JP5175493B2 - Aromatic polycarbonate resin composition, molded article using the same, and method for producing molded article - Google Patents

Description

The present invention relates to an aromatic polycarbonate resin composition, and more particularly to a flame retardant aromatic polycarbonate resin composition excellent in the production of thin molded articles.
More specifically, it has excellent fluidity, thermal stability that can withstand high temperature molding, that is, good mechanical properties such as impact resistance even at high temperature molding, and flame retardancy and color development. The present invention relates to an excellent aromatic polycarbonate resin composition and 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 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 in applications such as electrical and electronic equipment casings, home appliances, etc. In order to meet these demands, aromatic polycarbonate resins include halogenated compounds and phosphorous compounds. A number of techniques for making flame retardant by blending siloxane compounds, polyfluoroethylene and the like have been proposed. In recent years, electrical and electronic equipment casings such as cell phone battery packs and storage medium covers have been thinned year by year for the purpose of miniaturization, weight reduction, high functionality, and the like. For this reason, for electrical and electronic equipment casings, it has excellent fluidity that enables thin-wall molding and thermal stability that can withstand high-temperature molding, that is, mechanical properties such as impact resistance are excellent even at high-temperature molding. There is a demand for resin materials that are excellent in flame retardancy and color development.

  For such demands, for example, (A) aromatic polycarbonate resin, (B) phosphate ester flame retardant, (C) polytetrafluoroethylene, (D) scaly inorganic filler, (E) poly A composite in which one or more vinyl monomers are graft-polymerized to a composite rubber having a structure in which the organosiloxane rubber component and the polyalkyl (meth) acrylate rubber component cannot be separated from each other. A resin composition obtained by blending a rubber-based graft copolymer or a mixture of the composite rubber-based graft copolymer and a vinyl polymer has been proposed (Patent Document 1). However, Patent Document 1 does not describe the content of the polyorganosiloxane rubber component in the composite rubber-based graft copolymer of component (E), and the thickness of the test piece used for the evaluation of combustibility is also 1. There is no description about the flammability of the thin test piece.

A resin composition comprising (A) a polycarbonate resin, (B) a composite rubber-based graft copolymer, (C) a halogen-free phosphate ester compound, and (D) polytetrafluoroethylene, wherein (B) the composite The rubber-based graft copolymer has a structure in which the polyorganosiloxane rubber component 1 to 99% by weight and the polyalkyl acrylate rubber component 99 to 1% by weight are intertwined with each other so that the average particle size is 0. A flame retardant polycarbonate resin composition obtained by graft-polymerizing one or two or more vinyl monomers to a composite rubber having a diameter of 0.01 μm to 0.6 μm has been proposed (Patent Document 2). However, the content ratio of the polyorganosiloxane rubber component and the polyalkylacrylate rubber component in the component (B) is widely described as described above, and there is no description regarding the content of the polyorganosiloxane rubber component.
Moreover, as evaluation of staying heat stability, although the presence or absence of silver generation | occurrence | production of a component is described, there is no description regarding color developability.

  Silicone grafted with a vinyl polymer composed of one or more vinyl monomer units on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate with respect to 100 parts by weight of a thermoplastic resin such as polycarbonate. / Acrylic composite rubber-based graft copolymer, wherein the graft copolymer has a number average particle size of 300 to 2000 nm, a polyorganosiloxane content of 20 to 70% by mass, and a composite rubber content of 70 to 90 There has been proposed a resin composition containing 1 to 100 parts by weight of a silicone / acrylic composite rubber-based graft copolymer, which is characterized by mass% (Patent Document 3). However, Patent Document 3 does not describe the impact resistance of a high-temperature molded test piece. Moreover, the thickness of the test piece used for flame retardance evaluation is as thick as 1.6 mm, and there is no description regarding the flame retardance of a thin-walled test piece.

0.1 to 30 parts by weight of a phosphoric acid ester is blended with 100 parts by weight of the resin composition of 99.5 to 50% by weight of the polycarbonate resin (A) and 0.5 to 50% by weight of the liquid crystalline resin (B). A resin composition for a battery pack housing member of a portable device in which a portion having a maximum projection surface thickness of 0.6 mm or less is 100 mm ² or more has been proposed (Patent Document 4). However, Patent Document 4 has no specific description regarding flame retardancy, impact resistance and appearance.

JP-A-7-228764 Japanese Patent Laid-Open No. 11-21441 JP 2004-359889 A JP 2002-348460 A

 The object of the present invention is to have excellent fluidity capable of forming a thin-walled molded product having a flat plate portion having a thickness of 0.8 mm or less in whole or in part, and heat stability that can withstand high-temperature molding, that is, Another object of the present invention is to provide an aromatic polycarbonate resin composition and a molded article that have excellent mechanical properties such as impact resistance even when molded at high temperatures, and are excellent in flame retardancy and color development.

As a result of the study of the above cited references 1 to 4, the present inventors have found that there are the following problems.
When the resin composition described in the example of the cited document 1 is injection-molded at a cylinder temperature of 300 ° C. or higher, the color developability (colorability by the colorant) and the impact strength are greatly reduced, and the practicality is inferior.
In addition, although the resin composition described in the example of the cited document 2 is described as being ductile fracture in an Izod impact strength test when injection molded at a molding temperature of 280 ° C., it is injected at a cylinder temperature of 300 ° C. or higher. When molded, the impact strength is greatly reduced. In addition, since the resin composition has poor fluidity and is not suitable for thin-walled molded product applications, when the molecular weight of the polycarbonate resin is lowered in order to obtain the desired fluidity, the intended combustibility cannot be obtained.
When the resin composition described in the example of the cited document 3 is used and a thin container having a flat plate portion of 0.8 mm or less is formed entirely or partially, flame retardancy and fluidity are insufficient. In addition, the impact resistance which is the object of the present invention cannot be satisfied.
Furthermore, even when the resin composition described in the example of the cited document 4 was used, a thin container having a flat plate portion of 0.8 mm or less was entirely or partially molded at a cylinder temperature of 300 ° C. or higher. In this case, the impact strength was lowered, and particularly, in the vicinity of the gate of the molded product, delamination was likely to occur, and the practical value was low.

