers such as cyclohexyl methacrylate; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenyl Maleimide monomers such as maleimide, N-methylmaleimide and N-cyclohexylmaleimide; Glycidyl group-containing monomers such as glycidyl methacrylate; Vinyl ether monomers such as vinyl methyl ether and vinyl ethyl ether; Vinyl acetate and vinyl butyrate And carboxylic acid vinyl monomers such as ethylene, propylene and isobutylene; and diene monomers such as butadiene, isoprene and dimethylbutadiene. These monomers can be used alone or in admixture of two or more.

The organic polymer used in the present invention is composed of (A) an aromatic vinyl resin, an aromatic vinyl monomer, a (meth) acrylate monomer, a vinyl cyanide monomer. An organic polymer containing at least one monomer selected from the group is preferred, and an organic polymer containing at least a (meth) acrylate monomer is more preferred.
One or more monomers selected from aromatic vinyl monomers, (meth) acrylic acid ester monomers, and vinyl cyanide monomers in the organic polymer used in the present invention. The content of is preferably 10% by weight or more.

 In the present invention, as the coated polyfluoroethylene, for example, Metabrene A-3800, KA-5503 manufactured by Mitsubishi Rayon Co., Ltd., Poly TS AD001 manufactured by PIC, or the like can be used.

The blending amount of (C) polyfluoroethylene in the present invention is 0.01 to 1 part by weight and 0.05 to 0.9 part by weight with respect to 100 parts by weight of (A) aromatic polycarbonate resin. Preferably, it is 0.1-0.7 weight part. When the blending amount of (C) polyfluoroethylene is less than 0.01 parts by weight, the flame retardancy may be reduced. On the other hand, when it exceeds 1 part by weight, the appearance of the molded product may be deteriorated.
Furthermore, the blending ratio [(B) / (C)] of (B) phosphorus flame retardant and (C) polyfluoroethylene described above is a resin composition having a well-balanced performance by further improving the flame retardancy of the thin-walled portion. From the point of obtaining a thing, it is 0.1-1000 normally, Preferably it is 1-100, More preferably, it is 2-60.

(D) Polyorganosiloxane-containing graft copolymer The (D) polyorganosiloxane-containing graft copolymer used in the present invention can be produced, for example, by the production method disclosed in Japanese Patent Application Laid-Open No. 2003-238639.
That is, (D) the polyorganosiloxane-containing graft copolymer is (Y) 0.5 to 10 parts by weight of the first vinyl monomer in the presence of 40 to 90 parts by weight of the polyorganosiloxane particles. And (Z) 5 to 50 parts by weight of the second vinyl monomer is further polymerized.

The (X) polyorganosiloxane particles have a toluene insoluble content (the amount of toluene insoluble when 0.5 g of the (X) polyorganosiloxane particles are immersed in 80 ml of toluene at room temperature for 24 hours) of 95% by weight or less, and further 50% by weight. % Or less, particularly 20% by weight or less is preferable from the viewpoint of flame retardancy and impact resistance.
Specific examples of (X) polyorganosiloxane particles include polydimethylsiloxane particles, polymethylphenylsiloxane particles, dimethylsiloxane-diphenylsiloxane copolymer particles, and the like. These may be used alone or in combination of two or more.

(Y) The first vinyl monomer is (y-1) a polyfunctional monomer, that is, 100 to 50% by weight of a polyfunctional monomer containing two or more polymerizable unsaturated bonds in the molecule. And (y-2) a vinyl monomer composed of 0 to 50% by weight of other copolymerizable monomers.
(Y) A 1st vinyl-type monomer is used in order to improve a flame-retardant effect and an impact-resistant improvement effect.
(Y) The first vinyl monomer contains (y-1) a polyfunctional monomer, preferably 100 to 80% by weight, more preferably 100 to 90% by weight, (y-2) Other Is preferably 0 to 20% by weight, more preferably 0 to 10% by weight. (Y-1) By including a polyfunctional monomer in a proportion of 50% by weight or more, and (y-2) by including other copolymerizable monomers in a proportion of 50% by weight or less. The impact resistance improving effect of the finally obtained (D) polyorganosiloxane-containing graft copolymer tends to be further improved, which is preferable.

 (Y-1) The polyfunctional monomer is a compound containing two or more polymerizable unsaturated bonds in the molecule, and specific examples thereof include allyl methacrylate, triallyl cyanurate, and divinylbenzene. . These may be used alone or in combination of two or more. Among these, the use of allyl methacrylate is particularly preferred from the viewpoint of economy and effects.

