JP5164827B2 - Thermoplastic resin composition, molded product thereof, and device casing thereof - Google Patents

Description

  The present invention relates to a thermoplastic resin composition containing a polycarbonate copolymer, an aromatic polycarbonate resin, and an amorphous styrenic resin, a molded body thereof, and an apparatus housing thereof. More specifically, a polycarbonate copolymer having a specific structural unit, an aromatic polycarbonate resin other than the polycarbonate copolymer, and a thermoplastic resin composition containing an amorphous styrenic resin, and the thermoplastic resin composition The present invention relates to a molded body and an equipment casing to be obtained.

Polycarbonate resins (hereinafter sometimes abbreviated as PC) are mainly produced from bisphenol A and are excellent in heat resistance, impact resistance, etc., and are therefore widely used in automobiles, electrical appliances / electronics fields and the like. In the fields of automobiles, electric appliances / electronics, the thickness of products has been reduced in order to reduce the weight of products, but polycarbonate resins have a problem that satisfactory molded products cannot be obtained because of low fluidity. Therefore, in order to improve the fluidity of polycarbonate resin, blends with acrylonitrile-butadiene-styrene copolymer (ABS resin) and acrylonitrile-styrene copolymer (AS resin) are the mainstream, but ABS resin is blended. As a result, not only fluidity but also impact resistance and chemical resistance can be improved. In recent years, products that have conventionally used PC / ABS blends (for example, OA, electrical equipment casings) are becoming thinner in order to reduce the weight of the products. From such a background, it is necessary to further improve the fluidity of the resin.
Moreover, the resin blend as described above often deteriorates the weld appearance of the molded product. In order to improve this, measures, such as addition of a compatibilizing agent, are taken.

In general, increasing the amount of styrene resin and decreasing the molecular weight of polycarbonate resin are effective for improving fluidity. However, an increase in the amount of styrene-based resin tends to cause a decrease in mechanical strength and flame retardancy, and there is a concern about a decrease in mechanical strength by reducing the molecular weight of the polycarbonate resin.
On the other hand, various fluidity improvers have been studied for increasing the fluidity of PC / styrene resin compositions (see, for example, Patent Documents 1 to 3). However, the above method has problems such as deterioration of the balance between mechanical strength and fluidity, and cost increase due to an increase in components.

JP 2008-115249 A JP 2007-284436 A JP 2004-162013 A

  The present invention has been made to solve the above-mentioned problems, and includes a polycarbonate resin and a styrene resin, and is excellent in fluidity, mechanical strength, flame retardancy and moldability, and has an improved weld appearance. An object of the present invention is to provide a thermoplastic resin composition, a molded body thereof, and an apparatus housing thereof.

［式中、Ｒ¹及びＲ²は、それぞれ独立に、炭素数１〜６のアルキル基を示す。Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、−Ｓ−、−ＳＯ−、−ＳＯ₂−、−Ｏ−、−ＣＯ−、下記式（ｉ）又は（ｉｉ）で示される二価基である。ａ及びｂは、それぞれ独立に、０〜４の整数であり、ａが２以上の場合、複数のＲ¹は互いに同一であっても異なっていてもよく、ｂが２以上の場合、複数のＲ²は互いに同一であっても異なっていてもよい。］

［式中、Ｒ³及びＲ⁴は、それぞれ独立に、炭素数１〜３のアルキル基を示し、Ｙは、炭素数２〜１５の直鎖状又は分岐状アルキレン基を示す。ｃ及びｄは、それぞれ独立に、０〜４の整数であり、ｃが２以上の場合、複数のＲ³は互いに同一であっても異なっていてもよく、ｄが２以上の場合、複数のＲ⁴は互いに同一であっても異なっていてもよい。ｎは２〜４５０の整数であり、複数の（Ｙ−Ｏ）は、互いに同一であっても異なっていてもよい。］
２．前記（Ｂ）成分が、アクリロニトリル−ブタジエン−スチレン共重合体、アクリロニトリル−スチレン共重合体、メタクリル酸メチル−ブタジエン−スチレン共重合体、ハイインパクトポリスチレン、及びアクリロニトリル−（エチレン／プロピレン／ジエン）−アクリル酸メチル−スチレン共重合体から選ばれる少なくとも一種以上である、上記１に記載の熱可塑性樹脂組成物、
３．前記（Ａ−１）成分、（Ａ−２）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ｃ）ゴム状弾性体を１〜５０質量部含有する上記１又は２に記載の熱可塑性樹脂組成物、
４．前記（Ａ−１）成分、（Ａ−２）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ｄ）塩素原子及び／又は臭素原子を含有しない難燃剤を０．０１〜１００質量部含有する上記１〜３のいずれかに記載の熱可塑性樹脂組成物、
５．前記（Ａ−１）成分、（Ａ−２）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ｅ）無機充填材を１〜１００質量部含有する上記１〜４のいずれかに記載の熱可塑性樹脂組成物、
６．前記（Ａ−１）成分、（Ａ−２）成分及び（Ｂ）成分の合計量１００質量部に対し、（Ｆ）ドリッピング防止剤を０．０２〜２質量部含有する上記１〜５のいずれかに記載の熱可塑性樹脂組成物、
７．前記（Ｆ）成分がポリテトラフロロエチレン(ＰＴＦＥ)である上記６に記載の熱可塑性樹脂組成物、
８．上記１〜７のいずれかに記載の熱可塑性樹脂組成物から得られる成形体、及び
９．上記１〜７のいずれかに記載の熱可塑性樹脂組成物から得られる機器筐体、
を提供する。 As a result of intensive studies to solve the above problems, the present inventor has obtained a polycarbonate copolymer having a specific amount of a specific structural unit and a viscosity number in a specific range, other than the polycarbonate copolymer. It has been found that the above problems can be solved by a thermoplastic resin composition containing an aromatic polycarbonate resin and an amorphous styrene resin in a specific ratio. The present invention has been completed based on such findings.
That is, the present invention
1. (A-1) 5 to 95% by mass of a polycarbonate copolymer, (A-2) 0 to 90% by mass of an aromatic polycarbonate resin other than the polycarbonate copolymer, and (B) 2 to 95% by mass of an amorphous styrene resin. The (A-1) polycarbonate copolymer comprises a structural unit represented by the following general formula (I) and a structural unit 1 represented by the following general formula (II): A thermoplastic resin composition characterized by having a viscosity number of 30 to 71 and (A-1) the polycarbonate copolymer,

[In formula, R < ¹ > and R < ² > shows a C1-C6 alkyl group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, or -SO. _{-, - SO 2 -, -} O -, - CO-, a divalent group represented by the following formula (i) or (ii). a and b are each independently an integer of 0 to 4, and when a is 2 or more, a plurality of R ^{1 s} may be the same or different from each other, and when b is 2 or more, R ² may be the same as or different from each other. ]

[Wherein, R ³ and R ⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are each independently an integer of 0 to 4, and when c is 2 or more, a plurality of R ^{3 s} may be the same or different from each other, and when d is 2 or more, a plurality of R ⁴ may be the same as or different from each other. n is an integer of 2 to 450, and a plurality of (YO) may be the same as or different from each other. ]
2. The component (B) is acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, high impact polystyrene, and acrylonitrile- (ethylene / propylene / diene) -acrylic. 2. The thermoplastic resin composition according to 1 above, which is at least one selected from acid methyl-styrene copolymers,
3. 3. Said 1 or 2 which contains 1-50 mass parts of (C) rubber-like elastic bodies with respect to 100 mass parts of total amounts of said (A-1) component, (A-2) component, and (B) component. Thermoplastic resin composition,
4). 0.01-100 mass of flame retardant which does not contain (D) chlorine atom and / or bromine atom with respect to 100 mass parts of total amount of said (A-1) component, (A-2) component, and (B) component. The thermoplastic resin composition according to any one of 1 to 3 above,
5. Any one of the above 1 to 4 containing 1 to 100 parts by mass of (E) inorganic filler with respect to 100 parts by mass of the total amount of component (A-1), component (A-2) and component (B). The thermoplastic resin composition according to the description,
6). 1 to 5 containing 0.02 to 2 parts by mass of (F) anti-dripping agent with respect to 100 parts by mass of the total amount of the components (A-1), (A-2) and (B). Any one of the thermoplastic resin compositions,
7). The thermoplastic resin composition according to 6 above, wherein the component (F) is polytetrafluoroethylene (PTFE),
8). 8. A molded product obtained from the thermoplastic resin composition according to any one of 1 to 7, and An equipment housing obtained from the thermoplastic resin composition according to any one of 1 to 7 above,
I will provide a.