 Under such circumstances, in order to solve the above-mentioned problems, the present inventors have studied, and as a result, the aromatic polycarbonate resin has a Si content in the composite rubber-based graft copolymer within a specific range. By blending specific amounts of silicone / acrylic composite rubber-based graft copolymer having a number average particle size, phosphorus flame retardant and anti-dripping agent, it can withstand excellent fluidity capable of thin-wall molding and high-temperature molding. Flame retardant aromatics that are suitable as resin materials for electrical and electronic equipment casings that have only thermal stability and excellent mechanical properties such as impact resistance, flame retardancy, and color development The present inventors have found that a polycarbonate resin composition can be obtained and completed the present invention.

（一般式（１）中、Ｒ¹、Ｒ²およびＲ³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、ｈ、ｉおよびｊは、各々独立に０または１を示す。）
一般式（２）

（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。）
（１０）前記（Ｃ）リン系難燃剤が下記の一般式（２）で表されるリン系化合物である（１）〜（９）のいずれかに記載の芳香族ポリカーボネート樹脂組成物。
一般式（２）

（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。）
（１１）（１）〜（１０）のいずれかに記載の芳香族ポリカーボネート樹脂組成物を成形してなる成形品。
（１２）肉厚０．８ｍｍ以下の平板部を有する、（１１）に記載の成形品。
（１３）前記成形品が電気・電子機器筐体である、（１１）または（１２）に記載の成形品。
（１４）前記成形品が電池パックまたは小型補助記憶装置の外郭部を構成する容器である、（１１）または（１２）に記載の成形品。
（１５）（１）〜（１０）のいずれかに記載の芳香族ポリカーボネート樹脂組成物を用いる工程を含み、０．８ｍｍ厚試験片のＵＬ９４規格における難燃性がＶ−０またはＶ−１であり、肉厚０．８ｍｍ以下の平板部を有する成形品の製造方法。 Specifically, the present invention has been achieved by the following means.
(1) Vinyl composed of one or more vinyl monomer units in a composite rubber containing (B) polyorganosiloxane and polyalkyl (meth) acrylate with respect to 100 parts by weight of (A) aromatic polycarbonate resin A silicone / acrylic composite rubber-based graft copolymer grafted with a base polymer, wherein the Si content in the composite rubber graft copolymer detected by the ICP / AES method is 9% by weight or less, and The number average particle size of the graft copolymer is 300 nm or more, 1-12 parts by weight of a silicone / acrylic composite rubber-based graft copolymer, (C) 2-20 parts by weight of a phosphorus flame retardant, D) An aromatic polycarbonate resin composition comprising 0.01 to 1.5 parts by weight of an anti-dripping agent.
(2) The aromatic polycarbonate resin composition according to (1), wherein the flame retardancy in the UL94 standard of a 0.8 mm-thick test piece molded from the aromatic polycarbonate resin composition is V-0 or V- An aromatic polycarbonate resin composition, which is 1.
(3) The aromatic polycarbonate resin composition according to (1) or (2), wherein (D) the anti-dripping agent is polyfluoroethylene.
(4) The aromatic polycarbonate resin composition according to any one of (1) to (3), wherein the number average particle diameter of the (B) graft copolymer is 2000 nm or less.
(5) Furthermore, (E) Silicate filler is blended with 0.01 to 12 parts by weight with respect to 100 parts by weight of (A) aromatic polycarbonate resin, and any of (1) to (4) The aromatic polycarbonate resin composition described in 1.
(6) The aromatic polycarbonate resin composition according to (5), wherein the (E) silicate filler is talc.
(7) The aromatic polycarbonate resin composition according to any one of (3) to (6), wherein the polyfluoroethylene is polyfluoroethylene coated with an organic polymer.
(8) The aromatic polycarbonate resin composition according to (7), wherein the polyfluoroethylene content ratio in the polyfluoroethylene coated with the organic polymer is 40 to 95% by weight.
(9) The (C) phosphorus-based flame retardant is at least one 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 (1) to (8), which is a compound.
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.
(10) The aromatic polycarbonate resin composition according to any one of (1) to (9), wherein the (C) 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.
(11) A molded product obtained by molding the aromatic polycarbonate resin composition according to any one of (1) to (10).
(12) The molded product according to (11), which has a flat plate portion having a thickness of 0.8 mm or less.
(13) The molded product according to (11) or (12), wherein the molded product is an electric / electronic device casing.
(14) The molded product according to (11) or (12), wherein the molded product is a container that forms an outer portion of a battery pack or a small auxiliary storage device.
(15) including a step of using the aromatic polycarbonate resin composition according to any one of (1) to (10), and flame retardancy in UL94 standard of a 0.8 mm-thick test piece is V-0 or V-1. A method for producing a molded product having a flat plate portion having a thickness of 0.8 mm or less.

  The polycarbonate resin composition of the present invention has excellent fluidity capable of forming a thin molded product having a flat plate portion having a thickness of 0.8 mm or less in whole or in part, and has thermal stability that can withstand high temperature molding. It has excellent mechanical properties such as impact resistance even when molded at high temperature, and is excellent in flame retardancy and color development. Therefore, it is suitable as a resin material for thin-walled electrical and electronic equipment housings such as battery packs for mobile phones, mobile stereos, mobile personal computers, etc., and containers that form the outer parts of small auxiliary storage devices such as memory cards and SD cards. It is.

  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 addition, the thin molded product in the present invention is a molded product used for an electric / electronic device casing, for example, a battery pack (cell phone battery pack, etc.) or a container constituting an outer portion of a small auxiliary storage device. , A molded product having a flat plate portion of 0.8 mm or less in whole or in part.

(A) Aromatic polycarbonate resin The (A) aromatic polycarbonate resin used in the present invention is a branched product obtained by reacting an aromatic hydroxy compound or a small amount thereof with a diester of phosgene or carbonic acid. It may be a thermoplastic aromatic polycarbonate polymer or copolymer. (A) The manufacturing method of aromatic polycarbonate resin is not specifically limited, A well-known method, ie, a phosgene method (interfacial polymerization method), a melting method (transesterification method), etc. are employ | adopted. In the present invention, an aromatic polycarbonate resin produced by a melting method and having an adjusted terminal OH group amount can also be used.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxydiphenyl etc. are mentioned, Preferably bisphenol A is mentioned. In addition, for the purpose of further improving the flame retardancy, it has a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound and / or a siloxane structure, and contains phenolic OH groups at both ends. It is also possible to use polymers or oligomers.