 (Y-2) Specific examples of other copolymerizable monomers include aromatic vinyl monomers such as styrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, Examples thereof include (meth) acrylic acid ester monomers such as ethyl acrylate, methyl methacrylate and ethyl methacrylate, and carboxyl group-containing vinyl monomers such as (meth) acrylic acid and maleic acid. Two or more of these may be used in combination.

(Z) The second vinyl monomer is a component constituting (D) a polyorganosiloxane-containing graft copolymer, and (D) the polyorganosiloxane-containing graft copolymer is blended with a thermoplastic resin. In order to improve the flame retardancy and impact resistance, the components used to ensure the compatibility of the graft copolymer and the thermoplastic resin and to uniformly disperse the graft copolymer in the thermoplastic resin But there is.
(Z) Examples of the second vinyl monomer include (y-2) other in the above (Y) second vinyl monomer such as methyl methacrylate, butyl methacrylate, styrene, acrylonitrile and the like. The same monomer as the copolymerizable monomer can be used, and two or more types may be used in combination.
(Z) The second vinyl monomer preferably has a polymer solubility parameter of 9.15 to 10.15 [(cal / cm ³ ) ^1/2 ], ^{9.17~10.10 [(cal / cm 3)} 1/2] more preferably, still more preferably ^{9.20~10.05 [(cal / cm 3)} 1/2]. By setting the solubility parameter within the above range, the flame retardancy tends to be further improved, which is preferable.

The (D) polyorganosiloxane-containing graft copolymer used in the present invention comprises (X) 40 to 90 parts by weight, preferably 60 to 80 parts by weight, more preferably 60 to 75 parts by weight of polyorganosiloxane particles. Under (Y) 0.5-10 parts by weight of the first vinyl monomer, preferably 1-5 parts by weight, more preferably 2-4 parts by weight, and (Z) second Is obtained by polymerizing 5 to 50 parts by weight, preferably 15 to 39 parts by weight, more preferably 21 to 38 parts by weight.
(X) When the ratio of the polyorganosiloxane particles is too small or too large, the flame retarding effect is low.
In addition, when the amount of (Y) the first vinyl monomer is too small, the flame retarding effect and the impact resistance improving effect are lowered, and when it is too much, the impact resistance improving effect is lowered.
Furthermore, when (Z) the second vinyl monomer is too little or too much, the flame retarding effect is lowered in both cases.

A known seed emulsion polymerization can be applied to the (D) polyorganosiloxane-containing graft copolymer. For example, (X) radical polymerization of the first vinyl monomer in the latex of (X) polyorganosiloxane particles. And (Z) radical polymerization of the second vinyl monomer.
Further, both (Y) the first vinyl monomer and (Z) the second vinyl monomer may be polymerized in one stage or in two or more stages.

 The (D) polyorganosiloxane-containing graft copolymer obtained by the above method may be used by separating the polymer from the latex or may be used as it is. Examples of the method for separating the polymer include a usual method, for example, a method of coagulating, separating, washing, dehydrating and drying the latex by adding a metal salt such as calcium chloride, magnesium chloride, magnesium sulfate to the latex. . A spray drying method can also be used.

The blending amount of the (D) polyorganosiloxane-containing graft copolymer is 1 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 100 parts by weight of the (A) aromatic polycarbonate resin. 3 to 13 parts by weight, particularly preferably 4 to 12 parts by weight.
(D) If the polyorganosiloxane-containing graft copolymer exceeds 20 parts by weight, the rigidity may decrease, and if it is less than 1 part by weight, flame retardancy may decrease.

 In the present invention, the total amount of (B) the phosphorus-based flame retardant and (D) the polyorganosiloxane-containing graft copolymer is preferably based on (A) 100 parts by weight of the aromatic polycarbonate resin. It is 10 parts by weight or more, more preferably 12 parts by weight or more, and particularly preferably 14 parts by weight or more. By making the total of the blending amount of (B) the phosphorus-based flame retardant and (D) the polyorganosiloxane-containing graft copolymer 10 parts by weight or more, the flame retardancy tends to be improved, which is preferable.

