WO2015001895A1

WO2015001895A1 - Thermoplastic resin composition

Info

Publication number: WO2015001895A1
Application number: PCT/JP2014/064712
Authority: WO
Inventors: 敏樹門田
Original assignee: 三菱エンジニアリングプラスチックス株式会社
Priority date: 2013-07-03
Filing date: 2014-06-03
Publication date: 2015-01-08

Abstract

　Provided is a polycarbonate/ABS resin alloy having excellent flame-retardant properties, impact resistance, and appearance, as well as excellent impact strength during high-temperature molding. A thermoplastic resin composition characterized by containing 0.01-1 part by mass of a fluoropolymer (D) and 1-3.5 parts by mass of a graft copolymer (E) in which an aromatic vinyl compound and/or a (meth)acrylic ester compound are graft polymerized with a diene rubber with respect to 100 parts by mass of a base resin comprising 60-90% by mass of a polycarbonate resin (A), 5-20 parts by mass of an ABS resin (B) comprising 40-80% by mass of an aromatic vinyl monomer component (b1), 10-30% by mass of a cyanated vinyl monomer component (b2), 10-30% by mass of a diene rubber polymer component (b3), and 0-30% by mass of another monomer component (b4), and 5-20% by mass of a phosphoric acid ester compound (C) represented by formula (1), the number-average particle diameter of the diene rubber polymer component (b3) in the ABS resin (B) being 100-350 nm, and the number-average particle diameter of the graft copolymer (E) being 100-350 nm.

Description

Thermoplastic resin composition

The present invention relates to a thermoplastic resin composition, and more particularly, to a polycarbonate / ABS resin alloy composition which is excellent in flame retardancy, impact resistance and appearance, and also excellent in impact strength at high temperature molding.

Polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical characteristics, and is widely used in, for example, automotive materials, electrical / electronic equipment materials, housing materials, and other parts manufacturing materials in industrial fields. . In particular, the flame-retardant polycarbonate / styrene resin alloy composition is suitable as a member for electric / electronic devices such as computers, notebook computers, various portable terminals, printers, copying machines, and OA / information devices. in use.

Among these, polycarbonate / styrene resin alloy compositions flame-retarded with phosphorus flame retardants are extremely excellent in moldability due to the plasticizing effect of phosphorus flame retardants. It is a general composition (see, for example, Patent Documents 1 to 4).

In order to obtain thin and large molded products in recent years, the processing temperature has to be raised in order to obtain higher moldability, and the residence time tends to be extended. Resin alloys have the problem that high impact strength cannot be maintained.

Also, in general electrical / electronic equipment casings, ribs or self-tapping bosses are provided to increase the strength of the molded product. When trying to mold such a molded product provided with ribs and bosses with the polycarbonate / styrene resin alloy as described above, a streaky appearance defect occurs in the part after passing the ribs and bosses from the gate, There is also a problem that merchandise value is significantly impaired.

Japanese Patent No. 3638806 Japanese Patent No. 4080851 Japanese Patent No. 3655979 Japanese Patent No. 4157271

The present invention was devised in view of the above problems of the prior art, and provides a thermoplastic resin composition that is excellent in flame retardancy, impact resistance and appearance, and also excellent in impact strength during high temperature molding. For the purpose.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a thermoplastic resin composition comprising a polycarbonate resin and a styrene resin contains an ABS resin having a specific dispersed particle diameter, By containing a specific amount of a flame retardant and a fluoropolymer and a specific amount of a graft copolymer having a specific dispersed particle size, the flame retardant and impact resistance are balanced, and ribs and bosses are further provided. When molding a molded article provided with a good appearance, a good appearance was obtained, and even when molded under high temperature conditions, it was found that the decrease in impact strength was small, and the present invention was completed.
The present invention provides the following thermoplastic resin composition and molded article thereof.

[1] 60 to 90% by mass of the polycarbonate resin (A);
Aromatic vinyl monomer component (b1) 40-80% by mass, vinyl cyanide monomer component (b2) 10-30% by mass, diene rubber polymer component (b3) 10-30% by mass and other Monomer component (b4) 5 to 20% by mass of ABS resin (B) composed of 0 to 30% by mass, and a base resin composed of 5 to 20% by mass of phosphoric ester compound (C) represented by the following formula (1) For 100 parts by mass
0.01 to 1 part by mass of fluoropolymer (D), 1 to 3.5 parts by mass of graft copolymer (E) obtained by graft polymerization of aromatic vinyl compound and / or (meth) acrylic acid ester compound to diene rubber Contains,
The number average particle size of the diene rubbery polymer component (b3) in the ABS resin (B) is 100 to 350 nm, and the number average particle size of the graft copolymer (E) is 100 to 350 nm. A thermoplastic resin composition characterized by the above.

(Wherein R ¹ , R ² , R ³ and R ⁴ each 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, p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group.)

[2] The thermoplastic resin composition according to the above [1], further containing 0.5 to 3 parts by mass of talc (F) having an average particle diameter of 5 to 15 μm with respect to 100 parts by mass of the base resin.
[3] The thermoplastic resin composition according to the above [1] or [2], wherein the diene rubbery polymer component (b3) in the ABS resin (B) has a number average particle size of 130 to 280 nm.
[4] The thermoplastic resin composition according to any one of the above [1] to [3], wherein the graft copolymer (E) has a number average particle size of 130 to 280 nm.
[5] The thermoplastic resin composition according to any one of the above [1] to [4], wherein the proportion of the diene rubber polymer component (b3) having a particle size of 1000 nm or more is 2% or less.
[6] The thermoplastic resin as described in any one of [1] to [5] above, wherein the mass ratio ((B) / (E)) of the ABS resin (B) to the graft copolymer (E) is 4 to 25. Resin composition.
[7] The heat according to any one of [1] to [6], wherein a mass ratio ((E) / (F)) of the graft copolymer (E) to talc (F) is 1.4 to 5. Plastic resin composition.
[8] The thermoplastic resin composition according to any one of the above [1] to [7], wherein the flame retardancy by UL94 at a thickness of 1.5 mm is 5 VA or 5 VB.
[9] The thermoplastic resin composition according to any one of the above [1] to [8], wherein the flame retardancy by UL94 at a thickness of 1.2 mm is V-0.
[10] A molded article formed by molding the thermoplastic resin composition according to any one of [1] to [9].
[11] The molded article according to [10], which is a housing of at least one OA device selected from a printer, a copier, a projector, a modem, and a router.

According to the present invention, there are provided a polycarbonate / ABS resin alloy composition excellent in flame retardancy, impact resistance and appearance, and also excellent in impact strength at high temperature molding, and a molded article comprising the same.

FIG. 1 is a top view of a flat plate-shaped body used for appearance evaluation of Examples.

Hereinafter, although an embodiment, an example thing, etc. are shown and explained in detail about the present invention, the present invention is limited to an embodiment, an example, etc. shown below and is not interpreted.
In the present specification, “˜” is used to mean that the numerical values described before and after it are used as the lower limit and the upper limit unless otherwise specified. Further, “part” means a part by mass based on the mass standard unless otherwise specified.

[Overview]
The thermoplastic resin composition of the present invention comprises polycarbonate resin (A) 60 to 90% by mass, aromatic vinyl monomer component (b1) 40 to 80% by mass, vinyl cyanide monomer component (b2) 10 to 5-20 parts by mass of ABS resin (B) comprising 30% by mass, diene rubbery polymer component (b3) 10-30% by mass and other monomer component (b4) 0-30% by mass, and the above formula With respect to 100 parts by mass of the base resin composed of 5 to 20% by mass of the phosphate ester compound (C) represented by (1),
0.01 to 1 part by mass of fluoropolymer (D), 1 to 3.5 parts by mass of graft copolymer (E) obtained by graft polymerization of aromatic vinyl compound and / or (meth) acrylic acid ester compound to diene rubber Contains,
The number average particle size of the diene rubbery polymer component (b3) in the ABS resin (B) is 100 to 350 nm, and the number average particle size of the graft copolymer (E) is 100 to 350 nm. It is characterized by.
Further, the thermoplastic resin composition of the present invention preferably contains 0.5 to 3 parts by mass of talc (F) having an average particle diameter of 5 to 15 μm with respect to 100 parts by mass of the base resin.

[Polycarbonate resin (A)]
There is no restriction | limiting in the kind of polycarbonate resin (A) used for the thermoplastic resin composition of this invention. Moreover, 1 type may be used for polycarbonate resin (A), and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The polycarbonate resin is a polymer having a basic structure having a carbonic acid bond represented by the formula: — [— O—X—O—C (═O) —] —. In the formula, X is generally a hydrocarbon group, but for imparting various properties, X introduced with a hetero atom or a hetero bond may be used.