  In order to obtain a branched aromatic polycarbonate resin, phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tris ( 4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenylheptene-3,1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1 A polyhydroxy compound such as tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5- A compound such as bromuisatin may be used as part of the aromatic dihydroxy compound, and in this case, the amount of the compound used It is from 0.01 to 10 mol% based on the aromatic dihydroxy compound, preferably 0.1 to 2 mol%.

 The aromatic polycarbonate resin (A) used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl). And polycarbonate copolymers derived from propane and other aromatic dihydroxy compounds. As the aromatic polycarbonate resin, two or more kinds of resins may be mixed and used.

(A) In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol and and p-long chain alkyl-substituted phenols.
(A) The molecular weight of the aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 14,000 to 28,000, more preferably It is 16,000-26,000, More preferably, it is 18,000-24,000. By setting the viscosity average molecular weight to 14,000 or more, the mechanical strength tends to be improved, and by setting the viscosity average molecular weight to 28,000 or less, the fluidity is kept good and the molding of the thin-walled molded product tends to be easy. is there.

(B) Silicone / acrylic composite rubber-based graft copolymer (B) The composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate used in the present invention is composed of one or more vinyl monomer units. A silicone / acrylic composite rubber graft copolymer grafted with a vinyl polymer, wherein the Si content in the composite rubber graft copolymer detected by ICP / AES analysis is 9% by weight or less. And the graft copolymer has a primary particle size of 300 nm or more, and is abbreviated as “composite rubber graft copolymer” (hereinafter referred to as “composite rubber graft copolymer”). Can be produced by a method disclosed in known literature, for example, JP-A-2004-359889.

The composite rubber of the composite rubber-based graft copolymer (B) in the present invention has a structure in which polyorganosiloxane and polyalkyl (meth) acrylate are intertwined so that they cannot be separated from each other.
As the polyorganosiloxane constituting the composite rubber, for example, a polymer containing dimethylsiloxane units as constituent units is preferable. Examples of the dimethylsiloxane constituting the polyorganosiloxane include a dimethylsiloxane-based cyclic body having a 3-membered ring or more, and a 3- to 7-membered ring is preferable. Specific examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. These may be used alone or in admixture of two or more. Among these, the main component is preferably octamethylcyclotetrasiloxane from the viewpoint of easy control of the particle size distribution.

  As polyorganosiloxane, what contains the siloxane containing a vinyl polymerizable functional group as a structural component is preferable. Here, the siloxane containing a vinyl polymerizable functional group contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. Among the siloxanes containing vinyl polymerizable functional groups, various alkoxysilane compounds containing vinyl polymerizable functional groups are preferable in consideration of reactivity with dimethylsiloxane. These siloxanes containing vinyl polymerizable functional groups can be used alone or as a mixture of two or more.

 The polyorganosiloxane may be crosslinked with a siloxane-based crosslinking agent. Examples of the siloxane crosslinking agent include trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

  There is no restriction | limiting in particular as a manufacturing method of polyorganosiloxane, For example, the following manufacturing methods are employable. First, a latex is prepared by emulsifying a mixture containing dimethylsiloxane and a vinyl-polymerizable functional group-containing siloxane if necessary, or a mixture containing a siloxane-based crosslinking agent if necessary with an emulsifier and water. Is then polymerized at a high temperature using an acid catalyst, and then the acid is neutralized with an alkaline substance to obtain a polyorganosiloxane latex. For the preparation of latex, a method using a homogenizer is preferable because the particle size distribution tends to be narrow.

  The emulsifier used in the above production method is not particularly limited as long as dimethylsiloxane can be emulsified, but an anionic emulsifier is preferable. Examples of the anionic emulsifier include sodium alkylbenzene sulfonate and sodium polyoxyethylene nonylphenyl ether sulfate. Among these, sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable.

  Examples of the acid catalyst used for polymerization of polyorganosiloxane include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzenesulfonic acid, and aliphatic substituted naphthalenesulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These acid catalysts are used alone or in combination of two or more. Among these, the use of mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid that do not form micelles can narrow the particle size distribution of the polyorganosiloxane latex, which is further attributed to the emulsifier component in the polyorganosiloxane latex. This is preferable in that the appearance defect of the molded product can be reduced.

  The number average particle diameter of the polyorganosiloxane is preferably 150 nm or more, more preferably 150 to 2000 nm, in order to make the number average particle diameter of the composite rubber-based graft copolymer 300 nm or more. More preferably, it is 1000 nm. By setting the number average particle size of the polyorganosiloxane to 150 nm or more, the amount of polyalkyl (meth) acrylate required to obtain a composite rubber-based graft copolymer having the above particle size can be reduced. Can be suppressed.

The polyalkyl (meth) acrylate constituting the composite rubber is a polymer containing an alkyl (meth) acrylate unit and a polyfunctional alkyl (meth) acrylate unit as constituent components.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, and alkyl methacrylates such as 2-ethylhexyl methacrylate and n-lauryl methacrylate. Or two or more can be used together. Among these, n-butyl acrylate is particularly preferable in consideration of the impact resistance of the aromatic polycarbonate resin composition of the present invention and the gloss of the molded product.

Examples of the polyfunctional alkyl (meth) acrylate include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, and the like. These can be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in content of a polyfunctional alkyl (meth) acrylate unit, It is preferable that it is 0.1-2.0 weight% in 100 weight% of polyalkyl (meth) acrylate, 0.3- More preferably, it is 1.0% by weight. By setting the content of the polyfunctional alkyl (meth) acrylate to 0.1% by weight or more, there is a tendency that a reduction in impact strength due to a change in the morphology of the composite rubber can be suppressed, and the polyfunctional alkyl (meth) By setting the acrylate content to 2.0% by weight or less, the impact strength tends to be further improved.

  In order to produce a composite rubber composed of the above-mentioned polyorganosiloxane and polyalkyl (meth) acrylate, first, in the latex of the polyorganosiloxane component, the above alkyl (meth) acrylate component and the polyfunctional alkyl (meth) acrylate component Is added and impregnated in polyorganosiloxane, and then a radical polymerization initiator such as a known peroxide, an azo initiator, or a redox polymerization initiator in combination with an oxidizing agent / reducing agent is used. A polymerization initiator is preferred.