  According to the present invention, there are provided a thermoplastic resin composition that gives a molded article having excellent fluidity, mechanical strength, flame retardancy and moldability, and improved weld appearance, its molded body, and its equipment casing. Can do.

The thermoplastic resin composition of the present invention comprises (A-1) 5 to 95% by mass of a polycarbonate copolymer, (A-2) an aromatic polycarbonate resin other than the polycarbonate copolymer (hereinafter referred to as (A-2) aroma. 0 to 90% by mass and (B) 2 to 95% by mass of amorphous styrenic resin, preferably (A-1) polycarbonate copolymer 5 to 90. % By weight, (A-2) 0 to 70% by weight of an aromatic polycarbonate resin and (B) 5 to 70% by weight of an amorphous styrenic resin, more preferably 10 to 90% by weight of a polycarbonate copolymer, (A-2) 0-60 mass% of aromatic polycarbonate resin and (B) amorphous styrenic resin 5-70 mass% are contained. When the component (A-1), the component (A-2) and the component (B) are within the above ranges, the resulting thermoplastic resin composition is excellent in fluidity, mechanical strength and flame retardancy. A molded body obtained from the thermoplastic resin composition is excellent in appearance.
The thermoplastic resin composition of the present invention comprises (C) a rubbery elastic body, (D) a chlorine atom and / or bromine in addition to the component (A-1), the component (A-2) and the component (B). A flame retardant containing no atom, (E) an inorganic filler, (F) an anti-dripping agent and the like may be included.

<(A-1) Polycarbonate copolymer>
The (A-1) polycarbonate copolymer includes a structural unit composed of a dihydric phenol residue represented by the following general formula (I) (hereinafter sometimes abbreviated as a dihydric phenol residue), and the following general copolymer. And a structural unit composed of a phenol-modified diol residue represented by the formula (II) (hereinafter sometimes abbreviated as a phenol-modified diol residue).
The (A-1) polycarbonate copolymer has 1 to 30% by mass of the phenol-modified diol residue, preferably 100 to 20% by mass, preferably 1 to 20% by mass of the phenol-modified diol residue. And 99 to 80% by mass of a dihydric phenol residue, more preferably 1 to 15% by mass of a phenol-modified diol residue and 99 to 85% by mass of a dihydric phenol residue. (A-1) In the polycarbonate copolymer, if the phenol-modified diol residue is less than 1% by mass, the resulting thermoplastic resin composition has insufficient fluidity, and if it exceeds 30% by mass, the resulting heat is obtained. The heat resistance of the plastic resin composition decreases.

[In formula, R < ¹ > and R < ² > shows a C1-C6 alkyl group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, -SO- , —SO ₂ —, —O—, —CO—, a divalent group represented by the following formula (i) or (ii). a and b are each independently an integer of 0 to 4, and when a is 2 or more, a plurality of R ^{1 s} may be the same or different from each other, and when b is 2 or more, R ² may be the same as or different from each other. ]

[Wherein, R ³ and R ⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are each independently an integer of 0 to 4, and when c is 2 or more, a plurality of R ^{3 s} may be the same or different from each other, and when d is 2 or more, a plurality of R ⁴ may be the same as or different from each other. n is an integer of 2 to 450, and a plurality of (YO) may be the same or different from each other. ]

  The (A-1) polycarbonate copolymer is a phenol-modified diol copolymer polycarbonate and can be produced by a conventional production method called an interfacial polymerization method. For example, it can be produced by a method of reacting at least a carbonate precursor such as a dihydric phenol, a phenol-modified diol and phosgene. Specifically, for example, in an inert solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, a catalyst or a branching agent is added as necessary, and at least a dihydric phenol, a phenol-modified diol and It can be produced by reacting a carbonate precursor such as phosgene.

  As said dihydric phenol, the compound represented by the following general formula (Ia) can be mentioned.

[In formula, R < ¹ > and R < ² > shows a C1-C6 alkyl group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, or -SO. _{-, - SO 2 -, -} O -, - CO-, a divalent group represented by the following formula (i) or (ii). a and b are each independently an integer of 0 to 4, and when a is 2 or more, a plurality of R ^{1 s} may be the same or different from each other, and when b is 2 or more, R ² may be the same as or different from each other. ]

In the general formulas (I) and (Ia), the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and isohexyl. Group, cyclopentyl group, cyclohexyl group and the like. a and b each represent the number of substitutions for R ¹ and R ² , and are integers from 0 to 4, preferably an integer from 0 to 2.
Specific examples of the alkylene group having 1 to 8 carbon atoms represented by X in the general formulas (I) and (Ia) include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylylene group, and a hexylene group. Specific examples of the alkylidene group having 2 to 8 carbon atoms include an ethylidene group and an isopropylidene group. Specific examples of the cycloalkylene group having 5 to 15 carbon atoms include a cyclopentylene group and a cyclohexylene group. Specific examples of the cycloalkylidene group having 5 to 15 carbon atoms include a cyclopentylidene group and a cyclohexylidene group.

  There are various dihydric phenols represented by the general formula (Ia), and 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A] is particularly preferable. Examples of bisphenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 2,2-bis (4-hydroxyphenyl) butane; (4-hydroxyphenyl) octane; 2,2-bis (4-hydroxyphenyl) phenylmethane; 2,2-bis (4-hydroxy-3-methylphenyl) propane; bis (4-hydroxyphenyl) naphthylmethane; 1 1,2-bis (4-hydroxy-t-butylphenyl) propane; 2,2-bis (4-hydroxy-3-bromophenyl) propane; 2,2-bis (4-hydroxy-3,5-tetramethylphenyl) ) Propane; 2,2-bis (4-hydroxy-3-chlorophenyl) propane; 2,2-bis (4-hydro) Bis-3,5-tetrachlorophenyl) propane; bis (hydroxyaryl) alkanes such as 2,2-bis (4-hydroxy-3,5-tetrabromophenyl) propane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane; 2,2′-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as norbornene, 4,4′-dihydroxyphenyl ether; dihydroxyaryl ethers such as 4,4′-dihydroxy-3,3′-dimethylphenyl ether, 4,4′-dihydroxy Diphenyl sulfide; 4,4′-dihydroxy-3,3′-dimethyldi Dihydroxy diaryl sulfides such as phenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide; dihydroxy diaryl sulfoxides such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide; 4,4′-dihydroxydiphenyl sulfone; Dihydroxy diaryl sulfones such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, dihydroxy diphenyls such as 4,4'-dihydroxydiphenyl, 9,9-bis (4-hydroxyphenyl) fluorene; Dihydroxydiarylfluorenes such as 9-bis (4-hydroxy-3-methylphenyl) fluorene, bis (4-hydroxyphenyl) diphenylmethane, 1,3-bis (4-hydroxyphenyl) adamantane; 2-bis (4-hydroxyphenyl) adamantane; dihydroxydiaryladamantanes such as 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, bis (4-hydroxyphenyl) diphenylmethane, 4,4′- [1,3-phenylenebis (1-methylethylidene)] bisphenol, 10,10-bis (4-hydroxyphenyl) -9-anthrone, 1,5-bis (4-hydroxyphenylthio) -2,3-di Examples include oxapentaene and α, ω-bishydroxyphenyl polydimethylsiloxane compounds. These dihydric phenols may be used alone or in combination of two or more.

  Examples of the phenol-modified diol include compounds represented by the following general formula (IIa).