 In the present invention, the resin composition includes, in addition to the above components, any conventionally known ultraviolet absorbers, antioxidants, heat stabilizers, colorants, as long as the effects of the present invention are not impaired. You may contain additives, such as a lubricant and a mold release agent, thermoplastic resins other than polycarbonate resin, an impact resistance improving agent, etc.

 As an antioxidant which may be used for this invention, Preferably a hindered phenolic antioxidant is mentioned. Specific examples include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxy Phenyl) 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-hydroxy Phenyl] methyl] phosphoate, 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- And di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol. Of the above, in particular pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4- Hydroxyphenyl) propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names Irganox 1010 and Irganox 1076.

The blending amount of the antioxidant is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the (A) aromatic polycarbonate resin. By setting the blending amount of the antioxidant to 0.01 parts by weight or more, the effect as an antioxidant tends to be exhibited more easily, and even if it exceeds 2 parts by weight, further effects as an antioxidant can be obtained. Since it is not, 2 parts by weight or less is economical.
A plurality of antioxidants can be used in combination.

 The heat stabilizer that may be used in the present invention is preferably a phosphite ester-based stabilizer, specifically, tris (nonylphenyl) phosphite, triphenylphosphite, tris (2,4-di-tert). -Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, tris (ethylphenyl) phosphite, tris (butylphenyl) phosphite and tris (hydroxyphenyl) phosphite For example, fights. Of these stabilizers, tris (2,4-di-tert-butylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite are particularly preferred.

The blending amount of the heat stabilizer is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 1 part by weight with respect to 100 parts by weight of the (A) aromatic polycarbonate resin. By setting the content to 0.01 parts by weight or more, the effect as a heat stabilizer tends to be exhibited more easily, and even if added in excess of 2 parts by weight, the effect as a further heat stabilizer is obtained. Therefore, 2 parts by weight or less is economical.
A plurality of heat stabilizers can be used in combination.

 As the release agent that may be used in the present invention, at least one selected from aliphatic carboxylic acids, aliphatic carboxylic acid esters, and polysiloxane silicone oils is preferably used. Among these, at least one selected from aliphatic carboxylic acid and aliphatic carboxylic acid ester is more preferably used.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Of these, preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

  Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc. can be mentioned. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.

  Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture based on myristyl palmitate), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester Mention may be made of stearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monosterate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate.

  The compounding amount of the release agent is preferably 2 parts by weight or less, more preferably 1 part by weight or less with respect to (A) 100 parts by weight of the aromatic polycarbonate resin. By setting it to 2 parts by weight or less, there is a tendency that degradation of hydrolysis resistance, mold contamination during injection molding, and the like can be more effectively suppressed. A plurality of these release agents may be used in combination.

 The production method of the resin composition used in the present invention is not particularly limited. For example, (1) (A) aromatic polycarbonate resin, (B) phosphorus flame retardant, (C) polyfluoroethylene, (D ) Polyorganosiloxane-containing graft copolymer, and a method of melt-kneading the stabilizer and release agent that are blended as necessary, or (2) (B) when the phosphorus-based flame retardant is liquid, After melt-kneading components other than (B) phosphorus flame retardant in advance, liquid (B) phosphorus flame retardant previously heated at 50 to 120 ° C. is added to the molten resin, and melt-kneaded. The method of doing is mentioned.