A composite rubber-based graft copolymer can be obtained by radical polymerization of one or more vinyl monomers in the presence of the composite rubber to form a graft portion made of a vinyl polymer on the composite rubber.
A specific production method includes a production method by emulsion graft polymerization. In this production method by emulsion graft polymerization, a vinyl monomer is added to the composite rubber latex, and graft polymerization is performed in a single step or multiple steps by a radical polymerization method to obtain a composite rubber-based graft copolymer latex. Next, this composite rubber-based graft copolymer latex is put into hot water in which a coagulant is dissolved, and salted out and solidified to separate the graft copolymer and collect it in powder form.

  The vinyl monomer is not particularly limited, and examples thereof include aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyltoluene, and methacrylic compounds such as methyl methacrylate, ethyl methacrylate, and 2-ethylhexyl methacrylate. Examples include acid esters, acrylic acid esters such as methyl acrylate, ethyl acrylate, and butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.

  In addition, for radical polymerization of the composite rubber and the vinyl monomer, the same radical polymerization initiator as that used for the production of the composite rubber composed of the polyorganosiloxane and polyalkyl (meth) acrylate should be used. Can do.

The number average particle diameter of the (B) composite rubber-based graft copolymer used in the present invention is 300 nm or more, preferably 400 nm or more, and more preferably 500 nm or more. (B) The upper limit of the number average particle size of the composite rubber-based graft copolymer is not particularly defined unless departing from the gist of the present invention, but is usually 2000 nm or less, preferably 1500 nm or less, more preferably Is 1000 nm or less. When the number average particle diameter of the composite rubber-based graft copolymer is less than 300 nm, the balance between the color development and the impact resistance at low temperature of the molded article made of the aromatic polycarbonate resin composition obtained is lowered. Further, by setting the number average particle diameter to 2000 nm or less, the impact resistance and surface appearance of the molded product made of the aromatic polycarbonate resin composition obtained tend to be further improved. The number average particle diameter of the composite rubber-based graft copolymer in the present invention is the primary of the composite rubber-based graft copolymer dispersed in the aromatic polycarbonate resin of the matrix by observation with a transmission electron microscope (TEM). It is a value obtained by measuring the particle diameter. Specifically, for example, it can be obtained in the following manner.
An ultrathin slice having a thickness of 100 nm cut out from the resin composition pellet of the present invention was further stained with osmium tetroxide vapor for 60 minutes and further with ruthenium tetroxide vapor for 60 minutes, and then observed with a TEM. Using the image obtained by TEM observation, the primary particle diameter (average diameter) of 30 composite rubber graft copolymers dispersed in the matrix was measured, and the number average was used as the number average particle diameter in the present invention. .

  (B) The composite rubber content in the composite rubber-based graft copolymer is preferably 70 to 90% by weight in 100% by weight of the composite rubber-based graft copolymer. By making the content of the composite rubber 70% by weight or more, impact resistance tends to be further improved, and by making it 90% by weight or less, the color developability and dispersibility are maintained while maintaining good impact resistance. It tends to improve.

  Further, the Si content in the (B) composite rubber-based graft copolymer is 9% by weight or less, preferably 7% by weight or less, more preferably 5% by weight as a value detected by the ICP / AES method. % Or less. By setting the content to 9% by weight or less, good color development can be maintained. The lower limit of the Si content is not particularly defined, but is preferably 1% by weight or more, and more preferably 1.5% by weight or more from the viewpoint of further improving the impact resistance of the molded product.

(C) Phosphorus Flame Retardant The (C) phosphorus flame retardant in the present invention is preferably a phosphazene compound, a compound represented by the following general formula (1), and a compound represented by the following general formula (2) Although at least 1 sort (s) selected from the group which consists of is mentioned, It is not limited to these.

 Examples of the phosphazene compound include a cyclic phenoxy phosphazene compound, a chain phenoxy phosphazene compound, and a crosslinked phenoxy phosphazene compound.

(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.)
The phosphorus compound represented by the general formula (1) can be produced from phosphorus oxychloride or the like by a known method. Specific examples include triphenyl phosphate, tricresyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri (isopropylphenyl) phosphate, diphenyl cresyl phosphate, tributyl phosphate, and the like.

(In General Formula (2), R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently 0 or each independently the number of carbon atoms optionally substituted with an alkyl group having 1 to 6 carbon atoms or an alkyl group. 6 to 20 aryl groups, p, q, r and s are each independently 0 or 1, t is an integer of 1 to 5, X is an arylene group, and t is 2 or more. Sometimes t repeating units may be the same or different.)

The phosphorus compound represented by the general formula (2) is a condensed phosphate ester having t of 1 to 5, but in the case of a mixture of plural types of condensed phosphate esters having different t, t is a mixture thereof. Calculated as the average value of. X represents an arylene group, and 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 each independently represent an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms which may be substituted with an alkyl group, Are each independently a group derived from phenol, cresol, xylenol.

Among the above-mentioned (C) phosphorus-based flame retardants, in the present invention, the compound represented by the general formula (2) is more preferable because it is excellent in workability and thermal stability and the amount of gas generated during molding is small. preferable. Particularly preferably, in the general formula (2), X is a group 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 groups derived from cresol or xylenol, respectively.
When X in the general formula (2) is a group derived from resorcinol, phenyl-resorcin-polyphosphate, cresyl-resorcin-polyphosphate, phenyl-cresyl-resorcin-polyphosphate, xylyl-resorcin-polyphosphate, phenyl-p Preferred examples include -tert-butylphenyl resorcin polyphosphate, phenyl isopropylphenyl resorcin polyphosphate, cresyl xylyl resorcin polyphosphate, phenyl isopropylphenyl diisopropylphenyl resorcin polyphosphate, and the like.

 When X in the general formula (2) is a group derived from bisphenol A, phenyl, bisphenol, polyphosphate, cresyl, bisphenol, polyphosphate, phenyl, cresyl, bisphenol, polyphosphate, xylyl, bisphenol, polyphosphate, phenyl Preferred examples include -p-tert-butylphenyl / bisphenol / polyphosphate, phenyl / isopropylphenyl / bisphenol polyphosphate, cresyl / xylyl / bisphenol / polyphosphate, phenyl / isopropylphenyl / diisopropylphenyl / bisphenol polyphosphate, and the like.

  Examples of the (C) phosphorus flame retardant of the present invention include “TPP” (triphenyl phosphate), “CR733S” (resorcinol bis (diphenyl phosphate)), “CR741” (bisphenol) from Daihachi Chemical Industry Co., Ltd. A bis (diphenyl phosphate)), "PX200" (resorcinol bis (dixylenyl phosphate)), and ADEKA Corporation "ADEKA STAB FP700" (bisphenol A bis (diphenyl phosphate)) are easily sold. Is available.