［式中、Ｒ³及びＲ⁴は、それぞれ独立に、炭素数１〜３のアルキル基を示し、Ｙは、炭素数２〜１５の直鎖状又は分岐状アルキレン基を示す。ｃ及びｄは、それぞれ独立に、０〜４の整数であり、ｃが２以上の場合、複数のＲ³は互いに同一であっても異なっていてもよく、ｄが２以上の場合、複数のＲ⁴は互いに同一であっても異なっていてもよい。ｎは２〜４５０の整数であり、複数の（Ｙ−Ｏ）は、それぞれにおいて互いに同一であっても異なっていてもよい。］

[Wherein, R ³ and R ⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are each independently an integer of 0 to 4, and when c is 2 or more, a plurality of R ^{3 s} may be the same or different from each other, and when d is 2 or more, a plurality of R ⁴ may be the same as or different from each other. n is an integer of 2 to 450, and a plurality of (YO) may be the same or different from each other. ]

Specific examples of the alkyl group represented by R ³ and R ⁴ in the general formulas (II) and (IIa) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
Specific examples of the C2-C15 linear or branched alkylene group represented by Y in the general formulas (II) and (IIa) include an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, and An isopentylene group etc. are mentioned. C and d each independently represent the number of substitutions of R ³ and R ⁴ , is an integer of 0 to 4, and is preferably an integer of 0 to 2. n is preferably 2 to 200, more preferably 6 to 70.

  The phenol-modified diol represented by the general formula (IIa) is a compound derived from hydroxybenzoic acid or an alkyl ester thereof, an acid chloride and a polyether diol. The phenol-modified diol can be synthesized by the methods proposed in JP-A-62-279222, JP-A-60-79072, JP-A-2002-173465, etc. It is desirable to appropriately purify the phenol-modified diol obtained. As the purification method, for example, the system is depressurized after the reaction, and excess raw material (for example, parahydroxybenzoic acid) is distilled off. The method of doing is desirable.

Representative examples of the hydroxybenzoic acid alkyl ester include hydroxybenzoic acid methyl ester and hydroxybenzoic acid ethyl ester. Examples of the polyether diol include those represented by HO— (Y—O) _n —H, and specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Polytetramethylene glycol is particularly preferable from the viewpoints of availability and hydrophobicity. The repeating number n of the ether part of the polyether diol is an integer of 2 to 450, preferably 2 to 200, more preferably 6 to 70. When n is 2 or more, the efficiency at the time of copolymerizing the phenol-modified diol is good, and when n is 450 or less, there is an advantage that the decrease in heat resistance of the PC copolymer is small.
Representative examples of acid chlorides include those obtained from hydroxybenzoic acid and phosgene, and more specifically those obtained by the method described in Japanese Patent No. 2652707. Hydroxybenzoic acid or an alkyl ester thereof may be any of a para isomer, a meta isomer, and an ortho isomer, but the para isomer is preferable from the viewpoint of the copolymerization reaction. Ortho forms may be inferior in copolymerization reactivity due to steric hindrance to hydroxyl groups.

(A-1) In the production process of the polycarbonate copolymer, the phenol-modified diol is preferably used as a methylene chloride solution as much as possible in order to prevent its alteration and the like. When it cannot be used as a methylene chloride solution, it can be used as an alkaline aqueous solution such as NaOH.
(A-1) In the polycarbonate copolymer, if the amount of the phenol-modified diol is increased, the fluidity is improved, but the heat resistance is lowered. Therefore, the copolymerization amount of the phenol-modified diol is preferably selected according to the desired balance between fluidity and heat resistance. If the amount of phenol-modified diol copolymerization exceeds 30% by mass, as shown in JP-A-62-79222, it becomes elastomeric and may not be applicable to the same applications as general PC resins. In order to maintain heat resistance of 100 ° C. or higher, the amount of the phenol-modified diol residue contained in the polycarbonate copolymer needs to be 1 to 30% by mass, preferably 1 to 20% by mass, more preferably Is 1 to 15% by mass.

  As the molecular weight regulator, various kinds can be used as long as they are usually used for polymerization of polycarbonate resin. Specifically, as monohydric phenol, for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol M-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho position, meta position or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl); Le) fluorene; 4- (1-adamantyl) phenol and the like. Among these monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

  As the catalyst, a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, or a quaternary phosphonium salt can be preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine, dimethylaniline and the like, and examples of the tertiary amine salt include hydrochlorides and bromates of these tertiary amines. Etc. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, and tetrabutylammonium bromide. Examples thereof include butylphosphonium chloride and tetrabutylphosphonium bromide. These catalysts may be used alone or in combination of two or more. Among the above catalysts, tertiary amines are preferable, and triethylamine is particularly preferable.

  There are various kinds of the inert organic solvent. For example, dichloromethane (methylene chloride); trichloromethane; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; -Tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene, toluene, acetophenone, and the like. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.

  Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane; 4,4 ′-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl. ] Ethylidene] bisphenol; α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene; 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl]- A compound having three or more functional groups such as 4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene; phloroglysin, trimellitic acid, and isatin bis (o-cresol) can also be used.

The (A-1) polycarbonate copolymer requires a viscosity number of 30 to 71 (equivalent to Mv (viscosity average molecular weight) = 10,000 to 28,100), preferably 37 to 62 (Mv). = 13,100 to 24,100). If the viscosity number is less than 30, the mechanical properties are inferior. If the viscosity number exceeds 70, the copolymerization effect of the comonomer is not sufficiently exhibited. In addition, a large amount of comonomer is required to exhibit high fluidity, but when the viscosity number exceeds 71, the heat resistance is greatly reduced with respect to the use of the comonomer. The viscosity number is a value measured according to ISO 1628-4 (1999).
The (A-1) polycarbonate copolymer preferably has a flow value (Q value) at 280 ° C. of 30 × 10 ⁻² mL / s or more, and more preferably 40 × 10 ⁻² mL / s or more. The flow value (Q value) is a melt viscosity measured with an elevated flow tester in accordance with JIS K7210. When the flow value (Q value) is 30 × 10 ⁻² mL / s or more, (A− 1) The melt viscosity of the polycarbonate copolymer does not become too high.

<(A-2) Aromatic polycarbonate resin>
(A-2) The aromatic polycarbonate resin other than the above polycarbonate copolymer is not particularly limited as long as it is other than the above (A-1) polycarbonate copolymer, and various resins can be used. A polymer having a structural unit represented by the formula (III) is preferred.

In the general formula (III), R ⁵ and R ⁶ are each a halogen atom (for example, chlorine, fluorine, bromine, iodine) or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, An isopropyl group, various butyl groups (n-butyl group, isobutyl group, sec-butyl group, tert-butyl group), various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups).
p and q are each an integer of 0 to 4, and when p is 2 to 4, a plurality of R ⁵ may be the same or different from each other, and when q is 2 to 4, a plurality R ⁶ may be the same as or different from each other.
Z is an alkylene group having 1 to 8 carbon atoms or an alkylidene group having 2 to 8 carbon atoms (for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, ethylidene group, isopropylidene group, etc.), A cycloalkylene group having 5 to 15 carbon atoms or a cycloalkylidene group having 5 to 15 carbon atoms (for example, a cyclopentylene group, a cyclohexylene group, a cyclopentylidene group, a cyclohexylidene group), or a single bond, —SO ₂ -, -SO-, -S-, -O-, a -CO- bond, or a divalent group represented by the following formula (iii) or formula (iv).

  The polymer can be easily produced by reacting the dihydric phenol represented by the general formula (IV) with a carbonate precursor such as phosgene.

［式中、Ｒ⁵、Ｒ⁶、Ｚ、ｐ及びｑは、上記一般式（ＩＩＩ）と同じである。］

[Wherein, R ⁵ , R ⁶ , Z, p and q are the same as those in the general formula (III). ]

That is, for example, it can be produced by a reaction of a dihydric phenol and a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight regulator. It can also be produced by a transesterification reaction between a dihydric phenol and a carbonate precursor such as a carbonate compound.
Various things can be mentioned as a dihydric phenol represented by the said general formula (IV).
In particular, 2,2-bis (4-hydroxyphenyl) propane [common name, bisphenol A] is preferable.
Examples of dihydric phenols other than bisphenol A include bis (4-hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; bis (1,2-bis (4-hydroxyphenyl) ethane, etc. 4-hydroxyphenyl) alkane, 1,1-bis (4-hydroxyphenyl) cyclohexane; bis (4-hydroxyphenyl) cycloalkane such as 1,1-bis (4-hydroxyphenyl) cyclodecane, 4,4′-dihydroxy Examples include diphenyl, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone. .
In addition, hydroquinone etc. are mentioned as dihydric phenol.
These dihydric phenols may be used alone or in combination of two or more.
Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

(A-2) The aromatic polycarbonate resin may be a homopolymer using one of the above dihydric phenols, or may be a copolymer using two or more.
Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.
The polyfunctional aromatic compound is generally called a branching agent, and specifically, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4-hydroxy Phenyl) -1,3,5-triisopropylbenzene, 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl Benzene, phloroglucin, trimellitic acid, isatin bis (o-cresol) and the like.