In the aromatic polycarbonate resin composition of the present invention, the flame retardancy in the UL94 standard of a 0.6 mm thick test piece is V-0 or V-1. The flame retardancy of the aromatic polycarbonate resin composition depends on the composition ratio and production conditions of the aromatic polycarbonate resin composition, the type of raw material, the production method, and the like. For example, (B) a phosphorus flame retardant and (C) Polyfluoroethylene compounding ratio [(B) / (C) ratio], (B) Phosphorus flame retardant and (D) Polyorganosiloxane-containing graft copolymer total compounding amount [((B) + ( D)) Amount], in the case of producing an aromatic polycarbonate resin composition by melt-kneading, adjusting the conditions at the time of melt-kneading, etc., even in a thin portion without reducing physical properties other than flame retardancy It is easier to achieve a high flame retardant level such as
The (B) / (C) ratio (weight ratio) is preferably 0.1 to 1000, more preferably 1 to 100, and even more preferably 2 to 60. The amount of ((B) + (D)) is preferably 10 parts by weight or more, more preferably 12 parts by weight or more, and still more preferably 14 parts by weight or more with respect to 100 parts by weight of (A) aromatic polycarbonate resin.
In addition, in order to improve the dispersibility of each component, to further improve the ability to prevent molten resin drip during combustion by fibrils of (C) polyfluoroethylene, and to perform stable kneading, production of an aromatic polycarbonate resin composition It is necessary to choose the method carefully. As a method for producing the aromatic polycarbonate resin composition, a melt kneading method using a twin screw extruder having equipment capable of devolatilization from a vent port as a kneader is preferable. (B) Ingredients other than the phosphorus-based flame retardant, that is, (A), (C), (D) and optional additive components are previously prepared using a mixer such as a tumbler, a Henschel mixer, a ribbon blender, a Banbury mixer, etc. It is preferable to mix them. In melt kneading, the barrel temperature is preferably set to 350 ° C. or lower, more preferably 240 to 320 ° C. By setting it as such temperature conditions, performance can be improved more about a flame retardance, impact strength, etc. When the (B) phosphorus flame retardant is in a liquid state, it is effective to add it from various blocks such as a gear pump and a plunger pump from a block in the middle of the extruder. During the melt-kneading, it is preferable to appropriately adjust the barrel temperature and the screw speed so that the extruder can be operated with a capacity of preferably 60 to 90% of the maximum torque. By adopting such means, it is possible to further improve the performance in terms of flame retardancy, impact strength and the like.
By adopting any of the above conditions within the resin composition range defined in the present invention, or by combining a plurality of conditions, the physical properties other than flame retardancy are maintained well, and 0 It becomes easier to set the flame retardancy of the 6 mm thickness test piece in the UL94 standard to the V-0 or V-1 level.

 The aromatic polycarbonate resin composition thus obtained can be used to obtain a molded product using any conventionally known various molding methods, but it has excellent fluidity, even when it is a thin molded product, Since both reduction of white spot foreign matter and good flame retardancy can be achieved, it is suitable for molding a thin resin container by an injection molding method. When molding a thinner molded product, for example, a molded product having a thickness of 0.6 mm or less by the injection molding method, the resin temperature at the time of injection molding is higher than the temperature applied to molding of a conventional polycarbonate resin composition. It is preferable to set a higher temperature, preferably 305 to 360 ° C, more preferably 310 to 350 ° C, and even more preferably 315 to 340 ° C. When the conventional resin composition is used, there is a problem that white spot foreign matter is likely to be generated on the surface of the thin container when the resin temperature at the time of molding is increased in order to mold the thin container. By using the resin composition of the present invention which is superior in thermal stability compared to the resin composition, it is possible to produce a thin container having a good appearance even in the relatively high temperature range as described above. Become.

In the present invention, the thin-walled molded product is a molded product having a flat plate portion of 0.6 mm or less, or preferably a molded product having a flat plate portion of 1 cm ² or more and 0.6 mm or less. “Partial” means 25% or more of the total area of the molded product. Further, the “flat plate portion” refers to a portion excluding irregularities such as ribs and bosses, windows, holes and the like, and may be flat or curved.
For example, the thin molded product of the present invention refers to a battery pack (for example, a box or lid used for a battery pack of a mobile phone) or a container (for example, a cover for a memory card, SD card, etc.) that constitutes an outer portion of a small auxiliary storage device. Etc.) and the like, and refers to a resin container having a flat plate portion of 0.6 mm or less in whole or in part. As a form of a preferable thin-walled molded article, for example, as shown in FIG. 1, it is a resin container including a container body (box body) and a lid body for sealing the container body, and the container body (box body) It is a resin container having a flat plate portion having an average thickness of 0.6 mm or less that is recessed by a rising piece. Further, based on the usage of electric / electronic parts, the area of the flat plate portion is 1 to 100 cm ² , the height of the rising piece is 0.5 to 10 mm, and the thickness of the rising piece is the rigidity of the container body. From the viewpoint of increasing the storage efficiency of the stored items, the thickness is usually 0.3 to 1.2 mm.

 EXAMPLES The present invention will be described more specifically with reference to the following examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

[raw materials]
(A) Aromatic polycarbonate resin Poly-4,4-isopropylidenediphenyl carbonate: “Iupilon (registered trademark) H-2000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 20,000 (hereinafter abbreviated as PC) )

（式中 ｔ₁は１．１である。）
（ｂ−２）縮合リン酸エステル：旭電化工業社製「アデカスタブ ＦＰ５００」

（式中 ｔ₂は１．０１である。）
（ｂ−３）トリフェニルホスフェート：大八化学工業社製
（ｂ−４）臭素化ポリカーボネートオリゴマー：三菱エンジニアリングプラスチックス（株）製「ユーピロン（登録商標）ＦＲ−５３」 (B) Flame retardant (b-1) Condensed phosphate ester: “ADK STAB FP700” manufactured by Asahi Denka Kogyo Co., Ltd.