(D) Anti-dripping agent The (D) anti-dripping agent in the present invention refers to a compound having a property of preventing dripping of a resin during combustion, and specific examples include, for example, fluororesin, silicon oil, silica and the like. Can be mentioned. Among these, a fluorine-based resin is preferable from the viewpoint of flame retardancy of the resin composition. In addition, the structure which serves as (E) silicate filler which will be described later (D) may also be used.

  As the fluorine-based resin, preferably, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, vinylidene fluoride, And polyfluoroethylene such as polychlorotrifluoroethylene. Among these, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, and tetrafluoroethylene / ethylene copolymer are preferable. A fluoroethylene / hexafluoropropylene copolymer is more preferred, and polytetrafluoroethylene is more preferred.

As polyfluoroethylene, what has fibril formation ability is preferable. Such polyfluoroethylene has a high anti-dripping ability because it easily disperses in the resin and tends to form a fibrous structure by bonding polymers together.
Examples of polyfluoroethylene having fibril-forming ability include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon F201L manufactured by Daikin Chemical Industries, Ltd., and the like. The aqueous dispersion is commercially available under trade names such as Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Industries, Ltd.

  In order to improve the appearance of the molded product, it is preferable to use a specific coated polyfluoroethylene coated with an organic polymer (hereinafter sometimes abbreviated as “coated polyfluoroethylene”). The content of polyfluoroethylene in the coated polyfluoroethylene is preferably 40 to 95% by weight, more preferably 43 to 80% by weight, further preferably 45 to 70% by weight, and particularly preferably 47 to 60% by weight. . By setting the content of polyfluoroethylene in the coated polyfluoroethylene to 40% by weight or more, flame retardancy tends to be further improved, and by setting it to 95% by weight or less, Occurrence is suppressed and the appearance tends to be improved.

  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.

  Examples of such coated polyfluoroethylene include Metabrene A-3800, A-3700, KA-5503 manufactured by Mitsubishi Rayon Co., Ltd., and Poly TS AD001 manufactured by PIC.

(E) Silicate Filler The aromatic polycarbonate resin composition of the present invention preferably contains (E) a silicate filler in order to improve flame retardancy, rigidity and dimensional stability. The silicate filler has a large effect of preventing molten resin drip during combustion, and can further improve the flame retardancy of the resin composition. (E) Specific examples of the silicate filler include kaolin, talc, clay, mica, montmorillonite, wollastonite, natural silica, synthetic silica, various glass fillers, zeolite and diatomaceous earth, or a mixture thereof. However, talc, mica and wollastonite are preferred, and talc is most preferred from the balance of flame retardancy and dimensional stability. Talc is particularly effective in preventing molten resin drip during combustion among the above silicate fillers.
Talc is not particularly limited, but is preferably 1.0 to 9.0 μm, more preferably 1.5 to 8.8 in terms of a number average particle diameter measured by a sedimentation method (Asada method) using a light transmission particle size distribution analyzer. The talc is 0 μm, more preferably 2.0 to 7.0 μm. When the number average particle diameter is 1.0 μm or more, flame retardancy tends to be improved, and when it is 9.0 μm or less, the appearance of the molded product tends to be further improved.
The content of the Fe component and the Al component in talc is preferably 0.001 to 0.4% by weight, more preferably 0.001 to 0.2% by weight as Fe ₂ O ₃ and Al ₂ O ₃ , respectively. preferable.

  The (E) silicate filler used in the present invention has various couplings for the purpose of increasing the affinity or interfacial bond strength with (A) aromatic polycarbonate and (B) composite rubber-based graft copolymer. Agents can also be used. As the coupling agent, silane-based, chromium-based and titanium-based coupling agents are usually used. Among them, those containing silane coupling agents such as epoxy silane compounds such as γ-glycidoxypropyltrimethoxysilane, vinyltrichlorosilane compounds and γ-aminopropyltriethoxysilane compounds are preferable. At this time, in order to improve mechanical strength and kneadability, treatment with various surfactants such as nonionic / cationic / anionic types and dispersants such as fatty acids, metal soaps, and various resins may be performed. preferable.

The blending amount of the components (A) to (E) constituting the aromatic polycarbonate resin composition of the present invention is such that (B) the composite rubber-based graft copolymer is 1 with respect to 100 parts by weight of the (A) aromatic polycarbonate resin. -12 parts by weight, (C) 2-20 parts by weight of a phosphorus flame retardant, and (D) 0.01-1.5 parts by weight of an anti-dripping agent.
Moreover, when mix | blending (E) silicate filler, 0.01-12 weight part is preferable with respect to 100 weight part of said (A) aromatic polycarbonate resin.
(B) If the compounding amount of the composite rubber-based graft copolymer is less than 1 part by weight, the impact resistance and flame retardancy are insufficient, and if it exceeds 12 parts by weight, the rigidity is lowered. The blending amount of the component (B) is more preferably 2 to 10 parts by weight, still more preferably 3 to 8 parts by weight.
(C) When the blending amount of the phosphorus-based flame retardant is less than 2 parts by weight, the flame retardancy and fluidity are insufficient, and when it exceeds 20 parts by weight, the mechanical characteristics are lowered, the load deflection temperature is lowered, and the mold deposit is reduced. May occur. More preferably, the amount of component (C) is 3 to 18 parts by weight, more preferably 4 to 15 parts by weight.
(D) When the blending amount of the anti-dripping agent is less than 0.01, the flame retardancy is insufficient, and when it exceeds 1.5 parts by weight, the appearance of the molded product is deteriorated. The compounding amount of the component (D) is more preferably 0.05 to 1.0 part by weight, still more preferably 0.05 to 0.8 part by weight. When coating polyfluoroethylene is blended as an anti-dripping agent, it is blended so that the amount of polyfluoroethylene in the coating polyfluoroethylene falls within the range of the blending amount of the anti-dripping agent.
(E) By adding 0.01 parts by weight or more of a silicate filler, rigidity and dimensional stability can be improved more effectively, and by making it 12 parts by weight or less, impact resistance is further improved. It tends to improve. More preferably, the amount of component (E) is 1 to 10 parts by weight, more preferably 2 to 8 parts by weight.