The polycarbonate resin can be classified into an aromatic polycarbonate resin in which the carbon directly bonded to the carbonic acid bond is an aromatic carbon, and an aliphatic polycarbonate resin in which the carbon is an aliphatic carbon, either of which can be used. Of these, aromatic polycarbonate resins are preferred from the viewpoints of heat resistance, mechanical properties, electrical characteristics, and the like.

Although there is no restriction | limiting in the specific kind of polycarbonate resin (A), For example, the polycarbonate resin formed by making a dihydroxy compound and a carbonate precursor react is mentioned. At this time, in addition to the dihydroxy compound and the carbonate precursor, a polyhydroxy compound or the like may be reacted. Alternatively, a method of reacting carbon dioxide with a cyclic ether using a carbonate precursor may be used.
The polycarbonate resin (A) may be linear or branched. Furthermore, the polycarbonate resin (A) may be a homopolymer composed of one type of repeating unit or a copolymer having two or more types of repeating units. At this time, the copolymer can be selected from various copolymerization forms such as a random copolymer and a block copolymer. In general, such a polycarbonate polymer is a thermoplastic resin.

Among the monomers used as the raw material for the polycarbonate resin (A), as an example of the aromatic dihydroxy compound,
Dihydroxybenzenes such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene (ie, resorcinol), 1,4-dihydroxybenzene;
Dihydroxybiphenyls such as 2,5-dihydroxybiphenyl, 2,2′-dihydroxybiphenyl, 4,4′-dihydroxybiphenyl;
2,2′-dihydroxy-1,1′-binaphthyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1, , 7-dihydroxynaphthalene, dihydroxynaphthalene such as 2,7-dihydroxynaphthalene;

2,2'-dihydroxydiphenyl ether, 3,3'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 1,4-bis (3-hydroxyphenoxy) Dihydroxydiaryl ethers such as benzene and 1,3-bis (4-hydroxyphenoxy) benzene;

2,2-bis (4-hydroxyphenyl) propane (ie, bisphenol A),
1,1-bis (4-hydroxyphenyl) propane,
2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-methoxy-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-methoxy-4-hydroxyphenyl) propane,
1,1-bis (3-tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane,
2- (4-hydroxyphenyl) -2- (3-cyclohexyl-4-hydroxyphenyl) propane,
α, α'-bis (4-hydroxyphenyl) -1,4-diisopropylbenzene,
1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene,
Bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) cyclohexylmethane,
Bis (4-hydroxyphenyl) phenylmethane,
Bis (4-hydroxyphenyl) (4-propenylphenyl) methane,
Bis (4-hydroxyphenyl) diphenylmethane,
Bis (4-hydroxyphenyl) naphthylmethane,
1,1-bis (4-hydroxyphenyl) ethane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-naphthylethane,
1,1-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
1,1-bis (4-hydroxyphenyl) octane,
2,2-bis (4-hydroxyphenyl) octane,
1,1-bis (4-hydroxyphenyl) hexane,
2,2-bis (4-hydroxyphenyl) hexane,
4,4-bis (4-hydroxyphenyl) heptane,
2,2-bis (4-hydroxyphenyl) nonane,
1,1-bis (4-hydroxyphenyl) decane,
1,1-bis (4-hydroxyphenyl) dodecane,
Bis (hydroxyaryl) alkanes such as;

1,1-bis (4-hydroxyphenyl) cyclopentane,
1,1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,4-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,5-dimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxy-3,5-dimethylphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-propyl-5-methylcyclohexane,
1,1-bis (4-hydroxyphenyl) -3-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -4-tert-butyl-cyclohexane,
1,1-bis (4-hydroxyphenyl) -3-phenylcyclohexane,
1,1-bis (4-hydroxyphenyl) -4-phenylcyclohexane,
Bis (hydroxyaryl) cycloalkanes such as;

Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene;

Dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide;

Dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide;

Dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone;

Of these, bis (hydroxyaryl) alkanes are preferred, and bis (4-hydroxyphenyl) alkanes are preferred, and 2,2-bis (4-hydroxyphenyl) propane (ie, in terms of impact resistance and heat resistance) Bisphenol A) is preferred.
In addition, 1 type may be used for an aromatic dihydroxy compound and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of monomers used as raw materials for aliphatic polycarbonate resins include ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethylpropane-1, 3-diol, 2-methyl-2-propylpropane-1,3-diol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, decane-1,10-diol Alkanediols such as

Cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,4-diol, 1,4-cyclohexanedimethanol, 4- (2-hydroxyethyl) cyclohexanol, 2,2,4, Cycloalkanediols such as 4-tetramethyl-cyclobutane-1,3-diol;

Glycols such as ethylene glycol, 2,2'-oxydiethanol (ie, diethylene glycol), triethylene glycol, propylene glycol, spiro glycol and the like;

1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis ( 2-hydroxyethoxy) benzene, 2,3-bis (hydroxymethyl) naphthalene, 1,6-bis (hydroxyethoxy) naphthalene, 4,4′-biphenyldimethanol, 4,4′-biphenyldiethanol, 1,4- Aralkyldiols such as bis (2-hydroxyethoxy) biphenyl, bisphenol A bis (2-hydroxyethyl) ether, bisphenol S bis (2-hydroxyethyl) ether;

1,2-epoxyethane (ie ethylene oxide), 1,2-epoxypropane (ie propylene oxide), 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,4-epoxycyclohexane, 1-methyl -1,2-epoxycyclohexane, 2,3-epoxynorbornane, cyclic ethers such as 1,3-epoxypropane; and the like.

Among the monomers used as the raw material for the polycarbonate resin (A), carbonyl halides, carbonate esters and the like are used as examples of carbonate precursors. In addition, 1 type may be used for a carbonate precursor and it may use 2 or more types together by arbitrary combinations and a ratio.

Specific examples of the carbonyl halide include phosgene; haloformates such as a bischloroformate of a dihydroxy compound and a monochloroformate of a dihydroxy compound.

Specific examples of the carbonate ester include diaryl carbonates such as diphenyl carbonate and ditolyl carbonate; dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; biscarbonate bodies of dihydroxy compounds, monocarbonate bodies of dihydroxy compounds, and cyclic carbonates. And carbonate bodies of dihydroxy compounds such as

-Manufacturing method of polycarbonate resin (A) The manufacturing method of polycarbonate resin (A) is not specifically limited, Arbitrary methods are employable. Examples thereof include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer. Hereinafter, a particularly preferable one of these methods will be specifically described.

.. Interfacial polymerization method First, the case where a polycarbonate resin is produced by the interfacial polymerization method will be described. In the interfacial polymerization method, a dihydroxy compound and a carbonate precursor (preferably phosgene) are reacted in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, usually at a pH of 9 or higher. Polycarbonate resin is obtained by interfacial polymerization in the presence. In the reaction system, a molecular weight adjusting agent (terminal terminator) may be present as necessary, or an antioxidant may be present to prevent the oxidation of the dihydroxy compound.

The dihydroxy compound and the carbonate precursor are as described above. Of the carbonate precursors, phosgene is preferably used, and a method using phosgene is particularly called a phosgene method.

Examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene; It is done. In addition, 1 type may be used for an organic solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the alkali compound contained in the alkaline aqueous solution include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium hydrogen carbonate, among which sodium hydroxide and water Potassium oxide is preferred. In addition, an alkali compound may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The concentration of the alkali compound in the alkaline aqueous solution is not limited, but it is usually used at 5 to 10% by mass in order to control the pH in the alkaline aqueous solution of the reaction to 10 to 12. For example, when phosgene is blown, the molar ratio of the bisphenol compound to the alkali compound is usually 1: 1.9 or more in order to control the pH of the aqueous phase to be 10 to 12, preferably 10 to 11. Among these, it is preferable that the ratio is 1: 2.0 or more, usually 1: 3.2 or less, and more preferably 1: 2.5 or less.

Examples of the polymerization catalyst include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic rings such as N, N′-dimethylcyclohexylamine and N, N′-diethylcyclohexylamine Tertiary amines; aromatic tertiary amines such as N, N′-dimethylaniline and N, N′-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Pyridine; guanine; guanidine salt; and the like. In addition, 1 type may be used for a polymerization catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

Examples of the molecular weight regulator include aromatic phenols having a monohydric phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides and the like, among which aromatic phenols are preferred. Specific examples of such aromatic phenols include alkyl groups such as m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol. Examples thereof include substituted phenols; vinyl group-containing phenols such as isopropenyl phenol; epoxy group-containing phenols; carboxyl group-containing phenols such as o-hydroxybenzoic acid and 2-methyl-6-hydroxyphenylacetic acid; In addition, a molecular weight regulator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The amount used of the molecular weight regulator is usually 0.5 mol or more, preferably 1 mol or more, and usually 50 mol or less, preferably 30 mol or less, per 100 mol of the dihydroxy compound. By making the usage-amount of a molecular weight modifier into this range, the thermal stability and hydrolysis resistance of a thermoplastic resin composition can be improved.

