JPH0892456A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To impart anistatic properties and flame reatardancy a styrenic resin compsn. comprising a diene rubber and a vinyl cyanide copolymer by compounding the compsn. with a polyamide elastomer, a specific brominated polycarbonate, and Sb2 O3 . CONSTITUTION: This thermoplastic resin compsn. is prepd. by compounding 20-95wt.% styrenic resin compsn. comprising a vinyl cyanide-arom. vinyl copolymer (e.g. AS) and a copolymer formed by grafting a vinyl cyanide compd. and an arom. vinyl compd. onto a diene rubber (e.g. ABS) and having a rubber content of 2-60wt.% with 2-35wt.% polyamide elastomer, 2-35wt.% brominated polycarbonate oligomer represented by the formula (wherein (n) is 2-10), 1-15wt.% antimony trioxide, and 0-15wt.% chlorinated polyethylene having a chlorine content of 10-40wt.% and a melt flow rate of 2-20g/10min. The polycarbonate oligomer is generally prepd. by reacting a carbonate precursor with a brominated phenol compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermoplastic resin composition. More specifically, flame retardancy, mattness, containing a brominated polycarbonate oligomer of a specific structure,
And a thermoplastic resin composition having excellent antistatic properties.

[0002]

2. Description of the Related Art Acrylonitrile is used as a diene rubber component,
A so-called ABS resin containing a graft copolymer obtained by copolymerizing a vinyl cyanide compound such as methacrylonitrile and an aromatic vinyl compound component such as styrene and α-methylstyrene, has high impact resistance, mechanical strength, and Due to its excellent molding processability, it is widely used for OA equipment and home appliances as a quasi-engineering plastic having intermediate properties between general-purpose resins and engineering resins. In recent years, with the expansion of these applications, the development of materials having antistatic properties has been actively promoted for the purpose of preventing obstacles due to generation of static electricity and dust adhesion due to electrification.
As a method of semipermanently imparting antistatic property to a BS resin, a method of blending a polyamide elastomer such as polyether ester amide is known. (For example, JP-A-60-23435 and JP-A-61-24.
6244, JP-A-63-95251, JP-A-63-97653).

On the other hand, resins used for OA equipment and home appliances are required to have flame retardancy in addition to permanent antistatic property. As a flame-retardant method for the permanent antistatic ABS resin containing the polyamide elastomer, there is disclosed in Japanese Patent Laid-Open No. 62-2.
A method of adding an organic halogen compound as typified by Japanese Patent No. 32450 is known. This permanent antistatic flame-retardant ABS resin has a good surface gloss, but depending on the application, a so-called matte property with no gloss on the surface of the product may be desired.

Generally, as a delustering method for a thermoplastic resin molded article, (1) a method of blending an inorganic substance with a resin,
(2) A method of texturing the surface of the mold, (3) a method of surface-treating the surface of the molded product such as blasting or matting, (4) a method of blending a styrene-butadiene block copolymer, (5) ) A method of blending a polymer having a crosslinked structure with a resin is known. But,
Since the method (1) is a blend of a large amount of inorganic substances, impact resistance and moldability are remarkably reduced, the method (2) does not provide a sufficient matting effect, and the method (3) produces The productivity is remarkably inferior due to the problem of secondary processing cost. In the method (4) represented by JP-A-56-62847, a large amount of styrene-butadiene block copolymer must be blended in order to enhance the matting effect.
Heat resistance and rigidity decrease. Furthermore, the special fair 3-
In the method (5) represented by Japanese Patent No. 58379, it is necessary to copolymerize a polyfunctional compound such as a non-conjugated divinylbenzene compound with a vinyl compound to form a crosslinked structure.
Since the matting effect remarkably changes due to the change in the molecular weight of the crosslinked copolymer, it is difficult to control the molecular weight of the crosslinked copolymer.

When imparting flame retardancy to a thermoplastic resin that has been matted by the above-mentioned method, it is necessary to mix an organic halogen compound into the resin and compound it, so that there are many problems in productivity and profitability. There is. Furthermore, regarding styrene resins, UL standard 94 method (US: Underwriters
In order to obtain a flame retardancy level that conforms to Laboratories Inc. standard), it is essential to use the organic halogen compound and antimony trioxide in combination.