In addition to the above components (A) to (E), the aromatic polycarbonate resin composition of the present invention is blended with other resins and various resin additives as long as the object of the present invention is not impaired. can do.
Examples of other resins include polyethylene resins, polyolefin resins such as polypropylene resins, polyamide resins, polyester resins, polyacetal resins, polyimide resins, polyetherimide resins, polyurethane resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, A polymethacrylate resin, a phenol resin, an epoxy resin, etc. are mentioned.
These other resin components may be used as part of (A) the aromatic polycarbonate resin, and the amount used is preferably 50% by weight or less in (A) the aromatic polycarbonate resin, and 30% by weight. The following is more preferable. Two or more of these other resins may be used in combination.
Also, as resin additives, antioxidants, heat stabilizers, mold release agents, colorants, weather resistance improvers, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, Examples thereof include inorganic fillers other than (E) silicate fillers such as dispersants, antibacterial agents, glass fibers, glass flakes, carbon fibers, and metal fibers.
Two or more of these resin additives may be used in combination.

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. The 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. When the blending amount is 0.01 parts by weight or more, the effect as a heat stabilizer tends to be more easily exerted, and even when 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, melicic 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. 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, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, 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.

Examples of the colorant that can be used in the present invention include dyes, inorganic pigments, and organic pigments that are generally used in thermoplastic resin molded articles.
Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, acridine dyes, cyanine dyes, nitro dyes, and nigrosine. Inorganic pigments include oxide pigments such as titanium oxide, red pepper and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc sulfide and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. Etc. Examples of organic pigments include nitro pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Among these, the inorganic pigment may improve the flame retardancy of the resin composition. In particular, carbon black has a higher flame retardancy improving effect than other colorants. In addition, for the purpose of improving the handling property at the time of extrusion, a colorant that is masterbatched with a polystyrene resin, a polycarbonate resin, or an acrylic resin may be used as the colorant.

  The blending amount of the colorant is preferably 3 parts by weight or less, more preferably 1 part by weight or less with respect to 100 parts by weight of the (A) aromatic polycarbonate resin. In addition, inorganic pigments such as titanium oxide may be used for purposes other than coloring (for example, imparting light-shielding properties), and the blending amount in that case is usually 20 with respect to 100 parts by weight of (A) aromatic polycarbonate resin. The amount is not more than parts by weight, preferably not more than 15 parts by weight.

 The method for producing the aromatic polycarbonate resin composition of the present invention is not particularly limited. For example, (1) (A) aromatic polycarbonate resin, (B) silicone / acrylic composite rubber-based graft copolymer, C) a phosphorus-based flame retardant, (D) a dripping preventive, and (E) a silicate filler or a resin additive blended as necessary, and (2) (C) phosphorus When the flame retardant is liquid, a liquid (C) phosphorus flame retardant that has been separately heated at 50 to 120 ° C. after melt-kneading components other than (C) phosphorus flame retardant in advance A method of adding to a melted resin and melt-kneading can be mentioned.

In the aromatic polycarbonate resin composition of the present invention, the flame retardancy in the UL94 standard of a 0.8 mm thick test piece can be set to 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 types of raw materials, the production method, and the like. For example, (C) a phosphorus flame retardant and (D) Blending ratio of anti-dripping agent [(C) / (D) ratio], (B) Total blending amount of silicone / acrylic composite rubber-based graft copolymer and (C) phosphorus-based flame retardant [((B) + (C)) amount], in the case of producing an aromatic polycarbonate resin composition by melt kneading, by adjusting the conditions at the time of melt kneading, etc., in a thin portion without reducing physical properties other than flame retardancy It is easier to achieve the high flame retardant level as described above.
The (C) / (D) 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) + (C)) 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, when the dispersibility of each component is made better and (D) an anti-dripping agent, particularly polyfluoroethylene, is blended, the ability to prevent molten resin drip during combustion by fibrils of polyfluoroethylene is further improved and stable. In order to perform kneading, it is necessary to carefully select a method for producing the aromatic polycarbonate resin composition. 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. (C) Ingredients other than the phosphorus-based flame retardant, that is, (A), (B), (D) and optional additive components are previously prepared using a mixer such as a tumbler, Henschel mixer, ribbon blender, 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. In addition, when the (C) phosphorus-based flame retardant is in liquid form, 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.
Within the range of the composition of the aromatic polycarbonate resin composition defined in the present invention, by adopting any of the above conditions or by combining a plurality of conditions, physical properties other than flame retardancy It becomes easier to set the flame retardancy in the UL94 standard of the 0.8 mm thickness test piece to the V-0 or V-1 level while maintaining a good value.

  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 good appearance and 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 0.8 mm or less by an 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 set to a higher temperature, usually 290 to 360 ° C, preferably 305 to 360 ° C, more preferably 310 to 350 ° C, and even more preferably 315 to 340 ° C. When a conventional resin composition is used, if the resin temperature at the time of molding is increased in order to form a thin container, white spot foreign matter is generated on the surface of the thin container, and the appearance is liable to deteriorate. However, by using the resin composition of the present invention, which is superior in thermal stability compared to conventional resin compositions, even in the relatively high temperature range as described above, good impact resistance, appearance, color development It becomes possible to manufacture a thin-walled container having the properties and flame retardancy.

In the present invention, the thin-walled molded product is a molded product having a flat plate portion of 0.8 mm or less in whole or part, preferably a molded product having a flat plate portion having an area of 50 mm ² or more and a thickness of 0.8 mm or less. It is. “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 article of the present invention constitutes an outer case of an electronic / electric equipment casing, specifically a battery pack (for example, a box or lid used for a battery pack of a mobile phone) or a small auxiliary storage device. A resin container used for a container (for example, a cover of a memory card, an SD card, etc.) and the like, and a resin container having a flat plate part having a thickness of 0.8 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 with an average thickness of 0.8 mm or less that is recessed by a rising piece. Moreover, based on the usage aspect etc. of an electrical / electronic equipment part normally, the area of the said flat plate part is 1-100 cm < ² >, the height of a rising piece is 0.5-10 mm, and the thickness of a rising piece is the container main body. From the viewpoint of increasing the rigidity and increasing the accommodation efficiency of the contents, it is usually 0.3 to 1.2 mm.