In the reaction, the order of mixing the reaction substrate, reaction medium, catalyst, additive and the like is arbitrary as long as a desired polycarbonate resin is obtained, and an appropriate order may be arbitrarily set. For example, when phosgene is used as the carbonate precursor, the molecular weight regulator can be mixed at any time as long as it is between the reaction (phosgenation) of the dihydroxy compound and phosgene and the start of the polymerization reaction.
The reaction temperature is usually 0 to 40 ° C., and the reaction time is usually several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

-Melt transesterification method Next, the case where a polycarbonate resin is manufactured by the melt transesterification method is demonstrated. In the melt transesterification method, for example, a transesterification reaction between a carbonic acid diester and a dihydroxy compound is performed.

The dihydroxy compound is as described above.
On the other hand, examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, and di-tert-butyl carbonate; diphenyl carbonate; substituted diphenyl carbonate such as ditolyl carbonate, and the like. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable, and diphenyl carbonate is more preferable. In addition, 1 type may be used for carbonic acid diester, and it may use 2 or more types together by arbitrary combinations and a ratio.

The ratio of the dihydroxy compound and the carbonic acid diester is arbitrary as long as the desired polycarbonate resin can be obtained, but it is preferable to use an equimolar amount or more of the carbonic acid diester with respect to 1 mol of the dihydroxy compound. Is more preferable. The upper limit is usually 1.30 mol or less. By setting it as such a range, the amount of terminal hydroxyl groups can be adjusted to a suitable range.

In polycarbonate resins, the amount of terminal hydroxyl groups tends to have a large effect on thermal stability, hydrolysis stability, color tone, and the like. For this reason, you may adjust the amount of terminal hydroxyl groups as needed by a well-known arbitrary method. In the transesterification reaction, a polycarbonate resin in which the amount of terminal hydroxyl groups is adjusted can be usually obtained by adjusting the mixing ratio of the carbonic diester and the aromatic dihydroxy compound; the degree of vacuum during the transesterification reaction, and the like. In addition, the molecular weight of the polycarbonate resin usually obtained can also be adjusted by this operation.

When adjusting the amount of terminal hydroxyl groups by adjusting the mixing ratio of the carbonic acid diester and the dihydroxy compound, the mixing ratio is as described above.
Further, as a more aggressive adjustment method, there may be mentioned a method in which a terminal terminator is mixed separately during the reaction. Examples of the terminal terminator at this time include monohydric phenols, monovalent carboxylic acids, carbonic acid diesters, and the like. In addition, 1 type may be used for a terminal terminator and it may use 2 or more types together by arbitrary combinations and a ratio.

When a polycarbonate resin is produced by the melt transesterification method, a transesterification catalyst is usually used. Any transesterification catalyst can be used. Among them, it is preferable to use, for example, an alkali metal compound and / or an alkaline earth metal compound. In addition, auxiliary compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. In addition, 1 type may be used for a transesterification catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

In the melt transesterification method, the reaction temperature is usually 100 to 320 ° C. The pressure during the reaction is usually a reduced pressure condition of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be performed under the above-mentioned conditions while removing a by-product such as an aromatic hydroxy compound.

The melt polycondensation reaction can be performed by either a batch method or a continuous method. When performing by a batch type, the order which mixes a reaction substrate, a reaction medium, a catalyst, an additive, etc. is arbitrary as long as a desired aromatic polycarbonate resin is obtained, What is necessary is just to set an appropriate order arbitrarily. However, among them, the melt polycondensation reaction is preferably carried out continuously in consideration of the stability of the polycarbonate resin and the thermoplastic resin composition.

In the melt transesterification method, a catalyst deactivator may be used as necessary. As the catalyst deactivator, a compound that neutralizes the transesterification catalyst can be arbitrarily used. Examples thereof include sulfur-containing acidic compounds and derivatives thereof. In addition, a catalyst deactivator may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The amount of the catalyst deactivator used is usually 0.5 equivalents or more, preferably 1 equivalent or more, and usually 10 equivalents or less, relative to the alkali metal or alkaline earth metal contained in the transesterification catalyst. Preferably it is 5 equivalents or less. Furthermore, it is 1 ppm or more normally with respect to aromatic polycarbonate resin, and is 100 ppm or less normally, Preferably it is 20 ppm or less.

-Other matters regarding the polycarbonate resin (A) The molecular weight of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but the viscosity average molecular weight [Mv] converted from the solution viscosity is usually 10,000 or more. , Preferably 16,000 or more, more preferably 17,000 or more, and usually 40,000 or less, preferably 30,000 or less, more preferably 24,000 or less. By making the viscosity average molecular weight equal to or higher than the lower limit of the above range, the mechanical strength of the thermoplastic resin composition of the present invention can be further improved, which is more preferable when used for applications requiring high mechanical strength. . On the other hand, by making the viscosity average molecular weight not more than the upper limit of the above range, it is possible to suppress and improve the fluidity drop of the thermoplastic resin composition of the present invention, and to improve the molding processability and to facilitate the molding process. . Two or more types of polycarbonate resins having different viscosity average molecular weights may be mixed and used, and in this case, a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed.

The viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ Mv ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

The terminal hydroxyl group concentration of the polycarbonate resin (A) is arbitrary and may be appropriately selected and determined, but is usually 1,000 ppm or less, preferably 800 ppm or less, more preferably 600 ppm or less. Thereby, the residence heat stability and color tone of the thermoplastic resin composition of this invention can be improved more. In addition, the lower limit is usually 10 ppm or more, preferably 30 ppm or more, more preferably 40 ppm or more, particularly for polycarbonate resins produced by the melt transesterification method. Thereby, the fall of molecular weight can be suppressed and the mechanical characteristic of the thermoplastic resin composition of this invention can be improved more.

In addition, the unit of the terminal hydroxyl group concentration represents the mass of the terminal hydroxyl group with respect to the mass of the polycarbonate resin in ppm. The measuring method is a colorimetric determination by the titanium tetrachloride / acetic acid method (method described in Macromol. Chem. 88 215 (1965)).

The polycarbonate resin (A) is not limited to an embodiment including only one type of polycarbonate resin, and includes an embodiment including a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. It may be used in the sense) or may be used in combination with an alloy (mixture) of a polycarbonate resin and another thermoplastic resin. Further, for example, for the purpose of further improving flame retardancy and impact resistance, a polycarbonate resin is copolymerized with an oligomer or polymer having a siloxane structure; for the purpose of further improving thermal oxidation stability and flame retardancy A monomer, oligomer or polymer having a copolymer; a monomer, oligomer or polymer having a dihydroxyanthraquinone structure for the purpose of improving thermal oxidation stability; A copolymer with an oligomer or polymer having an olefin structure; a copolymer with a polyester resin oligomer or polymer for the purpose of improving chemical resistance; Good.

Further, in order to improve the appearance and fluidity of the molded product, the polycarbonate resin (A) may contain a polycarbonate oligomer. The viscosity average molecular weight [Mv] of this polycarbonate oligomer is usually 1,500 or more, preferably 2,000 or more, and usually 9,500 or less, preferably 9,000 or less. Furthermore, the polycarbonate ligomer contained is preferably 30% by mass or less of the polycarbonate resin (including the polycarbonate oligomer).

Further, the polycarbonate resin (A) may be not only a virgin raw material but also a polycarbonate resin regenerated from a used product (so-called material-recycled polycarbonate resin). Examples of the used products include: optical recording media such as optical disks; light guide plates; vehicle window glass, vehicle headlamp lenses, windshields and other vehicle transparent members; water bottles and other containers; eyeglass lenses; Examples include architectural members such as glass windows and corrugated sheets. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.
However, the recycled polycarbonate resin is preferably 80% by mass or less, more preferably 50% by mass or less, among the polycarbonate resins contained in the thermoplastic resin composition of the present invention. Recycled polycarbonate resin is likely to have undergone deterioration such as heat deterioration and aging deterioration, so when such polycarbonate resin is used more than the above range, hue and mechanical properties can be reduced. It is because there is sex.