[0006]

The object of the present invention is to solve the above-mentioned drawbacks of the prior art and to have excellent matting performance and good flame retardant performance without using a special matting technique. It is an object of the present invention to provide a thermoplastic resin composition which is excellent in antistatic property and productivity, has good moldability and mechanical properties, and has a matting property which does not depend on extrusion and molding conditions.

[0007]

The object of the present invention is to provide a graft copolymer obtained by graft-copolymerizing (A) (A-1) a diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound. (A-2) A styrene-based resin composition comprising a copolymer of a vinyl cyanide compound and an aromatic vinyl compound, wherein the rubber component content in the composition is 2 to 60% by weight. ) Polyamide elastomer, (C) Brominated polycarbonate oligomer represented by general formula (I),

[Chemical 2] (However, n in the formula represents an integer of 2 to 10.) (D) antimony trioxide, (E) chlorine content of 10 to 40% by weight, and 180
2 to 2 melt flow rate under C, 21.6kg load
A resin composition comprising chlorinated polyethylene in the range of 0 g / 10 minutes, the composition ratio of which is (A) 2
A thermoplastic resin composition of 0 to 95 wt% (B) 2 to 35 wt% (C) 2 to 35 wt% (D) 1 to 15 wt% (E) 0 to 15 wt%.

The present invention further comprises (F) a modified vinyl polymer having (F) at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, an amino group and an amide group.
To 30 parts by weight of a thermoplastic resin composition, and /
Alternatively, it is more preferable that the thermoplastic resin composition is prepared by blending (E) an anionic surfactant in an amount of 0.05 to 5 parts by weight.

The present invention will be described in detail below. The styrene resin composition (A) in the present invention is (A-
1) A composition comprising a graft copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a diene rubber component, and (A-2) a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is a thing.

Examples of the diene rubber in (A-1) include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer and isoprene rubber. To be

The vinyl cyanide compound to be grafted to the diene rubber component may be acrylonitrile, methacrylonitrile, ethacrylonitrile, etc., with acrylonitrile being particularly preferred. As the aromatic vinyl compound, styrene, α-methylstyrene, p
-Methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene, o, p-dichlorostyrene and the like can be mentioned, but styrene is particularly preferable. These can use 1 type (s) or 2 or more types. Further, if necessary, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) N-hexyl acrylate, cyclohexyl (meth) acrylate, (meth)
Chloromethyl acrylate and (meth) acrylic acid 2-
A compound selected from chloroethyl and the like may be copolymerized.

On the other hand, examples of the vinyl cyanide compound which is the constituent component of (A-2) include acrylonitrile, methacrylonitrile and ethacrylonitrile, with acrylonitrile being particularly preferred. As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene,
o-ethylstyrene, o-chlorostyrene and o, p
-Dichlorostyrene and the like can be mentioned, but styrene is particularly preferable. These can use 1 type (s) or 2 or more types. Further, if necessary, a part of the aromatic vinyl compound may be an unsaturated carboxylic acid alkyl ester such as methyl (meth) acrylate or ethyl (meth) acrylate, N-methylmaleimide, N-cyclohexylmaleimide, N-phenyl. Maleimide compounds such as maleimide, unsaturated dicarboxylic acids such as maleic acid, unsaturated dicarboxylic acid anhydrides such as maleic anhydride, and copolymerizable vinyl compounds represented by unsaturated amide compounds such as acrylamide may be substituted. I can.

The copolymers (A-1) and (A-2) can be produced by emulsion polymerization, suspension polymerization, bulk polymerization,
Any polymerization method such as solution polymerization may be used and is not particularly limited.

The content of the diene rubber component in the styrene resin composition (A) is preferably from 2 to 60% by weight, more preferably from 10 to 40% by weight, from the viewpoint of mechanical strength and fluidity. The content of the (A) styrene resin composition in the thermoplastic resin composition needs to be in the range of 20 to 95% by weight, preferably 45 to 90% by weight. If it is less than 20% by weight, mechanical strength such as impact resistance is not sufficient, which is not preferable. On the other hand, if it exceeds 95% by weight, the contents of the polyamide elastomer and the brominated polycarbonate oligomer flame retardant component become small, so that the antistatic property and the flame retardancy level decrease, which is not preferable.