  EXAMPLES The present invention will be described more specifically below with reference to 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) )

(B) Graft copolymer (b-1) Methyl methacrylate, butyl acrylate, dimethyl siloxane copolymer: “Metabrene S-2100” manufactured by Mitsubishi Rayon Co., Ltd., Si content 2.6 in the copolymer % By weight, number average particle size 80
0nm
(B-2) Methyl methacrylate, butyl acrylate, dimethylsiloxane copolymer: “Methbrene S-2001” manufactured by Mitsubishi Rayon Co., Ltd., Si content in the copolymer: 3.0% by weight, number average particle diameter 20
0nm
(B-3) “Methyl methacrylate, butyl acrylate, dimethylsiloxane copolymer:“ Metabrene S-2030 ”manufactured by Mitsubishi Rayon Co., Ltd., Si content in the copolymer: 9.5% by weight, number average particle Diameter 2
00nm
(B-4) Butadiene / alkyl acrylate / alkyl methacrylate copolymer (multilayer structure polymer, core layer is butadiene, shell layer is a copolymer of alkyl acrylate and alkyl methacrylate: Rohm and Haas “Paraloid EXL-2603”
(B-5) Alkyl acrylate / alkyl methacrylate copolymer (multi-layer structure polymer, core layer is alkyl acrylate, shell layer is alkyl methacrylate: “Paraloid EXL-2315” manufactured by Rohm and Haas.

（式中 ｔ₂は１．０１である。）
（ｃ−２）縮合リン酸エステル：（株）ＡＤＥＫＡ製「アデカスタブ ＦＰ７００」（ビスフェノールＡビス（ジフェニルホスフェート）

（式中 ｔ₁は１．１である。）
（ｃ−３）トリフェニルホスフェート：大八化学工業（株）製
（ｃ−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」 (C) Flame retardant (c-1) Condensed phosphate ester: “PX200” (resorcinol bis (dixylenyl phosphate)) manufactured by Daihachi Chemical Industry Co., Ltd.

(Where t ₂ is 1.01)
(C-2) Condensed phosphate ester: “ADEKA STAB FP700” (bisphenol A bis (diphenyl phosphate) manufactured by ADEKA Corporation

(Where t ₁ is 1.1)
(C-3) Triphenyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd. (c-4) Brominated polycarbonate oligomer: “Iupilon (registered trademark) FR-53” manufactured by Mitsubishi Engineering Plastics Co., Ltd.

(D) Anti-dripping agent (d-1) Polytetrafluoroethylene coated with an acrylic resin: “Maybrene A-3800” manufactured by Mitsubishi Rayon Co., Ltd. (the content of polytetrafluoroethylene in the coated polytetrafluoroethylene is 50% by weight.)
(D-2) Uncoated polytetrafluoroethylene: “Polyflon F-201L” manufactured by Daikin Industries, Ltd.
In addition, since the blending amounts of (d-1) and (d-2) accurately grasp the effect of the PTFE content in the coated PTFE, the blending amount of PTFE itself with respect to PC is almost the same throughout the examples and comparative examples. The amount was such that

(E) Silicate filler (e) Talc: “Micron White 5000S” manufactured by Hayashi Kasei Co., Ltd., number average particle size 2.8 μm, no surface treatment (F) mold release agent (f) pentaerythritol tetrastearate: cognis “VPG861”
(G) Thermal stabilizer (g) Tris (2,4-di-tert-butylphenyl) phosphite: “ADEKA STAB 2112” manufactured by ADEKA Corporation
(I) Colorant (h) Carbon black: “Mitsubishi Carbon Black # 1000” manufactured by Mitsubishi Chemical Corporation

[Examples 1 to 6 and Comparative Examples 1 to 4]
(C) The raw materials other than the flame retardant ADK STAB FP700 were blended so as to have the ratio (weight ratio) shown in Table 1, and mixed for 20 minutes with a tumbler. It was introduced from the hopper of the barrel 12 block configuration). 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 (C) the flame retardant was preheated to 80 ° C. and added by a gear pump from the third block counted from the hopper side of the twin screw extruder.

[Example 7 and Comparative Example 5]
Each raw material was blended so as to have the ratio (weight ratio) shown in Table 1, mixed for 20 minutes with a tumbler, and then from a hopper of a twin screw extruder (manufactured by Nippon Steel Works, TEX30HSST, barrel 12 block configuration). I put it in. 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.

  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.

[Evaluation method]
(1) Measurement of average particle diameter A section was cut out so that the surface perpendicular to the strand direction at the center of each resin composition pellet obtained by the method described above was an end surface. From the end face of the section, an ultrathin section having the orthogonal plane as a surface was prepared using a diamond knife with an ultramicrotome (Leica, Ultracut UCT) equipped with a sample cooling device (cryo unit). The set cutting conditions are a sample chamber temperature of −105 ° C. and a sample thickness of 100 nm.
After the ultrathin sections were loaded on a copper grid, the surface of the sections were stained by exposure to osmium tetroxide vapor for 60 minutes and further to ruthenium tetroxide vapor for 60 minutes. The stained ultrathin section was observed with a transmission electron microscope (JEOL Ltd., 1200EXII type) at an acceleration voltage of 100 kV. A photograph was taken at the time of observation, and an image was recorded on an electron microscope film FG (manufactured by Fuji Photo Film Co., Ltd .: size 5.9 × 8.2 cm).
The image recorded on the negative film was digitized with a film scanner (Konica Minolta Photo Imaging, Dimage Scan Multi F-3000 type). The resulting monochrome image is a composite rubber dispersed in a matrix using Image-Pro Plus Ver.4.5.1, manufactured by Nippon Rover Co., Ltd., after adjusting the contrast using Adobe Ver.7.0. Thirty primary particle diameters (average diameters) of the system graft copolymer were measured, and the number average was taken as the number average particle diameter.

(2) Determination of Si by ICP / AES (Inductively Coupled Plasma / Atom Emission Analysis) Method Regarding the silicone / acrylic composite rubber graft copolymers (d-1) to (d-3), the sample was subjected to sulfuric acid decomposition treatment and After alkali melting treatment, Si was quantified by ICP / AES (manufactured by JOBIN YVON, ICP emission spectrophotometer Ultima 2C). Here, the ICP / AES method is obtained by applying a high voltage to a gas such as argon to turn the gas into plasma, and further generating Joule heat due to overcurrent in the plasma by a high-frequency variable magnetic field. This is an analysis method using high-temperature plasma (inductively coupled plasma: ICP). A sample is introduced into this high-temperature inductively coupled plasma, the sample is atomized and thermally excited, and the element can be identified and quantified from the emission spectrum when it returns to the ground state.