[ABS resin (B)]
The ABS resin (B) contained in the thermoplastic resin composition of the present invention comprises an aromatic vinyl monomer component (b1) of 40 to 80% by mass, a vinyl cyanide monomer component (b2) of 10 to 30% by mass, This is an ABS resin (B) comprising 10 to 30% by mass of the diene rubbery polymer component (b3) and 0 to 30% by mass of the other monomer component (b4).

As the aromatic vinyl monomer component (b1) in the ABS resin (B), styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butyl Styrene, vinyl naphthalene, methoxy styrene, monobromo styrene, dibromo styrene, fluoro styrene, tribromo styrene and the like can be mentioned, and styrene is particularly preferable.
The ratio of the aromatic vinyl monomer component (b1) in the ABS resin (B) is in the range of 40 to 80% by mass, preferably 45% by mass or more, more preferably in 100% by mass of the ABS resin (B). Is 50% by mass or more, more preferably 55% by mass or more, preferably 75% by mass or less, more preferably 70% by mass or less, and further preferably 65% by mass or less.

Examples of the vinyl cyanide monomer component (b2) in the ABS resin (B) include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.
The proportion of the vinyl cyanide monomer component (b2) in the ABS resin (B) is in the range of 10 to 30% by mass, preferably 12% by mass or more, more preferably 100% by mass of the ABS resin (B). Is 14% by mass or more, more preferably 15% by mass or more, preferably 28% by mass or less, more preferably 26% by mass or less, and further preferably 25% by mass or less.

As the diene rubbery polymer component (b3) of the ABS resin (B), for example, rubber components such as polybutadiene, polyisoprene, styrene-butadiene copolymer are used, and the diene rubbery polymer component (b3). The ratio in the ABS resin (B) is in the range of 10 to 30% by mass, preferably 13% by mass or more, more preferably 14% by mass or more, and still more preferably 15% in 100% by mass of the ABS resin (B). It is at least mass%, preferably at most 28 mass%, more preferably at most 26 mass%.

Further, it may be a copolymer of other monomer component (b4) copolymerizable therewith. In this case, examples of other copolymerizable vinyl monomers include maleimide, N-methylmaleimide, N- Maleimide monomers such as cyclohexylmaleimide and N-phenylmaleimide, acrylamide monomers such as acrylamide and N-methylacrylamide, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated acids such as acrylic acid and methacrylic acid Glycidyl acrylate, glycidyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methoxypolyethylene glycol methacrylate, and the like.
The proportion of the other monomer component (b4) in the ABS resin (B) is in the range of 0 to 30% by mass, preferably 20% by mass or less, more preferably 100% by mass of the ABS resin (B). It is 10 mass% or less.

Specific examples of the ABS resin (B) are preferably acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene-N-phenylmaleimide copolymer, and the like. Illustrated.

The ABS resin (B) contained in the thermoplastic resin composition of the present invention is characterized in that the number average particle size of the diene rubbery polymer component (b3) in the ABS resin (B) is 100 to 350 nm. And Thus, it has been found that the thermoplastic resin composition of the present invention is excellent in impact resistance and solves the above-mentioned problem that a streaky appearance defect occurs in the portion after passing through the rib or boss from the gate. .
Here, the number average particle diameter of the diene rubber polymer component (b3) in the ABS resin (B) is measured by a scanning electron microscope (SEM). Specifically, the thermoplastic resin composition (pellet) of the present invention is 300 from an image observed at an applied voltage of 2.0 kV and a magnification of 10,000 using a scanning electron microscope “SU8020” manufactured by Hitachi High-Technology Corporation. It is defined as the number average particle size of the individual particles.
The number average particle diameter of the diene rubbery polymer component (b3) in the ABS resin (B) is preferably 130 to 280 nm. Further, in the ABS resin (B), the proportion of the diene rubbery polymer component (b3) having a particle size of 1000 nm or more is preferably 2% or less.

The ABS resin is usually produced by a method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and any method can be used. In the present invention, it is preferable to use an ABS resin produced by reducing the particle size of the diene rubbery polymer component (b3) by emulsion polymerization.
In addition, such ABS resin (B) can be appropriately selected from commercially available ones.

In the present invention, the ABS resin is not limited to an embodiment including only one type of ABS resin, and may include, for example, an embodiment including a combination of a plurality of types of ABS resins having different monomer compositions and molecular weights. You may combine other resin, such as resin.
When combining in this way, what was obtained by melt-kneading in advance may be used when producing the thermoplastic resin composition of the present invention, or may be used collectively when producing the resin composition of the present invention.
When combined as described above, the ABS resin in the resulting thermoplastic resin composition contains 40 to 80% by mass of the aromatic vinyl monomer component (b1) and 10 to 30 vinyl cyanide monomer component (b2). It is sufficient to satisfy the ranges of mass%, diene rubbery polymer component (b3) 10 to 30 mass%, and other monomer component (b4) 0 to 30 mass%.

[Phosphate ester compound (C)]
The thermoplastic resin composition of the present invention contains a phosphate ester compound (C) represented by the following formula (1).

(In the formula (1), R ¹ , R ² , R ³ and R ⁴ each 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. , P, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X ¹ represents an arylene group.)

The phosphate ester compound represented by the above formula (1) may be a mixture of compounds having different numbers of k. In the case of such a mixture of condensed phosphate esters having different k, k is a value of the mixture. Average value. k is usually an integer of 0 to 5, and in the case of a mixture of compounds having different k numbers, the average k number is preferably 0.5 to 2, more preferably 0.6 to 1.5, and even more preferably Is in the range of 0.8 to 1.2, particularly preferably 0.95 to 1.15.

X ¹ represents a divalent arylene group such as resorcinol, hydroquinone, bisphenol A, 2,2′-dihydroxybiphenyl, 2,3′-dihydroxybiphenyl, 2,4′-dihydroxybiphenyl, 3,3 ′. -Dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxybiphenyl, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1, Divalent derivatives derived from dihydroxy compounds such as 6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene It is a group. Of these, divalent groups derived from resorcinol, bisphenol A, and 3,3′-dihydroxybiphenyl are particularly preferable.

Further, p, q, r and s in the formula (1) each represent 0 or 1, and preferably 1 in particular.

R ¹ , R ² , R ³ and R ⁴ each 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. Examples of such aryl groups include phenyl group, cresyl group, xylyl group, isopropylphenyl group, butylphenyl group, tert-butylphenyl group, di-tert-butylphenyl group, p-cumylphenyl group, and the like. Group, cresyl group and xylyl group are more preferred.

As a specific example of the phosphate ester compound represented by the formula (1),
Triphenyl phosphate (TPP), tricresyl phosphate (TCP), trixylenyl phosphate (TXP), cresyl diphenyl phosphate (CDP), 2-ethylhexyl diphenyl phosphate (EHDP), tert-butylphenyl diphenyl phosphate, bis- ( aromatic phosphates such as tert-butylphenyl) phenyl phosphate, tris- (tert-butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate;
Condensed phosphate esters such as resorcinol bis-diphenyl phosphate (RDP), resorcinol bis-dixylenyl phosphate (RDX), bisphenol A bis-diphenyl phosphate (BDP), biphenyl bis-diphenyl phosphate;
Etc.

The acid value of the phosphate ester compound represented by the formula (1) is preferably 0.2 mgKOH / g or less, more preferably 0.15 mgKOH / g or less, still more preferably 0.1 mgKOH / g or less, Especially preferably, it is 0.05 mgKOH / g or less. The lower limit of the acid value can be substantially zero. On the other hand, the content of the half ester is more preferably 1.1 parts by mass or less, and still more preferably 0.9 parts by mass or less. When the acid value exceeds 0.2 mgKOH / g or the half ester content exceeds 1.5 mg, the thermoplastic resin composition of the present invention tends to be deteriorated in thermal stability and hydrolysis resistance.

[Content Ratio of Polycarbonate Resin (A), ABS Resin (B), and Phosphate Ester Compound (C)]
In the thermoplastic resin composition of the present invention, the content ratio of the polycarbonate resin (A), the ABS resin (B), and the phosphate ester compound (C) is the polycarbonate resin (A), the ABS resin (B), and the phosphate ester compound. Based on the total of 100 mass% of (C), the polycarbonate resin (A) is 60 to 90 mass%, the ABS resin (B) is 5 to 20 mass parts, and the phosphoric ester compound (C) is 5 to 20 mass%. .
If the polycarbonate resin (A) exceeds the above range and the ABS resin (B) is too small, the molding processability of the thermoplastic resin composition is lowered, and the polycarbonate resin (A) is less than 60% by mass and the ABS resin (B). When there is too much, mechanical strength of a thermoplastic resin composition, heat resistance, a flame retardance, etc. will be inferior.
The preferred content ratio of the polycarbonate resin (A) is 63% by mass or more, more preferably 65% by mass or more, 85% by mass or less, more preferably 80% by mass or less, and the ABS resin (B) is preferably 8% by mass. It is at least 10 mass%, more preferably at least 10 mass%, preferably at most 19 mass%, more preferably at most 18 mass%.