(Where t ₁ is 1.1)
(B-2) Condensed phosphate ester: “Adeka Stub FP500” manufactured by Asahi Denka Kogyo Co., Ltd.

(Where t ₂ is 1.01)
(B-3) Triphenyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd. (b-4) Brominated polycarbonate oligomer: “Iupilon (registered trademark) FR-53” manufactured by Mitsubishi Engineering Plastics Co., Ltd.

(C) Polytetrafluoroethylene (c-1) coated polytetrafluoroethylene: “Metabrene A-3800” manufactured by Mitsubishi Rayon Co., Ltd. (The content ratio of polytetrafluoroethylene in the coated polytetrafluoroethylene is 50% by weight. .)
(C-2) Polytetrafluoroethylene: “Polyflon F-201L” manufactured by Daikin Industries, Ltd.

(D) Graft copolymer (d-1) "Kane Ace MR-01" manufactured by Kaneka Corporation
(D-2) Graft copolymer having polyorganosiloxane particles of less than 40 parts by weight: “Methbrene S-2001” manufactured by Mitsubishi Rayon Co., Ltd.
(D-3) Polybutadiene core / polymethylmethacrylate shell copolymer (multilayer polymer): “Paraloid EXL-2603” manufactured by Kureha Chemical Industry Co., Ltd.

(E) Release agent Pentaerythritol tetrastearate: “VPG861” manufactured by Cognis
(F) Thermal stabilizer Tris (2,4-di-tert-butylphenyl) phosphite: “Adeka Stub 2112” manufactured by Asahi Denka Kogyo Co., Ltd.

[Examples 1-4, 6-8, and Comparative Examples 1-4]
After blending raw materials other than the flame retardant (B) so as to have the ratio (weight ratio) shown in Table 1 and mixing for 20 minutes with a tumbler, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30HSST, barrel 12) Block). Each resin composition shown in Table 1 was melt-kneaded under conditions of a barrel temperature of 280 ° C., a screw rotation speed of 200 rpm, and an extrusion speed of 15 kg / hour to prepare pellets of the resin composition. Note that (B) the flame retardant was preheated to 80 ° C. and added from the third block counted from the hopper side of the twin-screw extruder using a gear pump.

[Example 5 and Comparative Example 5]
After mixing the raw materials of (A) to (E) so as to have the ratio (weight ratio) shown in Table 1 and mixing for 20 minutes with a tumbler, a twin-screw extruder (TEX30HSST manufactured by Nippon Steel Works, barrel 12) Block). Each resin composition shown in Table 1 was melt-kneaded under conditions of a barrel temperature of 280 ° C., a screw rotation speed of 200 rpm, and an extrusion speed of 15 kg / hour to prepare pellets of the resin composition.

[Comparative Example 6]
In Example 7, pellets of the resin composition were produced in the same manner as in Example 7 except that the barrel temperature was changed to 360 ° C.

[Comparative Example 7]
In Example 7, a resin composition was produced in the same manner as in Example 7 except that the barrel temperature was changed to 240 ° C. The torque when melt-kneaded under the above conditions was 92% of the maximum torque of the extruder.

  The obtained resin composition was dried at 80 ° C. for 5 hours, then injection molded by the following method, and various evaluations were performed using the obtained test pieces. The results are shown in Table 1.

[Method for evaluating physical properties of molded products]
(1) Flame retardancy Each resin composition pellet obtained by the above-described method is injection molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. using an injection molding machine manufactured by Nippon Steel Works, J50EP. A test piece having a length of 127 mm, a width of 12.7 mm, and a wall thickness of 0.6 mm was obtained. About the obtained test piece, the combustion test was done based on UL94 specification. V-0 is most preferable, V-1 and V-2 are in order, and NG is not applicable to the UL94 standard.

(2) Charpy impact strength Pellets of each resin composition obtained by the above-described method were injected on an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. Molding was performed to obtain an ISO test piece. The notched Charpy impact strength was measured according to the ISO 179 standard. The Charpy impact strength is preferably higher.