  The (A-2) aromatic polycarbonate resin having such characteristics is commercially available as an aromatic polycarbonate resin such as Toughon A1700, A1900, A2200, and A2500 (trade name, manufactured by Idemitsu Kosan Co., Ltd.).

  Moreover, as said (A-2) aromatic polycarbonate resin, a polycarbonate-polyorganosiloxane copolymer (henceforth, PC-POS copolymer) besides the homopolymer manufactured only using said dihydric phenol. Or a polycarbonate resin containing a PC-POS copolymer, which is preferable because it improves impact resistance and flame retardancy. As the (A-2) aromatic polycarbonate resin, a PC-POS copolymer alone is more preferable.

  There are various types of PC-POS copolymers. Preferably, a polycarbonate part having a structural unit represented by the following general formula (III) and a structure represented by the following general formula (V): It consists of a polyorganosiloxane part having a structural unit.

［式中、Ｒ⁵、Ｒ⁶、Ｚ、ｐ及びｑは、上記と同じである。］

[Wherein, R ⁵ , R ⁶ , Z, p and q are the same as above. ]

［式中、Ｒ⁷、Ｒ⁸及びＲ⁹は、それぞれ独立に、水素原子、炭素数１〜５のアルキル基（例えば、メチル基、エチル基、プロピル基、ｎ−ブチル基、イソブチル基など）又はフェニル基であり、ｒ及びｓは、それぞれ０又は１以上の整数であるが、ｒとｓとの合計は１以上の整数である。］

[Wherein, R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group, etc.) Or r and s are each an integer of 0 or 1 or more, but the sum of r and s is an integer of 1 or more. ]

  Here, the polymerization degree of the polycarbonate part is preferably 3 to 100, and the polymerization degree of the polyorganosiloxane part is preferably 2 to 500.

The PC-POS copolymer is a block comprising a polycarbonate part having a structural unit represented by the general formula (III) and a polyorganosiloxane part having a structural unit represented by the general formula (V). It is a copolymer.
Such a PC-POS copolymer has, for example, a polycarbonate oligomer (hereinafter abbreviated as a PC oligomer) constituting a polycarbonate part produced in advance and a reactive group at the terminal constituting the polyorganosiloxane part. A polyorganosiloxane (for example, polydimethylsiloxane (PDMS), polydialkylsiloxane such as polydiethylsiloxane or polymethylphenylsiloxane) is dissolved in a solvent such as methylene chloride, chlorobenzene, chloroform, etc., and a sodium hydroxide aqueous solution of bisphenol And triethylamine or trimethylbenzylammonium chloride as a catalyst, and can be produced by interfacial polycondensation reaction.
Further, a PC-POS copolymer produced by the method described in Japanese Patent Publication No. 44-30105 or the method described in Japanese Patent Publication No. 45-20510 can also be used.

Here, the PC oligomer having the structural unit represented by the general formula (III) is a solvent method, that is, in the presence of a known acid acceptor or molecular weight regulator in a solvent such as methylene chloride. ) And a carbonate precursor such as phosgene or a carbonic acid ester compound can be easily produced.
For example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator, by reaction between a dihydric phenol and a carbonate precursor such as phosgene, or like a dihydric phenol and a carbonate compound. It can be produced by transesterification with a carbonate precursor.
As the carbonic acid ester compound, the same ones as described above can be used, and as the molecular weight regulator, a terminal terminator described later can be used.

In the present invention, the PC oligomer used for the production of the PC-POS copolymer may be a homo-oligomer using one of the above dihydric phenols, or a co-oligomer using two or more. Good.
Further, it may be a thermoplastic random branched carbonate oligomer obtained by using a polyfunctional aromatic compound in combination with the above dihydric phenol.

  Furthermore, as the (A-2) aromatic polycarbonate resin used in the present invention, a polycarbonate having a terminal group represented by the following general formula (VI) is also suitable.

［式中、Ｒ¹⁰は炭素数１〜３５のアルキル基を示し、ｔは０〜５の整数を示す。］

[Wherein R ¹⁰ represents an alkyl group having 1 to 35 carbon atoms, and t represents an integer of 0 to 5. ]

In the general formula (VI), R ¹⁰ is an alkyl group having 1 to 35 carbon atoms, and may be linear or branched.
The bond position of R ¹⁰ may be any of p-position, m-position and o-position, but p-position is preferred.
The polycarbonate having a terminal group represented by the general formula (VI) can be easily produced by reacting a dihydric phenol with phosgene or a carbonate compound.

For example, in a solvent such as methylene chloride, by reaction of a dihydric phenol with a carbonate precursor such as phosgene in the presence of a catalyst such as triethylamine and a specific end-stopper, or like dihydric phenol and diphenyl carbonate. It is produced by a transesterification reaction with a carbonate precursor.
Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (IV).
Further, it may be a homopolymer using one kind of the above dihydric phenol or a copolymer using two or more kinds.
Furthermore, the thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound together with the said bihydric phenol may be sufficient.

Examples of the carbonate compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
As the terminal terminator, a phenol compound in which the terminal group represented by the general formula (VI) is formed may be used. That is, it is a phenol compound represented by the following general formula (VII).

［式中、Ｒ¹⁰は炭素数１〜３５のアルキル基を示し、ｔは０〜５の整数を示す。］

[Wherein R ¹⁰ represents an alkyl group having 1 to 35 carbon atoms, and t represents an integer of 0 to 5. ]

These alkylphenols include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol, docosylphenol, tetracosylphenol, hexacosylphenol, octacosy. Examples include ruphenol, triacontylphenol, dotriacontylphenol, and tetratriacontylphenol. These may be one kind or a mixture of two or more kinds.
In addition, these alkylphenols may be used in combination with other phenolic compounds as long as the effects are not impaired.
The aromatic polycarbonate produced by the above method has a terminal group represented by the general formula (VI) at one or both ends of the molecule.

  (A-2) The viscosity average molecular weight of the aromatic polycarbonate resin is preferably 14,000 to 30,000 from the viewpoint of heat resistance and impact resistance, and more preferably from the viewpoint of balance such as mechanical properties. 15,000 to 22,000.

<(B) Amorphous styrene resin>
Specific examples of the (B) amorphous styrene resin include a rubber-modified styrene resin and / or a rubber-unmodified styrene resin. The rubber-modified styrenic resin refers to those containing a rubbery polymer in a matrix made of a vinyl aromatic polymer, and in the presence of the rubbery polymer, an aromatic vinyl monomer and, if necessary, A monomer mixture can be obtained by adding a copolymerizable vinyl monomer by a known polymerization method such as bulk polymerization, emulsion polymerization or suspension polymerization.
As the rubber-modified styrene resin and / or the rubber-unmodified styrene resin, various styrene resins can be used. In addition to the styrene monomer, acrylonitrile or methyl methacrylate is used in combination. The resulting rubber-modified styrene copolymer or rubber-unmodified styrene copolymer is preferable because the compatibility with polycarbonate is improved. Specifically, ABS resin (acrylonitrile-butadiene rubber-styrene copolymer), AES resin (acrylonitrile-ethylenepropylene rubber-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), MBS resin (Methyl methacrylate-butadiene rubber-styrene copolymer), AS resin (acrylonitrile-styrene copolymer), MS resin (methyl methacrylate-styrene copolymer), HIPS resin (high impact polystyrene), and the like. it can.

<(C) Rubber-like elastic body>
The rubber-like elastic body (C) is blended for improving impact resistance. Natural rubber, polyethylene such as low density polyethylene and high density polyethylene, polypropylene, impact modified polystyrene, polybutadiene, styrene / butadiene Copolymer, ethylene / propylene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / vinyl acetate copolymer, ethylene / glycidyl methacrylate copolymer, polyethylene terephthalate / poly (tetramethylene) Oxide) glycol block copolymers, polyester elastomers such as polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol block copolymers, butadiene-based core-shell elastomers such as MBS, Include core-shell elastomer of the acrylic, it may be used alone or in combination.
(C) The average particle diameter of the rubber-like elastic body is 100 to 500 nm, preferably 200 to 400 nm. (C) When the average particle diameter of the rubber-like elastic body is within the above range, the dispersibility is excellent and the effect of improving the impact resistance is large.