The content of the phosphate ester compound (C) is 5 to 20% by mass, preferably 8% by mass or more, more preferably 10% by mass or more, preferably 19% by mass or less, more preferably It is 18 mass% or less, More preferably, it is 17 mass% or less. When the content of the phosphate ester compound (C) is less than 5% by mass, the flame retardancy is insufficient, and when it exceeds 20% by mass, the heat resistance and mechanical properties are significantly decreased.

[Fluoropolymer (D)]
The thermoplastic resin composition of the present invention comprises 0.01 to 1 mass of fluoropolymer (D) with respect to a total of 100 mass parts of polycarbonate resin (A), ABS resin (B) and phosphoric ester compound (C). Contains. One type of fluoropolymer (D) may be used, or two or more types may be used in any combination and in any ratio.

Examples of the fluoropolymer (D) include a fluoroolefin resin. The fluoroolefin resin is usually a polymer or copolymer containing a fluoroethylene structure. Specific examples include difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer resin, and the like. Of these, tetrafluoroethylene resin and the like are preferable. Examples of the fluoroethylene resin include a fluoroethylene resin having a fibril forming ability.

Examples of the fluoroethylene resin having a fibril forming ability include “Teflon (registered trademark) 6J”, “Teflon (registered trademark) 640J” manufactured by Mitsui DuPont Fluorochemical Co., Ltd. ”,“ Polyflon FA500B ”,“ Polyflon FA500H ”and the like. Furthermore, examples of commercially available aqueous dispersions of fluoroethylene resin include “Teflon (registered trademark) 31-JR” manufactured by Mitsui DuPont Fluoro Chemical Co., “Fluon D-210C” manufactured by Daikin Industries, Ltd. Furthermore, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used. Examples of such a fluoroethylene polymer include polystyrene-fluoroethylene composites, polystyrene-acrylonitrile-fluoroethylene. Examples include composites, polymethyl methacrylate-fluoroethylene composites, polybutyl methacrylate-fluoroethylene composites, etc. Specific examples include “Metablene A-3800” manufactured by Mitsubishi Rayon Co., Ltd. and “Blendex” manufactured by GE Specialty Chemical Co., Ltd. 449 "and the like. In addition, 1 type may contain the dripping inhibitor and 2 or more types may contain it by arbitrary combinations and a ratio.

The fluoropolymer (D) in the present invention preferably has a standard specific gravity value of 2.15 to 2.22. When the standard specific gravity is less than 2.15, the appearance of the molded product tends to deteriorate, which is not preferable. On the other hand, when the standard specific gravity exceeds 2.22, the drip resistance tends to decrease, such being undesirable. The standard specific gravity value is preferably 2.155 to 2.215, more preferably 2.16 to 2.1, particularly preferably 2.16 to 2.20, and 2.165. Most preferred is ˜2.19. The standard specific gravity (also referred to as SSG) is a value measured by a water displacement method using a sample molded according to ASTM D4895.

The average particle size of the fluoropolymer (D) in the present invention is not particularly limited, but is preferably 300 to 1,000 μm. If the average particle size is less than 300 μm, the drip resistance of the thermoplastic resin composition of the present invention may be reduced, and if it exceeds 1,000 μm, the fluoropolymer tends to aggregate, In such a case, the appearance defect such as white spot foreign matter may be caused, which is not preferable. From such a viewpoint, the average particle size of the fluoropolymer is more preferably 350 to 800 μm, still more preferably 380 to 750 μm, and particularly preferably 400 to 700 μm.

As described above, the content of the fluoropolymer (D) is 0.01 parts by mass or more with respect to a total of 100 parts by mass of the polycarbonate resin (A), the ABS resin (B), and the phosphate ester compound (C). , Preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, particularly preferably 0.1 parts by weight or more, and 1 part by weight or less, preferably 0.8 parts by weight or less, More preferably, it is 0.7 mass part or less. When the content of the fluoropolymer (D) is less than 0.01 parts by mass of the above range, the flame retardancy effect due to the anti-dripping agent becomes insufficient, and when the content exceeds 1 part by mass, the thermoplastic resin Deterioration in appearance and mechanical strength of the molded product obtained by molding the composition are likely to occur.

[Graft Copolymer (E)]
The thermoplastic resin composition of the present invention contains a graft copolymer (E) obtained by graft polymerization of an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to a diene rubber.

Specific examples of the diene rubber constituting the graft copolymer (E) include polybutadiene rubber, polyisoprene rubber, butadiene-acrylic composite rubber, and styrene-butadiene rubber. These may be used alone or in admixture of two or more.
Among these, polybutadiene rubber and styrene-butadiene rubber are preferable from the viewpoint of mechanical properties and surface appearance.

The diene rubber is graft polymerized with an aromatic vinyl compound and / or a (meth) acrylic ester compound.
Examples of the (meth) acrylic acid ester compound to be graft-polymerized include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth ) Preferable examples include phenyl acrylate.
A (meth) acrylic acid ester compound may be used individually by 1 type, or may mix and use 2 or more types.

The aromatic vinyl compound to be graft-polymerized is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring, but preferably does not have a substituent such as a functional group. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene, etc. Is mentioned. Of these, styrene and α-methylstyrene are preferred, and styrene is particularly preferred.
Aromatic vinyl compounds can be used alone or in combination of two or more, and (meth) acrylic acid ester compounds can also be used in combination.

Furthermore, other graft copolymerizable monomers other than aromatic vinyl compounds and (meth) acrylic acid ester compounds can also be used in combination. Specific examples of such monomers include vinyl cyanide compounds, (Meth) acrylic acid compounds, epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, phthalic acid, itaconic acid, etc. And α, β-unsaturated carboxylic acid compounds and anhydrides thereof (eg, maleic anhydride). These monomer components may be used alone or in combination of two or more.
The graft copolymer (E) is different from the ABS resin (B) described above.

The graft copolymer (E) obtained by graft polymerizing an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to a diene rubber is a core / shell type graft copolymer in terms of impact resistance and surface appearance. The type is preferred. Among them, a core / shell type graft copolymer comprising a shell layer formed by graft copolymerization of an aromatic vinyl compound and / or a (meth) acrylic acid ester compound around a diene rubber as a core layer is provided. Particularly preferred.
In such a core / shell type graft copolymer, the rubber component is preferably contained in an amount of 40% by mass or more, more preferably 60% by mass or more. Moreover, what contains 10 mass% or more of an aromatic vinyl compound and (meth) acrylic acid is preferable.

Preferred examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer. Examples thereof include a polymer (MB), a methyl methacrylate-acrylic / butadiene rubber copolymer, and a methyl methacrylate-acrylic / butadiene rubber-styrene copolymer. Such rubbery polymers may be used alone or in combination of two or more.

Examples of the method for producing a graft copolymer (E) obtained by graft polymerization of an aromatic vinyl compound and / or a (meth) acrylic acid ester compound to a diene rubber include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Any of the manufacturing methods may be used.
The copolymerization method may be single-stage or multistage grafting, but multistage graft copolymerization is preferred.

The graft copolymer (E) contained in the thermoplastic resin composition of the present invention is characterized in that the number average particle diameter is 100 to 350 nm. A thermoplastic resin composition containing such a graft copolymer having no number average particle diameter tends to cause streak-like appearance defects in the portion after passing through the ribs and bosses from the gate described above.
Here, the number average particle diameter of the graft copolymer (E) is measured by a scanning electron microscope (SEM). Specifically, the thermoplastic resin composition (pellet) of the present invention is manufactured by Hitachi High-Technology Corporation. It is defined as the number average particle diameter of 300 particles from an image observed using a scanning electron microscope “SU8020” at an applied voltage of 2.0 kV and a magnification of 10,000 times.
The number average particle size of the graft copolymer (E) is preferably 130 to 280 nm, and more preferably 150 to 250 nm.

As the graft copolymer (E), it is preferable to use a graft copolymer produced by reducing the particle diameter by emulsion polymerization.
In addition, such a graft copolymer (E) can also be suitably selected from what is marketed, and can also be used.
In the present invention, the graft copolymer (E) is not limited to an embodiment including only one type, and may include, for example, a combination of a plurality of types of graft copolymers (E) having different monomer compositions and molecular weights. .