(3) Drop test of battery pack The pellets of each resin composition obtained by the above-described method were subjected to conditions of cylinder temperature 320 ° C. and mold temperature 80 ° C. using an injection molding machine, manufactured by Sodick Plustech, TR100EH. The battery pack lid and box shown in FIG. 1 were molded. In FIG. 1, the numbers surrounded by squares indicate the thickness of each part. The numbers other than those enclosed by the squares indicate the length of each part of the molded product. The unit is “mm”. A unit cell was incorporated into the obtained box and ultrasonically welded, and the lid was capped to obtain a battery pack. The obtained battery pack was dropped on a concrete surface from a height of 1.65 m on each of the six surfaces. This was defined as 1 cycle, and the test was repeated 3 cycles. The case where no crack was generated was indicated as ◯, and the case where crack was generated was indicated as x. In addition, when the fluidity was poor and the resin could not be completely filled in the mold, it was described as “unfillable”.

(4) Appearance of battery pack The resin composition pellets of Examples 3, 4, 6, and 7 and Comparative Examples 5 and 6 obtained by the above-described method were used in TR100EH manufactured by an injection molding machine Sodick Plustech Co., Ltd. Then, injection molding was performed under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C., and a battery pack lid shown in FIG. 1 was molded. After discarding the first 100 shots, another 1000 shots were molded, and the obtained 1000 lids were visually observed for white spots and silver molding defects. Regarding the white spot, the number average value of the confirmed number (/ one lid) is shown in Table 1. If the number of white spots is 20 or less, it can be determined that there is no problem as an actual molded product. Moreover, when silver was recognized by the molded article, it described as "silver." When there is silver, it cannot be used as an actual molded product.

(5) Mold contamination (evaluation of generated gas)
The resin composition pellets of Examples 4 and 5 and Comparative Example 5 obtained by the method described above were used in a mini mat 7 manufactured by Sumitomo Heavy Industries, Ltd., an injection molding machine, with a cylinder temperature of 300 ° C. and a mold temperature of 70. The molded piece was continuously subjected to 1000 shot injection molding using a vertical mold as shown in FIG. 2 under the condition of ° C., and the mold surface after 1000 shot molding due to the generated gas was observed. The case where there was no adhering matter was indicated as ◎, the case where adhering matter was slightly recognized but judged that there was no problem in normal continuous molding was indicated as ○, and the case where there were many adhering matters and it was judged that continuous molding was difficult was indicated as ×.
Note that the vertical mold shown in FIG. 2 is a mold designed to easily collect the generated gas at the pointed portion on the side opposite to the gate. The molded piece has a thickness of 3 mm, and the gate portion has a width of 1 mm and a thickness of 1 mm. In FIG. 2, the unit is “mm”.

From Table 1, the following became clear.
Even if the aromatic polycarbonate resin composition of the present invention is molded at a relatively high molding temperature of polycarbonate resin of 320 ° C., the resulting thin-walled molded product has flame retardancy, impact resistance, thermal stability, molding All of the product appearance was satisfied in a well-balanced manner (Examples 1 to 8). In particular, when molding is performed at a high temperature, there is a tendency that the strength of the molded product is reduced due to deterioration of the resin, and appearance defects such as white spots due to aggregation of silver and polyfluoroethylene occur. By using the resin composition, such a problem did not occur.
On the other hand, when a graft copolymer other than the graft copolymer specified in the present invention is blended, the flame retardancy achieved the purpose of the present application, as is clear from the comparison between Example 2 and Comparative Examples 1 and 2. The Charpy impact strength was slightly inferior.
When the graft copolymer of the present invention was not blended, the flame retardancy was at the V-2 level, the Charpy impact strength was greatly reduced, and the impact resistance of the battery pack was inferior (Comparative Example 3). Moreover, when not mix | blending a phosphorus flame retardant, the flame retardance could not achieve the objective of this application (comparative example 4).
When a flame retardant other than the flame retardant used in the present invention is blended, as is clear from the comparison between Examples 4 and 5 and Comparative Example 5, the fluidity is lowered and the mold is completely filled with the resin. In addition, the amount of generated gas was large and it was difficult to continuously form the battery pack. Further, the Charpy impact strength was lowered, and silver was confirmed in the obtained battery pack, and the appearance was poor.