(C) As the rubber-like elastic body, a core-shell type graft rubber-like elastic body is preferably used from the viewpoint of improving impact resistance.
The core-shell type graft rubber-like elastic body has a two-layer structure composed of a core and a shell. The core portion is in a soft rubber state, the shell portion on the surface thereof is in a hard resin state, and the graft rubber-like elastic body itself is in a powder state (particle state).
This core / shell type graft rubber-like elastic material was melt blended with a resin mixture comprising (A-1) a polycarbonate copolymer, (A-2) an aromatic polycarbonate resin, and (B) an amorphous styrene resin. Even after that, the particle state remains largely in its original form, and is uniform in (A-1) polycarbonate copolymer, (A-2) aromatic polycarbonate resin and (B) amorphous styrenic resin. Dispersion eliminates appearance defects such as pearl luster and jetting.

This core-shell type graft rubber-like elastic body is, for example, the presence of one or more graft rubber-like polymers obtained from monomers mainly composed of alkyl acrylate, alkyl methacrylate, and dimethylsiloxane. Below, what is obtained by polymerizing 1 type (s) or 2 or more types of vinyl-type monomers, such as styrene, is used suitably.
As these alkyl acrylates and alkyl methacrylates, those having an alkyl group having 2 to 10 carbon atoms, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Those obtained by using methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, etc. are preferred, and in particular, methyl acrylate, ethyl acrylate, Those obtained using methyl acrylate and ethyl methacrylate are preferred.
As an elastomer obtained using a monomer mainly composed of these alkyl acrylates, an alkyl acrylate of 70% by mass or more and a vinyl monomer copolymerizable therewith, such as methyl methacrylate, acrylonitrile, A copolymer obtained by reacting vinyl acetate, styrene or the like at a ratio of 30% by mass or less is preferably used.
Further, it may be crosslinked with a polyfunctional compound such as divinylbenzene, ethylene dimethacrylate, triallyl cyanurate, triallyl isocyanurate, or the like.
In the presence of the graft rubber-like polymer, aromatic vinyl compounds such as styrene and α-methylstyrene, acrylates such as methyl acrylate and ethyl acrylate, methacrylic acid such as methyl methacrylate and ethyl methacrylate You may use what is obtained by superposing | polymerizing or copolymerizing ester.
Further, these monomers were copolymerized with other vinyl monomers, for example, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl ester compounds such as vinyl acetate and vinyl propionate, and the like. It may be a thing.
As these polymers and copolymers, those obtained by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization are used. Among them, those obtained by emulsion polymerization are particularly preferred. Used for.

Further, as a core-shell type graft rubber-like elastic body, MAS resin elasticity obtained by graft copolymerization of styrene and methyl methacrylate at a ratio of 20 to 40% by mass to 60 to 80% by mass of an n-butyl acrylate polymer. The body is used.
In addition, a composite rubber having an average particle diameter of about 0.01 to 1 μm having a structure in which a polysiloxane rubber component 5 to 95% by mass and a poly (meth) acrylate rubber component 5 to 95% by mass cannot be separated from each other. A composite rubber graft copolymer obtained by graft copolymerization of at least one vinyl monomer can also be used.
Core-shell type graft rubber-like elastic bodies having these various forms include, as commercial products, Paraloid, KM-357P (manufactured by Rohm and Haas), Metabrene W450A, Metabrene W529, Metabrene S2001, Metabrene C223, S2200 ( Mitsubishi Rayon Co., Ltd.) and Kane Ace (Kaneka Co., Ltd.).
In the present invention, a rubber-like elastic body such as a polyamide / polyether block copolymer does not have a core-shell structure, and therefore has a large shape factor on impact resistance.

(C) The amount of the rubber-like elastic material is 100 parts by mass with respect to the total amount of (A-1) polycarbonate copolymer, (A-2) aromatic polycarbonate resin and (B) amorphous styrene resin. Preferably, it is 1-50 mass parts, More preferably, it is 3-30 mass parts, More preferably, it is 4-20 mass parts.
When the blending amount is within the above range, the fluidity of the resulting thermoplastic resin composition becomes good and the impact resistance is improved.

<(D) Flame retardant containing no chlorine atom and / or bromine atom>
In the present invention, (D) a flame retardant containing no chlorine atom and / or bromine atom (hereinafter sometimes abbreviated as (D) flame retardant) may be an organic alkali metal salt, organic alkaline earth metal salt, phosphorus An acid ester compound is mentioned.
There are various kinds of organic alkali metal salts and alkaline earth metal salts, and alkali metal salts and alkaline earth metal salts of organic acids or organic acid esters having at least one carbon atom.
Here, the organic acid or the organic acid ester is an organic sulfonic acid, an organic carboxylic acid, or the like.
On the other hand, the alkali metal is sodium, potassium, lithium, cesium or the like, and the alkaline earth metal is magnesium, calcium, strontium, barium or the like.
Of these, sodium, potassium, and cesium salts are preferably used.

Among the various organic alkali metal salts and alkaline earth metal salts, for example, in the case of organic sulfonic acid, the following general formula (VIII)
(C _n F _{2n + 1} SO ₃ ) _m M (VIII)
(In the formula, n represents an integer of 1 to 10, M represents an alkaline metal such as lithium, sodium, potassium or cesium, or an alkaline earth metal such as magnesium, calcium, strontium or barium, and m represents an atom of M. The price is shown.)
An alkali metal salt or alkaline earth metal salt of perfluoroalkanesulfonic acid represented by the formula is preferably used.

In the general formula (VIII), examples of the perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptane. Examples thereof include sulfonic acid and perfluorooctane sulfonic acid.
In particular, these potassium salts are preferably used.
Other examples include diphenylsulfone-3-sulfonic acid; diphenylsulfone-3,3′-disulfonic acid; alkali metal salts and alkaline earth metal salts of organic sulfonic acids such as naphthalene trisulfonic acid and polystyrene sulfonic acid. it can.

Examples of organic carboxylic acids include perfluoroformic acid, perfluoromethanecarboxylic acid, perfluoroethanecarboxylic acid, perfluoropropanecarboxylic acid, perfluorobutanecarboxylic acid, perfluoromethylbutanecarboxylic acid, perfluorohexanecarboxylic acid, perfluoroheptanecarboxylic acid, perfluoro. Examples include octanecarboxylic acid, and alkali metal salts and alkaline earth metal salts of these organic carboxylic acids are used.
Alkali metals and alkaline earth metals are the same as described above.

  There is no restriction | limiting in particular as a phosphate ester compound, What does not contain a halogen is preferable, for example, the following general formula (IX)

(R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom or an organic group, X represents a divalent or higher organic group, p is 0 or 1, and q is 1 or higher. And r represents an integer of 0 or more.)
It is a phosphate ester compound represented by these.
In the formula (IX), the organic group may or may not be substituted with an alkyl group, a cycloalkyl group, an aryl group, or the like.
In addition, examples of the substituent when substituted include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an arylthio group.
Further, an arylalkoxyalkyl group that is a combination of these substituents, or an arylsulfonylaryl group that is a combination of these substituents bonded by an oxygen atom, nitrogen atom, sulfur atom, or the like is used as a substituent. Etc.

In the formula (IX), the divalent or higher organic group X means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above organic group.
For example, it is derived from an alkylene group, a (substituted) phenylene group, or a bisphenol that is a polynuclear phenol.
Preferred examples include bisphenol A, hydroquinone, resorcinol, dihydroxydiphenyl, dihydroxynaphthalene and the like.

The phosphate ester compound may be a monomer, oligomer, polymer, or a mixture thereof.
Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate or substitution products thereof, condensate Etc. can be illustrated.