By containing the phosphate ester compound (C) and the fluoropolymer (D), and further the graft copolymer (E) in the polycarbonate resin and the ABS resin in amounts specified in the present invention, flame retardancy, A polycarbonate / ABS resin alloy having excellent impact properties and appearance, and also excellent impact strength during high-temperature molding can be achieved.

The content of the graft copolymer (E) is 1 to 3.5 parts by mass with respect to 100 parts by mass in total of the polycarbonate resin (A), the ABS resin (B) and the phosphate ester compound (C). When the content is less than 1 part by mass, the impact resistance improvement effect becomes insufficient. When the content exceeds 3.5 parts by mass, the appearance, heat resistance, and flame retardancy of the molded product obtained by molding the thermoplastic resin composition are insufficient. Decrease. The content is preferably 1.5 parts by mass or more, more preferably 1.8 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A), the ABS resin (B) and the phosphate ester compound (C). Moreover, it is preferably 3.4 parts by mass or less, more preferably 3.3 parts by mass or less.

The mass ratio ((B) / (E)) of the ABS resin (B) to the graft copolymer (E) is preferably in the range of 4-25. When the mass ratio ((B) / (E)) is in such a range, the synergistic effect that the dispersibility of the ABS resin (B) and the graft copolymer (E) in the polycarbonate resin (A) is improved. And can improve impact resistance and appearance defects. For example, when considering improvement in impact resistance, it can be realized by increasing only the graft copolymer (E), but the mass ratio ((B) / (E)) is out of this range and less than 4. In such a case, the effect of improving the impact resistance with respect to the increased amount of the graft copolymer (E) is reduced. On the other hand, undesirable phenomena such as poor appearance and reduced heat resistance and flame resistance are increased. Further, even when the mass ratio ((B) / (E)) is larger than 25, a sufficient improvement in impact resistance cannot be expected. The mass ratio ((B) / (E)) is more preferably 4.5 or more, more preferably 20 or less, and still more preferably 15 or less.

[Talc (F)]
The thermoplastic resin composition of the present invention preferably contains talc (F) having an average particle diameter of 5 to 15 μm. When the average particle size of talc (F) is less than 5 μm, the flame retardancy tends to deteriorate, and when the average particle size exceeds 15 μm, the impact resistance of the molded product tends to be lowered. Such talc (F) can be selected from commercially available talc. The average particle size of talc (F) is more preferably 6 μm or more, further preferably 7 μm or more, and particularly preferably 14 μm or less.
Here, the average particle size of talc (F) refers to D ₅₀ measured by particle size distribution by laser diffraction. As an apparatus capable of such measurement, there can be mentioned a “SALD-200V ER” type laser diffraction particle size distribution measuring apparatus manufactured by Shimadzu Corporation.

When talc (F) is contained, the preferable content of talc (F) in the thermoplastic resin composition is 100 parts by mass in total of the polycarbonate resin (A), the ABS resin (B), and the phosphate ester compound (C). Is 0.5 to 3 parts by mass. When the content is less than 0.5 parts by mass, the flame retardancy tends to be insufficient, and when it exceeds 3 parts by mass, the impact resistance is likely to decrease.
The content of talc (F) is more preferably 0.6 parts by mass or more, more preferably 100 parts by mass in total of the polycarbonate resin (A), the ABS resin (B), and the phosphate ester compound (C). It is 0.7 mass part or more, More preferably, it is 2.5 mass parts or less, More preferably, it is 2 mass parts or less.

When talc (F) is contained, the mass ratio ((E) / (F)) of the graft copolymer (E) to talc (F) is preferably in the range of 1.4 to 5. When the mass ratio ((E) / (F)) is in such a range, the dispersibility of the ABS resin (B) and the graft copolymer (E) in the polycarbonate resin (A) can be improved, and impact resistance can be improved. Property and appearance defects can be improved. That is, in addition to the mass ratio of the ABS resin (B) to the graft copolymer (E) described above, the mass ratio of (B), (E) and (F) is set to a specific range, so that the polycarbonate resin (A ) To find out that the dispersion state of each component can be appropriately controlled, and to simultaneously improve the properties that were difficult to improve at the same time, such as improved impact resistance, poor appearance, and improved flame retardancy. Became possible. When the mass ratio ((E) / (F)) is larger than 5, the flame retardancy is remarkably lowered, and when it is smaller than 1.4, the impact resistance is liable to be remarkably lowered. The mass ratio ((E) / (F)) is more preferably 1.45 or more, further preferably 1.5 or more, more preferably 4 or less, and still more preferably 3.5 or less.

[Carbon black]
The thermoplastic resin composition of the present invention preferably contains carbon black from the viewpoint of improving the high-quality feeling of the molded product. There are no restrictions on the production method of carbon black to be used, the raw material species, etc., and any conventionally known ones such as oil furnace black, channel black, acetylene black, ketjen black and the like can be used. Among these, oil furnace black is preferable from the viewpoint of colorability and cost.

The average particle size of the carbon black to be used may be appropriately selected and determined, but is preferably 5 to 60 nm, more preferably 7 to 55 nm, and particularly preferably 10 to 50 nm. By setting the average particle diameter within the above range, the aggregation of carbon black is suppressed and the appearance tends to be improved. The average particle diameter of carbon black can be obtained using a transmission electron microscope.

The nitrogen adsorption specific surface area of the carbon black used in the present invention is usually preferably less than 1000 m ² / g, and more preferably 50 to 400 m ² / g. By making the nitrogen adsorption specific surface area less than 1000 m ² / g, the fluidity of the thermoplastic resin composition of the present invention and the appearance of the molded product tend to be improved, which is preferable. The nitrogen adsorption specific surface area can be measured according to JIS K6217 (unit: m ² / g).

The DBP absorption of carbon black ^is preferably less than 300 cm 3/100 g, is preferably Among them 30 ^~ 200cm 3 / 100g. The DBP absorption amount by less than 300 cm ^3/100 g, preferably tends to increase the appearance of fluidity and a molded article of the thermoplastic resin composition of the present invention.

Incidentally, DBP absorption amount can be measured according to JIS K6217 (unit ^cm 3 / 100g). The carbon black used in the present invention is not particularly limited in pH, but is usually 2 to 10, preferably 3 to 9, and more preferably 4 to 8.

The carbon black used in the present invention can be used alone or in combination of two or more. Furthermore, carbon black can be granulated using a binder, and can also be used in a masterbatch that is melt-kneaded at a high concentration in another resin. By using the melt-kneaded master batch, the handling property during extrusion and the dispersibility improvement in the resin composition can be achieved. Examples of the resin include polystyrene resin, polycarbonate resin, acrylic resin, and the like.

The content of carbon black is preferably 0.0001 parts by mass or more, more preferably 0.0005 parts by mass or more, and still more preferably 0 with respect to 100 parts by mass in total of the polycarbonate resin (A) and the ABS resin (B). 0.001 part by mass or more, preferably 2 parts by mass or less, more preferably 1 part by mass or less. When the carbon black is less than the lower limit of the range, the appearance and jet blackness may be inferior, and when the carbon black content exceeds the upper limit of the range, the heat of the thermoplastic resin composition of the present invention. Stability may be reduced.

[Phosphorus stabilizer]
The thermoplastic resin composition of the present invention preferably contains a phosphorus stabilizer. Any known phosphorous stabilizer can be used. Specific examples include phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate, and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, etc. Particularly preferred.

Organic phosphite compounds include triphenyl phosphite, tris (monononylphenyl) phosphite, tris (monononyl / dinonyl phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, monooctyl Diphenyl phosphite, dioctyl monophenyl phosphite, monodecyl diphenyl phosphite, didecyl monophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylene bis (4,6-di- tert-butylphenyl) octyl phosphite and the like.
Specific examples of such organic phosphite compounds include, for example, “ADEKA STAB 1178”, “ADEKA STAB 2112”, “ADEKA STAB HP-10” manufactured by ADEKA, “JP-351” manufactured by Johoku Chemical Industry Co., Ltd., “ JP-360 ”,“ JP-3CP ”,“ Irgaphos 168 ”manufactured by BASF, and the like.
In addition, 1 type may contain phosphorus stabilizer and 2 or more types may contain it by arbitrary combinations and a ratio.

The content of the phosphorus stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the ABS resin (B). 0.03 parts by mass or more, and usually 1 part by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the phosphorus stabilizer is less than the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

[Phenolic stabilizer]
It is also preferable that the thermoplastic resin composition of the present invention contains a phenol-based stabilizer. As a phenol type stabilizer, a hindered phenol type antioxidant is mentioned, for example. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-( Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol, 2- [1- (2-hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di- ert- pentylphenyl acrylate.

Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Specific examples of such phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by ADEKA, and the like. Is mentioned.
In addition, 1 type may contain the phenol type stabilizer, and 2 or more types may contain it by arbitrary combinations and a ratio.