Examples of the (B) polyamide elastomer in the present invention include (a) a polyamide-forming component having 6 or more carbon atoms, and (b) a poly (alkylene oxide).
Examples include graft or block copolymers by reaction with glycol. Here, (a) an amide-forming component having 6 or more carbon atoms, specifically, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 1
Aminocarboxylic acids such as 1-aminoundecanoic acid and 12-aminododecanoic acid, or lactams such as caprolactam, enantolactam, capryllactam and laurolactam, hexamethylenediamine-adipate, hexamethylenediamine-sebacate and hexamethylene Nylon salts such as diamine-isophthalate may be mentioned.
Examples of the (b) poly (alkylene oxide) glycol include polyethylene oxide glycol and poly (1,2).
-Propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, ethylene oxide / propylene oxide block or random copolymer, ethylene oxide / tetrahydrofuran block Alternatively, a random copolymer or the like is used. The poly (alkylene oxide) glycol has a number average molecular weight of 200 to 6000, especially 30.
0 to 4000 is preferable. If necessary, (b)
Both ends of the component may be aminated or carboxylated.

The bond between the (a) polyamide-forming component having 6 or more carbon atoms and the (b) poly (alkylene oxide) glycol component of the present invention is usually an ester bond or an amide bond, but is not particularly limited thereto. It is also possible to use a third component such as dicarboxylic acid or diamine as a reaction component. As the dicarboxylic acid component in this case,
Those having 4 to 20 carbon atoms are preferable, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,
Aromatic dicarboxylic acids such as 7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,
Alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, fats such as succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedioic acid Group dicarboxylic acids are mentioned, and in particular, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferable from the viewpoint of polymerizability, color tone, and physical properties. On the other hand, as the diamine component, aromatic, alicyclic, and aliphatic diamines are used, and among them, aliphatic diamine hexamethylenediamine is preferable.

The content of the (B) polyamide elastomer in the thermoplastic resin composition must be 2 to 35% by weight, preferably 5 to 20% by weight. If the content is less than 2% by weight, the antistatic property is significantly reduced, while 3%
If it exceeds 5% by weight, the rigidity is lowered and the moldability is deteriorated, which is not preferable.

The method for polymerizing the polyamide elastomer (B) is not particularly limited, and a known method can be used. For example, a salt of an aminocarboxylic acid or a lactam or a dicarboxylic acid having 6 or more carbon atoms and a dicarboxylic acid (a)
And a dicarboxylic acid (c) are reacted to prepare a polyamide prepolymer having carboxylic acid groups at both ends, and poly (alkylene oxide) glycol (b) is reacted with this under vacuum, or the above (a), (b) ) And (c) are charged into a reaction tank and heated and reacted at high temperature in the presence or absence of water to produce a carboxylic acid-terminated polyamide elastomer, and then the polymerization proceeds under normal pressure or reduced pressure. The method is known. In addition, (a),
There is also a method in which the compounds (b) and (c) are simultaneously charged in a reaction tank, melt polymerization is carried out, and then the polymerization is carried out all at once under a high vacuum.

The brominated polycarbonate oligomer (C) in the present invention has the general formula (I)

[Chemical 3] (However, n in the formula represents an integer of 2 to 10.) and examples thereof include a low molecular weight brominated polycarbonate. Generally, it is obtained by reacting a carbonate precursor with a mixture of a brominated dihydric phenol and a monofunctional chain transfer agent, but is not particularly limited to this method. Examples of the brominated dihydric phenol compound include tetrabromobisphenol A, dibromobisphenol A, tribromobisphenol A, pentabromobisphenol A, hexabromobisphenol A, and the like, and tetrabromobisphenol A is particularly preferable. The chain transfer agent used to obtain the compound represented by the general formula includes organic hydroxy compounds such as alcohol and phenol, and particularly preferably,
It is a t-butyl substituted phenol.

The (C) brominated polycarbonate oligomer that can be used in the present invention has a degree of polymerization limited to 2 to 10. When the degree of polymerization is less than 2, volatilization occurs during molding and plate-out occurs on the surface of the molded product, while when the degree of polymerization is more than 10, compatibility with the base resin is unfavorable. The content of the (C) brominated polycarbonate oligomer in the thermoplastic resin composition needs to be 2 to 35% by weight, and preferably 5 to 20% by weight. When the content is less than 2% by weight, the matting property,
Also, the flame retardancy is remarkably lowered, while if it exceeds 35% by weight, impact resistance is lowered, which is not preferable.