However, among these, the compound represented by the above formula (IX) in which r is a phosphoric acid ester compound of 1 or more, or a phenyl group partially substituted with an alkyl group or the like is used at the time of molding. It may be preferable in terms of mold adhesion, heat resistance of molded products, moisture resistance, and the like.
Here, as commercially available halogen-free phosphate ester compounds, for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR-733S [resorcinol bis (diphenyl phosphate) manufactured by Daihachi Chemical Industry Co., Ltd. )], PX200 [1,3-phenylene-teslakis (2,6-dimethylphenyl) phosphate ester, PX201 [1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate ester, PX202 [4,4 '-Biphenylene-teslakis) 2,6-dimethylphenyl) phosphate ester, CR741 [bisphenol A bis (diphenyl phosphate)] and the like.

One type of the flame retardant (D) may be used, or two or more types may be used in combination.
The amount of (D) flame retardant added is preferably 100 parts by mass with respect to the total amount of (A-1) polycarbonate copolymer, (A-2) aromatic polycarbonate resin and (B) amorphous styrene resin. Is 0.01 to 100 parts by mass, and more preferably 0.05 to 50 parts by mass.
(D) When the flame retardant is an organic alkali metal salt and / or an organic alkaline earth metal salt, the amount is preferably 0.05 to 2 parts by mass, more preferably 0.05 to 1 part by mass.
(D) When a flame retardant is a phosphate ester compound, Preferably it is 2-100 mass parts, More preferably, it is 5-50 mass parts.

<(E) Inorganic filler>
The flame retardant polycarbonate resin composition of the present invention may contain (E) an inorganic filler in order to further improve the rigidity of the molded product and further the flame retardancy. (E) Specific examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, and potassium titanate fiber. Of these, plate-like talc and mica, and fibrous fillers are preferable. As the talc, magnesium hydrate silicate, which is commercially available, can be used. Moreover, the average particle diameter of (E) inorganic fillers, such as a talc, becomes like this. Preferably it is 0.1-50 micrometers, More preferably, it is 0.2-20 micrometers. By including these (E) inorganic fillers, particularly talc, in some cases, flame retardancy can be improved in addition to the rigidity improving effect.

  Here, the content of (E) inorganic filler is 100 parts by mass of the total amount of (A-1) polycarbonate copolymer, (A-2) aromatic polycarbonate resin and (B) amorphous styrene resin. On the other hand, it is preferably 1 to 100 parts by mass, and more preferably 2 to 50 parts by mass. (E) When the content of the inorganic filler is 1 part by mass or more, an effect of improving rigidity and flame retardancy is exhibited, and when it is 100 parts by mass or less, impact resistance and melt fluidity are suitable. Therefore, the content of (E) inorganic filler can be appropriately determined in consideration of the required properties and moldability of the molded product, such as the thickness of the molded product and the resin flow length.

<(F) Anti-dripping agent>
In the resin composition of the present invention, (F) an anti-dripping agent such as a polyfluoroolefin resin can be used for the purpose of preventing melt dripping during combustion in a flame retardancy test or the like. This polyfluoroolefin resin is usually a polymer and / or copolymer containing a fluoroethylene structure, such as difluoroethylene polymer, tetrafluoroethylene polymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetra It is a copolymer of fluoroethylene and fluorine-free ethylene monomer. Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000,000. As polytetrafluoroethylene that can be used in the present invention, all of the currently known types can be used.

  In addition, when polytetrafluoroethylene having a fibril forming ability is used, it is possible to impart higher melt dripping prevention property. Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned. Specific examples thereof include, for example, Teflon 6-J (Mitsui / Dupont Fluoro Chemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Kogyo Co., Ltd.), CD076 (Asahi IC Fluoropolymers Co., Ltd.) Etc.

  Other than those classified as type 3 above, for example, Algoflon F5 (manufactured by Montefluos), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. Polytetrafluoroethylene (PTFE) having the ability to form fibrils as described above, for example, tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, under a pressure of 6.9 to 690 kPa, It is obtained by polymerizing at a temperature of 0 to 200 ° C, preferably 20 to 100 ° C.

  The content of (F) anti-dripping agent is based on 100 parts by mass of the total amount of (A-1) polycarbonate copolymer, (A-2) aromatic polycarbonate resin and (B) amorphous styrene resin. The amount is preferably 0.02 to 2 parts by mass, and more preferably 0.05 to 1 part by mass. (F) If the blending amount of the anti-dripping agent is 0.02 parts by mass or more, sufficient melt dripping prevention in the intended flame retardancy is obtained, and if it is 2 parts by mass or less, flame retardancy is obtained. The appearance of the molded product is improved. Therefore, the amount of flame retardancy required for each molded product, for example, UL-94 V-0, V-1, V-2, etc. is appropriately determined in consideration of the amount of other components used. be able to.

  Next, the manufacturing method of the thermoplastic resin composition of this invention is demonstrated. The thermoplastic resin composition of the present invention includes the components (A-1), (A-2) and (B), and the components (C) to (F) used as necessary. It can be obtained by blending other additive components at an appropriate ratio in a blending ratio, and melt kneading. For the blending and kneading at this time, conventionally used equipment such as a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder or the like is used. Can be done. The heating temperature at the time of kneading is usually appropriately selected within the range of 240 to 280 ° C.

  The thermoplastic resin composition of the present invention is a hollow molding method, an injection molding method, an injection compression molding method, an extrusion molding method, a vacuum molding method, a pressure molding method, using the above melt-kneaded product or the obtained pellet as a raw material. Various molded bodies can be produced by hot bending molding, compression molding, calendar molding, rotational molding, and the like. As a molding method of the thermoplastic resin composition of the present invention, a pellet-shaped molding raw material is produced by the above melt-kneading method, and then this pellet is used to produce an injection molded body by injection molding or injection compression molding. Particularly preferred.

The thermoplastic resin composition of the present invention contains (A-1) a polycarbonate copolymer having a specific amount of a phenol-modified diol residue, so that the fluidity is excellent, and particularly the moldability in thin-wall molding becomes good. Moreover, the molded body obtained by using this has a good weld appearance and the like.
Therefore, the thermoplastic composition of the present invention is useful for equipment housings such as OA equipment, electrical equipment, and communication equipment, and is widely used in other fields such as automobile parts, building members, and home appliances.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Production Example 1 [Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate)]
Under a nitrogen atmosphere, 100 parts by mass of polytetramethylene glycol (PTMG, Mn (number average molecular weight) = 1,000) and 33.4 parts by mass of methyl p-hydroxybenzoic acid were added in the presence of 0.5 parts by mass of dibutyltin oxide. The mixture was heated at 220 ° C. and methanol was distilled off.
The reaction system was depressurized, and excess p-hydroxybenzoic acid methyl ester was distilled off. 5.0 parts by mass of the reaction product was dissolved in 30 parts by volume of methylene chloride. To this methylene chloride solution, 10 parts by volume of an 8% by mass aqueous sodium hydrogen carbonate solution was added, vigorously mixed for 20 minutes, and then the methylene chloride phase was collected by centrifugation. The methylene chloride phase was concentrated under reduced pressure to obtain polytetramethylene glycol-bis (4-hydroxybenzoate) which is a phenol-modified diol. As a result of quantifying p-hydroxybenzoic acid and methyl p-hydroxybenzoate in polytetramethylene glycol-bis (4-hydroxybenzoate) by the following method by HPLC (high performance liquid chromatography), p-hydroxybenzoic acid was obtained. Was less than 10 mass ppm, and methyl p-hydroxybenzoate was 0.2 mass%.

<Quantification of p-hydroxybenzoic acid and methyl p-hydroxybenzoate>
Quantification was performed by HPLC (high performance liquid chromatography) under the following conditions based on a calibration curve prepared with a standard product.
Column: OD Science ODS-3
Column temperature: 40 ° C
Solvent: 0.5% by mass phosphoric acid aqueous solution and acetonitrile volume ratio 1: 2 mixture Flow rate: 1.0 ml / min

Production Example 2 [Synthesis of polytetramethylene glycol-bis (4-hydroxybenzoate)]
In Production Example 1, polytetramethylene glycol (Mn = 1,000) was used in the same manner as in Production Example 1 except that polytetramethylene glycol (Mn = 2,000) was used instead of polytetramethylene glycol (Mn = 1,000). Bis (4-hydroxybenzoate) was obtained.