The content of the phenol-based stabilizer is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the polycarbonate resin (A) and the ABS resin (B). Usually, it is 1 part by mass or less, preferably 0.5 part by mass or less. When the content of the phenol-based stabilizer is less than the lower limit of the range, the effect as the phenol-based stabilizer may be insufficient, and the content of the phenol-based stabilizer exceeds the upper limit of the range. If this is the case, the effect may reach its peak and not economical.

[Release agent]
It is also preferable to contain a release agent. Preferable examples of the release agent include aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane silicone oils.

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

As the aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol, for example, the same one as the aliphatic carboxylic acid can be used. On the other hand, examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the term “aliphatic” is used as a term including alicyclic compounds.

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

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

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

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

Among these, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are more preferable.
The number average molecular weight of the aliphatic hydrocarbon is preferably 5,000 or less.
The aliphatic hydrocarbon may be a single substance, but even a mixture of various constituent components and molecular weights can be used as long as the main component is within the above range.

Examples of the polysiloxane silicone oil include dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, and fluorinated alkyl silicone.

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

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

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

Other resins Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer ( AS resins), styrene resins such as acrylonitrile-styrene-acrylic rubber copolymers (ASA resins), acrylonitrile-ethylenepropylene rubber-styrene copolymers (AES resins); polyolefin resins such as polyethylene resins and polypropylene resins; polyamides Resin; Polyimide resin; Polyetherimide resin; Polyurethane resin; Polyphenylene ether resin; Polyphenylene sulfide resin;
In addition, 1 type may contain other resin and 2 or more types may contain it by arbitrary combinations and ratios.

-Resin additive Examples of the resin additive include an ultraviolet absorber, a dye / pigment, an antistatic agent, an antifogging agent, an antiblocking agent, a fluidity improver, a plasticizer, a dispersant, and an antibacterial agent. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.
Hereinafter, the example of an additive suitable for the thermoplastic resin composition of this invention is demonstrated concretely.

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

Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2'-methylenebis [4 (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], among others, 2- (2′-hydroxy-5′-tert-octylphenyl) ) Benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], particularly 2- (2 ′ -Hydroxy-5'-tert-octylphenyl) benzotriazole is preferred.
Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Chemical Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Ltd. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “TINUVIN P”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 327” manufactured by BASF ”,“ Tinuvin 328 ”and the like.

Specific examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octoxy. Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 , 4′-dimethoxybenzophenone, and the like. Specific examples of such benzophenone compounds include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorve 103 ", joint “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, Chemipro Kasei “Chemsorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemsorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF "Ubinur 400", BASF "Ubinur M-40", BASF "Ubinur MS-40", Cytec Industries "Thiasorb UV9", "Thiasorb UV284", "Thiasorb UV531", " Siasorb UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by ADEKA, and the like.

Specific examples of the salicylate compound include, for example, phenyl salicylate, 4-tert-butylphenyl salicylate and the like. Specific examples of such salicylate compounds include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Pharmaceutical Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35”, “Ubinur N- 539 "and the like.

Examples of the triazine compound include a compound having a 1,3,5-triazine skeleton. Specific examples of such a triazine compound include, for example, “LA-46” manufactured by ADEKA and “tinuvin” manufactured by BASF. 1577ED "," Tinuvin 400 "," Tinuvin 405 "," Tinuvin 460 "," Tinuvin 477-DW "," Tinuvin 479 "and the like.

Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant, “B-CAP” manufactured by BASF, and the like.

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

-Dye / pigment Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.
Inorganic pigments include, for example, sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown , Titanium-cobalt green, cobalt green, cobalt blue, oxide-based pigments such as copper-chromium black, copper-iron-based black; chromic pigments such as yellow lead and molybdate orange; ferrocyan pigments such as bitumen Etc.

Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

Of these, titanium oxide, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.
In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

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

[Method for producing thermoplastic resin composition]
There is no restriction | limiting in the manufacturing method which manufactures the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include polycarbonate resin (A), ABS resin (B), phosphoric ester compound (C), fluoropolymer (D) and graft copolymer (E), and other blended as necessary. Are mixed in advance using various mixers such as a tumbler and a Henschel mixer, and then melt-kneaded with a mixer such as a Banbury mixer, roll, brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader or the like. A method is mentioned.

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

The thermoplastic resin composition of the present invention is flame retardant according to the UL94 test at a thickness of 1.5 mm in the UL94 test (combustion test of plastic materials for equipment parts) defined by US Underwriters Laboratories (UL). However, it has a very high flame retardancy of preferably 5 VA or 5 VB.
In addition, the thermoplastic resin composition of the present invention has a very high flame retardancy, preferably V-0, in the UL 94 test, with a UL94 test at a thickness of 1.2 mm.
Furthermore, the thermoplastic resin composition of the present invention has a flame retardancy of 5 VA or 5 VB at a thickness of 1.5 mm and a flame retardancy of V-0 at a thickness of 1.2 mm in the UL94 test. Is also preferable.

[Molded body]
The thermoplastic resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

Examples of molded articles include parts such as electrical / electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, and lighting equipment. Among these, it is particularly suitable for use in housings of electric / electronic devices and OA devices, and is particularly suitable for housings such as printers, copiers, projectors, modems and routers.

The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. A molding method using a hot runner method can also be used.
The obtained molded article of the present invention is excellent in flame retardancy, impact resistance and appearance.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

(Examples 1 to 4, Comparative Examples 1 to 4)
[Production of resin pellets]
Of the components listed in Table 1, components other than component C were blended in the proportions (mass ratios) listed in Tables 4 to 5, mixed for 20 minutes with a tumbler, and then manufactured by Nippon Steel Works, Ltd. equipped with 1 vent. Supply to the twin screw extruder (TEX30α) from the upstream feeder, and further knead in the form of a strand while supplying the C component from the middle of the barrel while rotating at 250 rpm, discharge rate 45 kg / hour, barrel temperature 260 ° C. The extruded molten resin was quenched in a water bath and pelletized using a pelletizer to obtain resin composition pellets.

In Table 1, the number average particle size of the butadiene rubber (b3) in the ABS resin (B) and the number average particle size of the graft copolymer (E) were measured by the methods described above.

[Preparation of test piece]
After drying the pellets obtained by the above-mentioned production method at 80 ° C. for 5 hours, injection is performed under the conditions of a cylinder temperature of 240 ° C. and a mold temperature of 40 ° C. using an SE100DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. It molded and the test piece for UL test of length 125mm, width 13mm, thickness 1.5mm, and 1.2mm was shape | molded.
Similarly, after the pellets obtained by the above-described production method were dried at 80 ° C. for 5 hours, the cylinder temperature was adjusted to 240 ° C. using an injection molding machine CYCAP M-2 (clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. Injection molding was carried out under the conditions of 0 ° C. and a mold temperature of 60 ° C. to form a 240 ° C. molded ISO multipurpose test piece (4 mm) and a 240 ° C. molded ISO multipurpose test piece (3 mm).
Further, injection molding was performed under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C., and a 260 ° C. molded ISO multipurpose test piece (3 mm) was molded.

[Flame retardance evaluation]
Evaluation of flame retardancy of each resin composition was performed by using the test pieces for UL test (1.5 mm thickness and 1.2 mm thickness) obtained above for 48 hours in a temperature-controlled room at a temperature of 23 ° C. and a humidity of 50%. Humidity adjustment was performed in accordance with the 94-5V standard and the 94-V standard of the UL94 test (combustion test of plastic materials for equipment parts) established by US Underwriters Laboratories (UL).
The 94-5V test uses a 1.5 mm-thick UL test specimen (two types of rod and plate), the afterflame time of the rod-shaped test piece after 5 seconds of flame contact, drip properties, The method of evaluating flame retardance from the presence or absence of through-holes in a plate-shaped test piece, and the determination criteria are as shown in Table 2 below. Those not satisfying any criteria of 5VA and 5VB were expressed as NR.
In Tables 4 to 5, “1.5 mm UL flame retardancy” is described.

In the 94-V test, a 1.2 mm thick UL test specimen was used, and the afterflame time and drip characteristics after a 10-second indirect flame was burned on a specimen of a predetermined size held vertically. In order to have flame retardancy of V-0, V-1, and V-2, it is necessary to satisfy the criteria shown in Table 3 below.

Here, the afterflame time is the length of time for which the test piece continues to burn with flame after the ignition source is moved away. The cotton ignition by the drip is determined by whether or not the labeling cotton, which is about 300 mm below the lower end of the test piece, is ignited by a drip from the test piece. In Tables 4 to 5, “1.2 mm UL flame retardancy” is used.