(3) Notched Charpy impact strength Pellets of each resin composition obtained by the method described above were molded at a cylinder temperature of 280 ° C or 330 ° C using an injection molding machine (SGMII Cycap manufactured by Sumitomo Heavy Industries, Ltd.). Injection molding was performed under the condition of a temperature of 80 ° C. to obtain a test piece in which the thickness of the test piece was changed to 3.0 mm in the ISO 179 standard. The notch was cut so that the notch radius was 0.25 mm and the remaining width was approximately 8.0 mm in accordance with the ISO 179 standard. The impact test was performed according to the ISO 179 standard. The Charpy impact strength is preferably higher.

(4) Flame retardancy The pellets of each resin composition obtained by the method described above were subjected to conditions of a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. using an injection molding machine (manufactured by Nippon Steel Works, J50EP). Injection molding was performed to obtain test pieces each having a length of 127 mm, a width of 12.7 mm, a wall thickness of 0.8 mm, and 1.0 mm. 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.

(5) Color development (colorability)
Visual evaluation was performed about the injection molded product produced on the same conditions as said (4) flame-retardant evaluation. Those having a high jetness of the surface appearance were marked with ○, and those with no jetness were marked with ×.

(6) Battery pack drop test The pellets of each resin composition obtained by the method described above were subjected to conditions of a cylinder temperature of 340 ° C. and a mold temperature of 80 ° C. using an injection molding machine (TR100H, manufactured by Sodick Plustech Co., Ltd.) Injection molding was performed below, and the lid and box of the battery pack 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, “not filled” was indicated.

From the results in Table 1, the following was found.
The aromatic polycarbonate resin composition of the present invention is excellent in flame retardancy and color development, and the impact resistance of the resulting thin-walled molded article is good even when it is molded at a relatively high molding temperature of 340 ° C. Thus, all of impact resistance, flame retardancy, and color development were satisfied in a well-balanced manner (Examples 1 to 7). 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.

Even if the Si content in the composite rubber-based graft copolymer is within the range of the present invention, the number average particle size is outside the range of the present invention (Comparative Example 1), or the Si content, the number average particle size. When both are outside the scope of the present invention (Comparative Example 2), as is clear from the comparison between Example 2 and Comparative Examples 1 and 2, the impact resistance of the molded article molded at high temperature is lowered, and the color developability. However, the purpose of the present application could not be achieved. In Comparative Example 1, flame retardancy was also reduced.
On the other hand, when a graft copolymer other than the composite rubber-based graft copolymer defined in the present invention is blended (Comparative Examples 3 and 4), as is clear from Comparative Examples of Example 2 and Comparative Examples 3 and 4, The impact resistance, flame retardancy and color development could not be satisfied in a well-balanced manner.

  When a flame retardant other than the phosphorus flame retardant used in the present invention is blended (Comparative Example 5), the fluidity is lowered and the resin cannot be completely filled in the battery pack mold, and the color developability is also insufficient. Met.

FIG. 1 shows a lid and a box of a battery pack manufactured in this embodiment.

The aromatic polycarbonate resin composition of the present invention has excellent fluidity capable of forming a thin-walled molded product having a flat plate portion of 0.8 mm or less in whole or in part, and has thermal stability that can withstand high-temperature molding. Therefore, the obtained molded article has good mechanical properties such as impact resistance, and has a comprehensively balanced performance of flame retardancy and color development.
Since the aromatic polycarbonate resin composition of the present invention has the above-mentioned performance, it is a small auxiliary for battery packs such as mobile phones, portable stereos, and mobile personal computers, and card-type information recording media such as memory cards and SD cards. It is suitable as a container constituting the outer portion of the storage device.

Claims (12)

(A) A vinyl polymer composed of one or more vinyl monomer units in a composite rubber containing (B) polyorganosiloxane and polyalkyl (meth) acrylate with respect to 100 parts by weight of an aromatic polycarbonate resin. Grafted silicone / acrylic composite rubber-based graft copolymer, wherein the Si content in the composite rubber graft copolymer detected by ICP / AES method is 1 wt% or more and 9 wt% or less, and 1 to 12 parts by weight of a silicone / acrylic composite rubber-based graft copolymer, wherein the graft copolymer has a number average particle diameter of 300 nm to 2000 nm , and (C) a phosphorus-based flame retardant 2 to 20 weight parts, an aromatic polycarbonate resin composition obtained by adding the (D) polyfluoroethylene 0.01 to 1.5 parts by weight, 2-screw press A kneading method using a machine as a kneading machine, including a step of kneading by setting the barrel temperature to 240 to 320 ° C., and a step of performing injection molding by setting the resin composition to a temperature of 315 to 360 ° C., A method of manufacturing a thin molded article ,
A method for producing a thin molded product , wherein 25% or more of the total area of the thin molded product is a flat plate portion having a thickness of 0.8 mm or less, and the area of the flat plate portion is 1 to 100 cm ² . Furthermore, (E) The manufacturing method of the thin molded article of Claim 1 formed by mix | blending 0.01-12 weight part with a silicate filler with respect to 100 weight part of (A) aromatic polycarbonate resin. The manufacturing method of the thin molded article of Claim 2 whose said (E) silicate filler is talc. The method for producing a thin molded article according to any one of claims 1 to 3 , wherein the polyfluoroethylene is polyfluoroethylene coated with an organic polymer. The manufacturing method of the thin molded article of Claim 4 whose polyfluoroethylene content rate in the polyfluoroethylene coat | covered with the said organic polymer is 40 to 95 weight%. The (C) 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 method for producing a thin-walled molded article according to any one of claims 1 to 5 .
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 method for producing a thin molded article according to any one of claims 1 to 6 , wherein the (C) 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 area of the flat plate part is 50 mm ² It is the above, The manufacturing method of the thin molded article of any one of Claims 1-7. The thin molded product is a resin container composed of a box and a lid for sealing the box, and the box has a flat plate portion with a thickness of 0.8 mm or less recessed by a surrounding rising piece. It is a container, The height of a rising piece is 0.5-10 mm, The thickness of a rising piece is 0.3-1.2 mm, It is any one of Claims 1-8 which is a resin container. Manufacturing method for thin molded article. The thin molded article manufactured by the manufacturing method of the thin molded article of any one of Claims 1-9. The thin molded article is an electric or electronic device housing, thin molded article according to claim 10. The thin molded article is a container constituting the outer portion of the battery pack or a small auxiliary storage device, thin molded article according to claim 10 or 11.

Images