The antimony trioxide (D) in the present invention is obtained by a sublimation method by melting molybdenum or antimony metal, but is not limited to this production method. Purity is preferably 99.5% by weight or more from the viewpoint of environment and safety. Further, it is preferable that the content of lead oxide in (D) antimony trioxide is 0.03% by weight or less, and the content of arsenic trioxide is 0.1% by weight or less. The content of (D) antimony trioxide in the thermoplastic resin composition needs to be 1 to 15% by weight, and preferably 3 to 12% by weight. If the content is less than 1% by weight, sufficient flame retardancy cannot be obtained, while 15
When the content exceeds the weight%, mechanical strength such as impact resistance decreases, which is not preferable.

By blending (E) chlorinated polyethylene, it is possible to further improve flame retardancy. (E) Examples of chlorinated polyethylene generally include chlorine content of 10 to 4
It is preferably 0% by weight and has a melt flow rate of 2 to 20 g / 10 minutes at 180 ° C. under a load of 21.6 kg.

Furthermore, when the thermoplastic resin composition of the present invention is blended with (F) a modified vinyl polymer having at least one functional group of a carboxyl group, an epoxy group, an amino group and an amide group, ( The compatibility of the resin component (A) and the polyamide elastomer component (B) is improved, the mechanical strength such as impact resistance is improved, and the layered releasability is also improved, which is preferable.

The (F) modified vinyl copolymer used in the present invention has a structure obtained by copolymerizing two or more vinyl monomers, and has a carboxyl group, an epoxy group, It has at least one functional group of an amino group and an amide group. The content of these functional groups may be a very small amount, or may be contained in a large amount as long as the performance such as appearance and fluidity is not impaired, and usually, the average amount of the functional group is substantially 1 It is sufficient if more than one functional group is present. The method of introducing at least one functional group of a carboxyl group, an epoxy group, an amino group, and an amide group into the (F) modified vinyl-based copolymer is not particularly limited, but a vinyl having the functional group is usually used. Examples thereof include a method of copolymerizing a vinyl monomer, a method of copolymerizing a predetermined vinyl monomer using a polymerization initiator having the above functional group, or a chain transfer agent.

Specific examples of the vinyl monomer having the above functional group, the polymerization initiator, and the chain transfer agent are as follows.

Examples of vinyl monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and itaconic acid, glycidyl acrylate, glycidyl methacrylate, and itaconic acid. Epoxy group-containing monomers such as glycidyl, (meth) acrylates such as aminoethyl acrylate, ethylaminopropyl methacrylate and phenylaminoethyl methacrylate
Aminoalkyl ester derivatives of acrylic acid, vinylamine derivatives such as N-acetylvinylamine, allylamine derivatives such as methallylamine, and monomers having an amino group such as aminostyrene, acrylamide, N
Examples thereof include monomers having an amide group such as methylmethacrylamide.

Examples of the polymerization initiator include an initiator having a carboxyl group such as γ, γ'-azobis (γ-cyanovaleic acid) and peroxysuccinic acid, and α, α'-azobis (γ-amino-α). , γ-divaleronitrile), and an initiator having an amino group such as p-aminobenzoyl peroxide.

Examples of chain transfer agents include mercaptopropion, 4-mercaptobenzoic acid, and chain transfer agents having a carboxyl group such as thioglycolic acid, mercaptomethylamine, N- (β-mercaptoethyl) -N-.
Examples include chain transfer agents having an amino group such as methylamine, bis- (4-aminophenyl) disulfide, and mercaptoaniline.

The polymerization method for copolymerizing the (F) modified vinyl copolymer may be any of suspension polymerization, bulk polymerization, emulsion polymerization, solution polymerization and the like and is not particularly limited.

The thermoplastic resin composition of the present invention contains the modified vinyl copolymer (F) in an amount of 0.1 to 50% by weight, particularly 0.5 to
The content of 10% by weight is preferable because it is suitable in terms of the balance between the delamination prevention property / the fluidity.

For the thermoplastic resin composition of the present invention,
It is preferable to add (G) an anionic surfactant because the antistatic property is further improved. As an example of the (G) anionic surfactant, a carboxylic acid-based or sulfonic acid-based alkali metal salt is generally used, and particularly, a sulfonic acid-based sodium salt and a potassium salt are preferable. Specific examples include sulfonic acid having an alkyl group such as octyl, nonyl, decyl, dodecyl, and undecyl, alkylbenzenesulfonic acid, and potassium and sodium salts of alkylnaphthalenesulfonic acid.