Production Example 3 (Production of polycarbonate copolymer)
(1) PC oligomer synthesis step To a 5.6 mass% sodium hydroxide aqueous solution, 2000 mass ppm of sodium dithionite is added to bisphenol A (BPA) to be dissolved later, and the BPA concentration is 13.5. BPA was dissolved so as to have a mass%, and an aqueous sodium hydroxide solution of BPA was prepared. A sodium hydroxide aqueous solution of BPA was continuously passed through a tubular reactor having an inner diameter of 6 mm and a pipe length of 30 m at a flow rate of 40 liter / hr and methylene chloride at a flow rate of 15 liter / hr, and phosgene at a flow rate of 4.0 kg / hr. I passed through continuously. The tubular reactor had a jacket portion, and the temperature of the reaction solution was kept at 40 ° C. or lower by passing cooling water through the jacket.
The reaction liquid sent out from the tubular reactor was continuously introduced into a baffled tank reactor having an internal volume of 40 liters equipped with a receding blade, and further a sodium hydroxide aqueous solution of BPA of 2.8 liter / hr, 25 mass% aqueous sodium hydroxide solution was supplied at a flow rate of 0.07 liter / hr, water was 17 liter / hr, and 1 mass% triethylamine aqueous solution was supplied at a flow rate of 0.64 liter / hr, and the reaction was carried out at 29-32 ° C. It was. The reaction liquid was continuously extracted from the tank reactor and allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase was collected. The polycarbonate oligomer solution thus obtained had an oligomer concentration of 329 g / liter and a chloroformate group concentration of 0.74 mol / liter.

(2) Polymerization step of PC copolymer In a tank reactor having an internal volume of 50 liters equipped with baffle plates and paddle-type stirring blades, 7.5 liters of the oligomer solution and 4.7 liters of methylene chloride were obtained in Production Example 1. 191 g of polytetramethylene glycol-bis (4-hydroxybenzoate) (MTM of PTMG chain = 1,000) and 4.4 ml of triethylamine were added, and 1389 g of a 6.4% by mass aqueous sodium hydroxide solution was added thereto with stirring. Then, the PC oligomer was reacted with polytetramethylene glycol-bis (4-hydroxybenzoate) for 10 minutes. Next, a methylene chloride solution of p-tert-butylphenol (PTBP) (95.6 g of PTBP dissolved in 0.3 liter of methylene chloride), a sodium hydroxide aqueous solution of BPA (266 g of NaOH and 0.9 g of sodium dithionite in water) A solution obtained by dissolving 443 g of BPA in an aqueous solution dissolved in 3.9 liters) was added, and a polymerization reaction was performed for 30 minutes. For dilution, 30 liters of methylene chloride was added and stirred for 10 minutes, and then the organic phase was separated into an organic phase containing a PC copolymer and an aqueous phase containing excess BPA and NaOH, and the organic phase was isolated.
The methylene chloride solution of the PC copolymer thus obtained was washed successively with 0.03 mol / liter sodium hydroxide aqueous solution and 0.2 mol / liter hydrochloric acid in an amount of 15% by volume with respect to the solution. Then, washing with pure water was repeated until the electric conductivity in the aqueous phase after washing became 0.01 μS / m or less. The methylene chloride solution of the PC copolymer obtained by washing was concentrated and ground, and the obtained flakes were dried at 100 ° C. under reduced pressure. The amount of polytetramethylene glycol-bis (4-hydroxybenzoate) residue determined by NMR was 6.4% by mass.
About the obtained PC copolymer, the viscosity number, the copolymerization amount, the glass transition temperature Tg, and the flow value (Q value) were measured by the following methods. The results are shown in Table 1.

(1) Measurement of viscosity number (VN) It was measured according to ISO 1628-4 (1999).
(2) Measurement of copolymerization amount (content) ¹ H-NMR of the copolymer was measured, and each proton (underlined part) was assigned as follows.
δ1.4-1.9: C H ₃ of _{BPA, -O-CH 2 -C H} 2 -C H 2 -CH 2 -
_{δ3.3-3.5: -O-C H 2 -CH} 2 -CH 2 -C H 2 -
δ4.3-4.4: -CO-O-C H 2 -CH 2 -CH 2 -CH 2 -
From each integrated value, after calculating the molar ratio of the phenol-modified diol residue represented by the above general formula (II) and the BPA residue represented by the above general formula (I), it was converted into mass and calculated. did. An example of the calculation is shown below.
<Calculation example>
When the integral value of δ1.4-1.9 is 858.6, the integral value of δ3.3-3.5 is 118.7, and the integral value of δ4.3-4.4 is 10.21,
Number of repetitions n = 118.7 ÷ 10.21 + 1 = 12.6
BPA = [(858.6-118.7-10.21) / 6] = 121.6
Phenol-modified diol = (10.1 / 2/4) = 2.55
The molar ratio of the BPA carbonate part is 97.9 mol% by the following calculation.
[(858.6-118.7-10.21) / 6] / {(10.1 / 2/4) + [(858.6-118.7-10.21) / 6]) × 100 = 97. 9 mol%
The molar ratio of the phenol-modified diol residue is 2.05 mol% according to the following calculation.
(10.1 / 2/4) / {(10.21 / 4) + [(858.6-118.7-10.21) / 6]} × 100 = 2.05 mol%
Therefore, the copolymerization amount [% by mass] of the phenol-modified diol residue is 8.9% by mass according to the following formula.
2.05 × (136 + 120 + 12.6 × 72 + 12 + 16) ÷ (2.05 × (136 + 120 + 12.6 × 72 + 12 + 16) + 97.9 × 254) × 100 = 8.9% by mass
(3) Measurement of glass transition temperature Tg It was measured according to ISO 11357.
(4) Flow value (Q value)
Using an elevated flow tester, the amount of molten resin (milliliter / sec) flowing out from a nozzle having a diameter of 1 mm and a length of 10 mm was measured under a pressure of 280 ° C. and 15.7 MPa according to JIS K7210. The flow value (Q value) increases with decreasing melt viscosity.

Production Example 4 (Production of polycarbonate copolymer)
In Production Example 3, instead of the polytetramethylene glycol-bis (4-hydroxybenzoate) obtained in Production Example 1 (MTM of PTMG chain = 1,000), the polytetramethylene glycol-bis obtained in Production Example 2 ( 4-hydroxybenzoate) (PCM copolymer in the same manner as in Production Example 3 except that the amount of PTMG chain Mn = 2,000) and the amount of PTBP added were changed to the amounts shown in Table 1. Got. The viscosity number, copolymerization amount, glass transition temperature Tg, and flow value (Q value) of the obtained PC copolymer were measured in the same manner as in Production Example 3. The results are shown in Table 1.

Production Example 5 (Flame retardant production)
(1) Production of PC oligomer 60 kg of bisphenol A was dissolved in 400 liters of a 5% by mass sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A.
Next, this aqueous solution of bisphenol A in sodium hydroxide maintained at room temperature at a flow rate of 138 liter / hour and methylene chloride at a flow rate of 69 liter / hour was passed through an orifice plate through a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. It was introduced, and phosgene was co-flowed into it and blown in at a flow rate of 10.7 kg / hour, and reacted continuously for 3 hours. The tubular reactor used here was a double tube, and the discharge temperature of the reaction solution was maintained at 25 ° C. through the jacket portion through cooling water. The pH of the effluent was adjusted to 10-11.
The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / liter.

(2) Production of reactive PDMS 1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% by mass sulfuric acid were mixed and stirred at room temperature for 17 hours. Thereafter, the oil phase was separated, 25 g of sodium bicarbonate was added, and the mixture was stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr (4 × 10 ² Pa) to remove low-boiling substances to obtain oil. To a mixture of 60 g 2-allylphenol and 0.0014 g platinum as platinum chloride-alcolate complex, 294 g of the oil obtained above was added at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature at 90 to 115 ° C. The product was extracted with methylene chloride and washed 3 times with 80 wt% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and heated to 115 ° C. in vacuo to remove the solvent. The obtained terminal phenol polycarbonate-polyorganosiloxane copolymer had 30 repeating dimethylsilanooxy units as measured by NMR.