  Even when the aromatic polycarbonate resin, phosphorus flame retardant, polyfluoroethylene and graft copolymer are blended within the range specified in the present invention, the barrel temperature during the resin composition melting and kneading is high (Comparative Example) 6) When the torque value of the extruder is high (Comparative Example 7), flame retardancy of V-1 level or higher cannot be achieved, and Charpy impact strength, impact resistance and appearance of the battery pack are inferior. It was a thing.

FIG. 1 shows a lid and a box of a battery pack manufactured in this embodiment. FIG. 2 is a schematic diagram of a vertical mold used for (5) mold contamination (evaluation of generated gas) in the embodiment of the present invention.

The flame retardant aromatic polycarbonate resin composition used in the present invention exhibits good flame retardancy and appearance even when it is molded into a thin molded product having a flat plate portion of 0.6 mm or less entirely or partially. . Moreover, since fluidity | liquidity and heat stability are favorable and it is excellent in productivity, the molded product obtained is excellent also in impact resistance, and has the performance which was able to balance comprehensively.
Since the flame-retardant aromatic polycarbonate resin composition of the present invention has the above-mentioned performance, battery packs such as mobile phones, portable stereos, and mobile personal computers, card-type information recording media such as memory cards and SD cards, etc. It is suitable as a container constituting the outer portion of the small auxiliary storage device.

Claims (8)

(A) 3 to 20 parts by weight of a phosphorus-based flame retardant, (C) 0.01 to 1 part by weight of polyfluoroethylene, and (D) a polyorganosiloxane-containing graft with respect to 100 parts by weight of an aromatic polycarbonate resin A flame-retardant aromatic polycarbonate resin composition for thin-wall molding comprising 1 to 20 parts by weight of a copolymer,
The (D) polyorganosiloxane-containing graft copolymer comprises (Y) 0.5 to 10 parts by weight of the first vinyl monomer in the presence of 40 to 90 parts by weight of the polyorganosiloxane particles. Polymerized, and further obtained by polymerizing (Z) 5 to 50 parts by weight of the second vinyl monomer,
The (Y) first vinyl monomer comprises (y-1) 100 to 50% by weight of a polyfunctional monomer and (y-2) 0 to 50% by weight of other copolymerizable monomers. A flame retardant according to UL94 standard of a 0.6 mm thickness test piece molded from the aromatic polycarbonate resin composition is V-0 or V-1 An aromatic polycarbonate resin composition.   The aromatic polycarbonate resin composition according to claim 1, wherein the (C) polyfluoroethylene is polyfluoroethylene coated with an organic polymer.  The aromatic polycarbonate resin composition according to claim 2, wherein the polyfluoroethylene content in the polyfluoroethylene coated with the organic polymer is 40 to 95% by weight. The (B) phosphorus flame retardant is at least one compound selected from the group consisting of a phosphazene compound, a compound represented by the following general formula (1), and a compound represented by the following general formula (2). The aromatic polycarbonate resin composition according to any one of claims 1 to 3.
General formula (1)

(In the general formula (1), R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group. , H, i and j each independently represent 0 or 1.)
General formula (2)

(In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl having 6 to 20 carbon atoms which may be substituted with an alkyl group. P, q, r and s are each independently 0 or 1, t is an integer of 1 to 5, and X is an arylene group, t is t when t is 2 or more. The repeating units may be the same or different. The aromatic polycarbonate resin composition according to any one of claims 1 to 4, wherein the (B) phosphorus flame retardant is a phosphorus compound represented by the following general formula (2).
General formula (2)

(In the general formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 6 carbon atoms or an aryl having 6 to 20 carbon atoms which may be substituted with an alkyl group. P, q, r and s are each independently 0 or 1, t is an integer of 1 to 5, and X is an arylene group, t is t when t is 2 or more. The repeating units may be the same or different.   The thin molded article which has a flat plate part with a thickness of 0.6 mm or less formed by shape | molding the aromatic polycarbonate resin composition of any one of Claims 1-5.  The thin-walled molded product according to claim 6, wherein the thin-walled molded product is a container constituting an outer portion of a battery pack or a small auxiliary storage device.  Including a step of using the aromatic polycarbonate resin composition according to any one of claims 1 to 5, wherein the flame retardancy in UL94 standard of a 0.6 mm-thick test piece is V-0 or V-1, A method for producing a thin molded product having a flat plate portion having a thickness of 0.6 mm or less.

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