The (G) in the thermoplastic resin composition of the present invention
The content of the anionic surfactant is 0.05 to 5% by weight.
Is appropriate from the viewpoint of the balance between antistatic property / mechanical strength and moldability, and is preferably 0.2 to 2% by weight.

To the thermoplastic resin composition of the present invention, within the range not impairing the object of the present invention, polyolefins such as vinyl chloride, polyethylene and polypropylene, polyamides such as nylon 6 and nylon 66, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethyl. Polyester such as terephthalate, polycarbonate, various elastomers can be added to improve the performance as a molding resin. Further, if necessary, various stabilizers such as antioxidants, heat stabilizers, ultraviolet absorbers, and light stabilizers, lubricants and plasticizers, pigments and dyes, glass fibers,
Inorganic fillers such as carbon fibers, mica and talc can also be added.

There is no particular limitation on the method for producing the thermoplastic resin composition of the present invention. For example, the above-mentioned (A),
(B), (C), (D), (E) mixture, or (A), (B), (C), (D), (E), (F) mixture, or the above A), (B), (C),
A mixture of (D), (E) and (G), or (A),
Melt-kneading a mixture of (B), (C), (D), (E), (F), and (G) and a mixture of various additives with a Banbury mixer, a roll, and a single-screw or multi-screw extruder. It is possible to adopt various methods such as

The thermoplastic resin composition obtained as described above can be molded by a known method such as injection molding, extrusion molding, blow molding or the like which is currently used for molding thermoplastic resins.

In order to explain the present invention more specifically, examples and comparative examples will be described below, but these examples do not limit the present invention. In addition, "%" represents weight% and "part" represents part by weight unless otherwise specified. With respect to general properties such as mechanical strength and heat resistance of the flame-retardant matte antistatic resin composition, a test piece was molded by injection molding and measured according to the following test method.

Tensile yield strength: ASTM D638 (23 ° C) Flexural modulus: ASTM D790 (23 ° C) Deflection temperature under load: ASTM D648 (1/4 inch, load stress 18.56kg / cm ² ) IZOD impact strength: ASTM
D256 (23 ° C 1/2 inch notch) MF
R (melt flow rate): ISO 1133 (2
20 ℃, 10kg load) Surface resistivity: ASTM D257 (23 ℃) Surface gloss is cylinder temperature 230 ℃, mold temperature 60 ℃
After molding a 120 × 80 × 3 mm test piece under the conditions described above, a digital variable angle gloss meter UGV-5D manufactured by Suga Test Instruments Co., Ltd. was used.
The surface reflected light of the test piece was measured at an incident angle of 60 degrees. For the delamination prevention property, the tensile test piece was bent and fractured, and the state of the fracture surface was visually observed. The criteria for evaluation are ⊚: extremely good, ∘: good, Δ: somewhat bad, and x: extremely bad. UL standard 94 method (USA: Underwriters Laborat
The test piece thickness was 1.5 mm.

[0038]

[Reference example]

(A) Resin composition (A-1) Graft polymer A1: Polybutadiene latex (rubber average particle size of 0.
2 μ, gel content 90%) 50 parts by weight (solid content), styrene 70% by weight, acrylonitrile 30% by weight
Emulsion polymerization of 50 parts of a monomer mixture consisting of 2,2'-methylenebis (4-methyl-6)
-T-butylphenol) per 1 part by weight of latex solid content 100 parts by weight, and tris (monodiphenyl)
1 part by weight of phosphite was added. Subsequently, this latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to obtain a powdery graft copolymer. A2: Polybutadiene latex (rubber average particle diameter 0.2 μ, gel content 90%) 50 parts by weight (solid content), styrene 25% by weight, acrylonitrile 10
50 parts by weight of a monomer mixture consisting of 50% by weight and 65% by weight of methyl methacrylate are emulsion-polymerized to obtain a latex.
1,2 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 1 part by weight of tris (monodiphenyl) phosphite were added to 100 parts by weight of the latex solid content. Subsequently, this latex was coagulated with sulfuric acid, neutralized with sodium hydroxide, washed, filtered, and dried to obtain a powdery graft copolymer.

(A-2) Copolymer A3: 75 parts of styrene and 25 parts of acrylonitrile were bulk polymerized to obtain a pellet-shaped copolymer. A4: Styrene 40 parts, acrylonitrile 30 parts, α-
30 parts of methylstyrene was suspension-polymerized to obtain a bead-shaped copolymer. A5: 40 parts of styrene, 30 parts of acrylonitrile, N-
30 parts of phenylmaleimide was emulsion-polymerized to obtain a copolymer.