(3) Production of PC-PDMS copolymer 182 g of the reactive polycarbonate-polyorganosiloxane copolymer obtained in (2) above was dissolved in 2 liters of methylene chloride, and the PC oligomer 10 obtained in (1) above. Liters were mixed. Thereto were added 26 g of sodium hydroxide dissolved in 1 liter of water and 5.7 ml of triethylamine, and the mixture was stirred and reacted at 500 rpm at room temperature for 1 hour.
After completion of the reaction, the above reaction system was added with 600 g of bisphenol A dissolved in 5 liters of a 5.2 mass% aqueous sodium hydroxide solution, 8 liters of methylene chloride and 96 g of p-tert-butylphenol, and brought to room temperature at 500 rpm. And stirred for 2 hours.
After the reaction, 5 liters of methylene chloride was added, and further washed with 5 liters of water, washed with 5 liters of 0.03 mol / liter aqueous sodium hydroxide, washed with 5 liters of 0.2 mol / liter hydrochloric acid, and washed with 5 liters of water. Two liters of water washing were sequentially performed, and finally methylene chloride was removed to obtain a flaky PC-PDMS copolymer. The obtained PC-PDMS copolymer was vacuum-dried at 120 ° C. for 24 hours. The viscosity average molecular weight was 17,000, and the PDMS content was 4.0% by mass.

The viscosity average molecular weight and PDMS content were measured as follows.
(1) Viscosity average molecular weight (Mv)
The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from the viscosity.
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83
(2) PDMS content
^It was determined based on the intensity ratio between the isopropyl methyl group peak of bisphenol A found at 1.7 ppm by ¹ H-NMR and the methyl group peak of dimethylsiloxane found at 0.2 ppm.

Examples 1-21
After drying the raw materials shown in Table 2, the components (A-1), (A-2) and (B) and the components (C) to (F) which are added as necessary are tumbled. And blended uniformly, then supplied to a vented twin screw extruder (model name: TEM35, manufactured by Toshiba Machine Co., Ltd.) and kneaded at a temperature of 280 ° C. to obtain a pellet-shaped thermoplastic resin composition. . The fluidity of the obtained pellet-shaped thermoplastic resin composition was evaluated. The results are shown in Table 2.
The obtained pellets were dried at 80 ° C. for 5 hours and then injection molded at a cylinder temperature of 260 ° C. and a mold of 40 ° C. using an injection molding machine to obtain a desired test piece. Using this test piece, the weld appearance, IZOD impact strength and flame retardancy were evaluated. The results are shown in Table 2.

The fluidity, weld appearance, IZOD impact strength and flame retardancy were evaluated as follows.
(1) Fluidity (spiral flow length / SFL)
The spiral flow length was measured at a molding temperature of 240 ° C., a mold temperature of 40 ° C., a wall thickness of 2 mm, a width of 10 mm, and an injection pressure of 125 MPa.
(2) Weld appearance Molded with a two-point gate using a tensile test piece mold, and the weld portion was visually observed. The case where the weld was almost inconspicuous was marked with ○, and the case where the weld was conspicuous was marked with ×.
(3) IZOD Impact Strength IZOD impact strength at 23 ° C. was measured in accordance with ASTM standard D-256 using a 3.2 mm (1/8 inch) thick test piece produced by an injection molding machine.
(4) Flame retardancy A combustion test was performed using a test piece having a thickness of 1.0 mm prepared according to UL standard 94. The determinations were V-0, V-1, and V-2, respectively, and others were out of specification.

Comparative Examples 1-9
Except having used the raw material shown in Table 3, it carried out similarly to Examples 1-21, and obtained the pellet-shaped resin composition.

The raw materials used in Examples 1 to 21 and Comparative Examples 1 to 9 are shown below.
(A-1) -1: Polycarbonate copolymer produced in Production Example 3 [PTMG, Mn (number average molecular weight) = 1,000]
(A-1) -2: Polycarbonate copolymer produced in Production Example 4 [PTMG, Mn (number average molecular weight) = 2,000]
(A-2): Aromatic polycarbonate resin (A2200, manufactured by Idemitsu Kosan Co., Ltd., Mv = 21,200)
(B-1): Amorphous styrene resin (acrylonitrile-styrene-butadiene copolymer, AT-05, manufactured by Nippon A & L Co., Ltd.)
(B-2): Amorphous styrene resin (acrylonitrile-styrene copolymer, 290FF, manufactured by Technopolymer Co., Ltd.)
(C): Rubber-like elastic body (Paraloid EXL2603, manufactured by Rohm and Haas)
(D-1): Flame retardant (phosphorous flame retardant, CR-741, manufactured by Daihachi Chemical Industry Co., Ltd.)
(D-2): Flame retardant produced in Production Example 5 (silicone copolymer polycarbonate, viscosity average molecular weight: 17,000, PDMS (polydimethylsiloxane) content: 4.0% by mass).
(D-3): Flame retardant (potassium perfluorobutane sulfonate, MegaFac F-114, manufactured by DIC Corporation)
(E): Inorganic filler (talc, TP-A25, manufactured by Fuji Talc Industrial Co., Ltd.)
(F): Anti-dripping agent (PTFE, AD938L, manufactured by Asahi Glass Co., Ltd.)

From Table 2, in Examples 1-21, the high fluidity PC / amorphous polystyrene type thermoplastic resin composition excellent in fluidity | liquidity and the weld appearance was obtained. This thermoplastic resin composition is superior to conventional PC / amorphous polystyrene resin compositions in terms of moldability and is useful not only for thin-wall molding, but also because of its excellent weld appearance, it has a multi-point gate appearance. It is good.
On the other hand, from Comparative Examples 1 to 9 shown in Table 3, if the amount of the copolymerized polycarbonate is not within the range of the present invention, the fluidity is low and it is not suitable for molding with a thin wall, and the weld appearance is poor. confirmed.

Claims (8)

(A-1) 5 to 95% by mass of a polycarbonate copolymer, (A-2) 0 to 90% by mass of an aromatic polycarbonate resin other than the polycarbonate copolymer, and (B) 2 to 95% by mass of an amorphous styrene resin. The (A-1) polycarbonate copolymer comprises a structural unit represented by the following general formula (I) and a structural unit 1 represented by the following general formula (II): And a viscosity number of the (A-1) polycarbonate copolymer is 30 to 71 , wherein the component (B) is , Acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, high impact polystyrene, and acrylonitrile - (ethylene / propylene / diene) - methyl acrylate - is at least one selected from styrene copolymer, a thermoplastic resin composition.

[In formula, R < ¹ > and R < ² > shows a C1-C6 alkyl group each independently. X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, -S-, or -SO. _{-, - SO 2 -, -} O -, - CO-, a divalent group represented by the following formula (i) or (ii). a and b are each independently an integer of 0 to 4, and when a is 2 or more, a plurality of R ^{1 s} may be the same or different from each other, and when b is 2 or more, R ² may be the same as or different from each other. ]

[Wherein, R ³ and R ⁴ each independently represents an alkyl group having 1 to 3 carbon atoms, and Y represents a linear or branched alkylene group having 2 to 15 carbon atoms. c and d are each independently an integer of 0 to 4, and when c is 2 or more, a plurality of R ^{3 s} may be the same or different from each other, and when d is 2 or more, a plurality of R ⁴ may be the same as or different from each other. n is an integer of 2 to 450, and a plurality of (YO) may be the same as or different from each other. ] The heat according to claim 1 , comprising 1 to 50 parts by mass of (C) a rubber-like elastic body with respect to 100 parts by mass of the total amount of the components (A-1), (A-2) and (B). Plastic resin composition. 0.01-100 mass of flame retardant which does not contain (D) chlorine atom and / or bromine atom with respect to 100 mass parts of total amount of said (A-1) component, (A-2) component, and (B) component. The thermoplastic resin composition according to claim 1 or 2 , comprising a part. Wherein component (A-1), relative to component (A-2) and (B) total 100 parts by mass of the component, any one of claims 1 to 3 containing 1 to 100 parts by mass of (E) an inorganic filler The thermoplastic resin composition described in 1. Wherein component (A-1), (A-2) component and (B) the total amount 100 parts by weight of components, according to claim 1-4, containing 0.02 to 2 parts by mass (F) dripping agent The thermoplastic resin composition according to any one of the above. The thermoplastic resin composition according to claim 5 , wherein the component (F) is polytetrafluoroethylene. The molded object obtained from the thermoplastic resin composition in any one of Claims 1-6 . The thermoplastic resin composition equipment cabinet obtained from product according to any one of claims 1-6.