[Shock resistance]
Using the 240 ° C. molded ISO multi-purpose test piece (3 mm) and 260 ° C. molded ISO multi-purpose test piece (3 mm) obtained by the above-described method, the Charpy impact strength with notch (unit: kJ / m ² ) is measured according to ISO 179. Measured and evaluated.
In Tables 4 to 5, they are expressed as “240 ° C. impact resistance” and “260 ° C. impact resistance”, respectively.
The ratio (%) of “260 ° C. impact resistance” when the value of “240 ° C. impact resistance” was 100 was determined as “impact resistance retention”. A larger value means that there is less deterioration in physical properties even at high temperature molding, which means that when molding a large and thin molded product, the decrease in physical properties is small and it is easy to design.

[Appearance evaluation]
FIG. 1 is a top view (viewed from the design surface on the front side) showing the shape of a flat molded body formed for appearance evaluation. The flat molded body is a rectangular flat plate having a length of 200 mm, a width of 150 mm, and a thickness of 2 mm. Molding is performed by injecting resin from the gate 1 provided at the right end of the flat molded body. On the back side of the flat molded body, ribs 2 having a length of 30 mm, a thickness of 1.1 mm, and a height of 5 mm in the resin flow direction are located at the positions shown in FIG. 1 (the unit of numerical values is mm). Three ribs 2 'having a length of 100 mm, a thickness of 1.1 mm, and a height of 5 mm are provided on the back surface side of the flat plate-shaped body in a direction perpendicular to the resin flow direction. .
The pellets obtained by the above production method were dried at 80 ° C. for 5 hours, and then injection molded under the conditions of a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. using an EC160 type injection molding machine manufactured by Toshiba Machine. The flat molded body is molded, passes through the rib 2 'perpendicular to the resin flow direction, and further passes through the three ribs 2 provided in the flow direction (the design surface of the three flow direction ribs 2 in FIG. 1). Observe visually the number of streaky appearance defects that occurred on the left side), and the number of streaky appearance defects of 0 to 3 is “pass” and 4 or more are “fail”. evaluated.

From Table 4 above, the polycarbonate resin (A), ABS resin (B), phosphate ester compound (C), fluoropolymer (D) and graft copolymer (E) defined in the present invention are defined in the present invention. The thermoplastic resin compositions of Examples contained in the range achieve 1.5 mm UL flame retardancy of 5 VB, 1.2 mm UL flame retardancy of V-0, excellent impact resistance, and high impact resistance retention. In the appearance evaluation, it can be seen that there are few streaky appearance defects.
On the other hand, Table 5 reveals the following. Comparative Example 1 has poor impact resistance because the content of the graft copolymer (E) is small, and Comparative Example 2 in which the content of the graft copolymer (E) exceeds the specified amount has poor flame retardancy. The appearance is also getting worse. Further, Comparative Example 3 in which the number average particle diameter of the graft copolymer (E) is large is poor in flame retardancy and appearance, and the diene rubbery polymer component (b3) in the ABS resin (B). In Comparative Example 4 having a large number average particle diameter, the 1.5 mm UL flame retardancy cannot achieve 5 VB, and the appearance deteriorates.
Therefore, from the above Examples and Comparative Examples, it was confirmed that the effects of excellent flame retardancy, impact resistance and appearance were obtained for the first time by the configuration of the present invention.

(Examples 5 to 15, Comparative Examples 5 to 8, Reference Examples 1 to 5)
[Production of resin pellets]
Of the components listed in Table 6 below, components other than component C were blended at the ratios (mass ratios) listed in Tables 7 to 10, mixed for 20 minutes with a tumbler, and then Nippon Steel Corporation with 1 vent. Supply to the twin screw extruder (TEX30α) from the upstream feeder, and knead under the conditions of a rotation speed of 250 rpm, a discharge rate of 45 kg / hour, and a barrel temperature of 260 ° C. while supplying the C component from the middle of the barrel. The molten resin extruded in the above was quenched in a water bath and pelletized using a pelletizer to obtain a resin composition pellet.

In Table 6, the number average particle diameter of the butadiene rubber (b3) in the ABS resin (B) and the number average particle diameter of the graft copolymer (E) were measured by the methods described above.

Flame retardancy, impact resistance and appearance were evaluated by the same methods as described above.
The results are shown in Table 7 below.

From Tables 7 to 8 above, the polycarbonate resin (A), ABS resin (B), phosphate ester compound (C), fluoropolymer (D) and graft copolymer (E) specified in the present invention are used in the present invention. The thermoplastic resin compositions of Examples 5 to 15 contained within the specified range achieve 1.5 mm UL flame retardancy of 5 VB, 1.2 mm UL flame retardance of V-0, excellent impact resistance, and impact resistance. The retention rate is also high, and the appearance evaluation shows that the occurrence of streaky appearance defects is small.

On the other hand, Tables 9 to 10 reveal the following. Comparative Example 5 is a comparative example in which the number average particle size of the diene rubbery polymer component (b3) in the ABS resin (B) is large and the appearance is poor, and the number average particle size of the graft copolymer (E) is large. In Example 6, the flame retardancy is poor and the appearance is also poor. Moreover, the comparative example 7 with little content of a graft copolymer (E) has bad impact resistance, and the external appearance is deteriorated with the comparative example 8 with too much content.
In Reference Example 1 in which the content of talc (F) is small, the 1.5 mmUL flame retardancy is 5 VB, but the 1.2 mmUL flame retardancy is V-1, and the flame retardance is slightly deteriorated. Reference Example 2 has low impact resistance due to a large content of talc (F), and Reference Examples 3 to 4 containing small talc particle sizes have a 1.2 mm UL flame retardancy of V-1. In Reference Example 5 in which the flammability is reduced and the particle size of talc is large, the impact resistance is reduced.

Since the thermoplastic resin composition of the present invention is a polycarbonate / ABS resin alloy that is excellent in flame retardancy, impact resistance and appearance, and also excellent in impact strength during high temperature molding, its industrial utility is high. There is something.

Claims

Polycarbonate resin (A) 60-90% by mass, aromatic vinyl monomer component (b1) 40-80% by mass, vinyl cyanide monomer component (b2) 10-30% by mass, diene rubber polymer 5 to 20 parts by mass of ABS resin (B) consisting of 10 to 30% by mass of component (b3) and other monomer component (b4) of 0 to 30% by mass, and a phosphate compound represented by the following formula (1) (C) For 100 parts by mass of the base resin composed of 5 to 20% by mass,
0.01 to 1 part by mass of fluoropolymer (D), 1 to 3.5 parts by mass of graft copolymer (E) obtained by graft polymerization of aromatic vinyl compound and / or (meth) acrylic acid ester compound to diene rubber Contains,
The number average particle size of the diene rubbery polymer component (b3) in the ABS resin (B) is 100 to 350 nm, and the number average particle size of the graft copolymer (E) is 100 to 350 nm. A thermoplastic resin composition characterized by the above.

(Wherein R 1 , R 2 , R 3 and R 4 each 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, p, q, r and s are each 0 or 1, k is an integer of 0 to 5, and X 1 represents an arylene group.)
2. The thermoplastic resin composition according to claim 1, further comprising 0.5 to 3 parts by mass of talc (F) having an average particle diameter of 5 to 15 μm with respect to 100 parts by mass of the base resin.
The thermoplastic resin composition according to claim 1 or 2, wherein the number average particle diameter of the diene rubbery polymer component (b3) in the ABS resin (B) is 130 to 280 nm.
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the number average particle diameter of the graft copolymer (E) is 130 to 280 nm.
The thermoplastic resin composition according to any one of claims 1 to 4, wherein the proportion of the diene rubbery polymer component (b3) having a particle size of 1000 nm or more is 2% or less.
The thermoplastic resin composition according to any one of claims 1 to 5, wherein a mass ratio ((B) / (E)) of the ABS resin (B) to the graft copolymer (E) is 4 to 25.
The thermoplastic resin composition according to any one of claims 1 to 6, wherein a mass ratio ((E) / (F)) of the graft copolymer (E) to talc (F) is 1.4 to 5.
The thermoplastic resin composition according to any one of claims 1 to 7, wherein the flame retardancy by UL94 at a thickness of 1.5 mm is 5 VA or 5 VB.
The thermoplastic resin composition according to any one of claims 1 to 8, wherein the flame retardancy by UL94 at a thickness of 1.2 mm is V-0.
A molded body formed by molding the thermoplastic resin composition according to any one of claims 1 to 9.
The molded article according to claim 10, which is a casing of at least one OA device selected from a printer, a copier, a projector, a modem, and a router.