(B) Polyamide Elastomer B1: 60 parts of nylon 6.6 salt, 30 parts of polyethylene glycol having a number average molecular weight of 800, and 10 parts of adipic acid are used in the presence of an antimony trioxide catalyst at 250 ° C. Polymerized for hours. The obtained polymer was discharged in a strand shape and cut to obtain a pellet-shaped polyamide elastomer.

(C) Brominated polycarbonate oligomer C1: "Fireguard" FG-7 manufactured by Teijin Chemicals Ltd.
500 (chemical formula II)

[Chemical 4] C2: "Iupilon" FR30 manufactured by Mitsubishi Gas Chemical Co., Inc.
(Chemical Formula III)

[Chemical 5] C3: Great Lakes Chemical Corporation BC-52
(Chemical formula IV)

[Chemical 6] (D) Antimony trioxide D1: "PA manufactured by Nippon Seiko Co., Ltd.
TOX-C "(purity 99% by weight or more, lead content 0.03
% Or less and an arsenic content of 0.1% or less) were used.

(E) Chlorinated polyethylene E1: "Daisolak" G220 (23% by weight chlorine content, 180 ° C., 21.6 kg load melt flow rate: 7 g / 10 minutes) manufactured by Daiso Co., Ltd. was used.

(F) Modified Vinyl Copolymer F1: 72 parts of styrene, 25 parts of acrylonitrile, and 3 parts of methacrylic acid were suspension polymerized to obtain a bead-shaped modified vinyl copolymer.

(G) G1: Sodium dodecylbenzene sulfonate (“Neurex powder F” manufactured by NOF CORPORATION) was used.

Examples 1 to 15 and Comparative Examples 1 to 11 (A) Styrene resin composition, (B) polyamide elastomer, (C) brominated polycarbonate oligomer, (D) antimony trioxide, (E) ) After blending chlorinated polyethylene, (F) modified vinyl copolymer, and (G) anionic surfactant in the proportions shown in Table 1, 40
mmφ single-screw extruder (cylinder temperature is from Examples 1 to 3,
8 to 17 and Comparative Examples 1 to 9 are 230 ° C., others are 2
Melt kneading was performed at 60 ° C.) to obtain a pellet resin.

The obtained pellets were manufactured by Toshiba Machine Co., Ltd. injection molding machine IS-50A (cylinder set temperature is from Example 1 to Example 1).
3, 8 to 17 and Comparative Examples 1 to 9 were set to 230 ° C., others were set to 260 ° C., and the mold temperature was set to 60 ° C.) to mold a test piece, and various characteristics were evaluated. The results are as shown in Tables 2-5.

[0047]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is particularly excellent in mattness, flame retardancy and antistatic property, and is also excellent in mechanical properties and prevention of delamination, so that it can be used for OA equipment and home appliances. It is suitable as a molding material for electric appliances.

[0048]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

Claims (3)

[Claims] 1. A graft copolymer obtained by graft-copolymerizing a vinyl cyanide compound and an aromatic vinyl compound with a diene rubber component (A) (A-1), and a vinyl cyanide compound (A-2). A composition comprising a copolymer of an aromatic vinyl compound, wherein the rubber component content in the composition is 2 to 6
0% by weight of styrene resin composition, (B) polyamide elastomer, (C) brominated polycarbonate oligomer represented by the general formula (I), (However, n in the formula represents an integer of 2 to 10.) (D) antimony trioxide, (E) chlorine content of 10 to 40% by weight, and 180
2 to 2 melt flow rate under C, 21.6kg load
A resin composition comprising chlorinated polyethylene in the range of 0 g / 10 minutes, the composition ratio of which is (A) 2
The thermoplastic resin composition is 0 to 95% by weight (B) 2 to 35% by weight (C) 2 to 35% by weight (D) 1 to 15% by weight (E) 0 to 15% by weight. 2. The thermoplastic resin composition 100 according to claim 1.
A thermoplastic resin composition obtained by blending 0.1 to 30 parts by weight of (F) a modified vinyl-based copolymer having at least one functional group of a carboxyl group, an epoxy group, an amino group, and an amide group with respect to parts by weight. Stuff. 3. The resin composition 100 according to claim 1 or 2.
(G) anionic surfactant is added to 0.05 parts by weight.
A thermoplastic resin composition containing 5 to 5 parts by weight.