JP2002088220A - Permanent antistatic thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in moldability, heat resistance, drop impact strength, and permanent antistatic properties without detriment to characteristics inherent in a styrene resin. SOLUTION: This composition is prepared by compounding a specific heat- resistant maleimide-containing ABS resin, a polyetheresteramide, and an elastomer modified with an unsaturated dicarboxylic acid and/or an anhydride thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a permanent antistatic property,
The present invention relates to a thermoplastic resin composition having excellent moldability, heat resistance and surface impact. The thermoplastic resin composition of the present invention is used for cassette halves, communication device housings such as mobile phones, housings of home electric appliances, copiers, fax parts, ventilation fan parts and the like.

[0002]

2. Description of the Related Art Conventionally, a maleimide copolymer has been added for the purpose of improving the heat resistance of an ABS resin or the like (US Pat. No. 3,642,949, US Pat.
652726, JP-A-57-98536, JP-A-57-125241). However, since the composition of the maleimide-based copolymer and the ABS resin has a high electric resistivity, there is a drawback in that dust adheres to the electronic devices and electrostatic damage due to charged electricity occurs in electronic devices.
As a method for imparting permanent antistatic properties to a resin for the purpose of improving these, a method of mixing a polyetheresteramide elastomer with a thermoplastic resin is known (Japanese Patent Application Laid-Open No. Sho 62-241945). Also, Japanese Patent Laid-Open No. 6-5
No. 7090 discloses a thermoplastic resin composition comprising a polyetheresteramide elastomer, an ABS-based graft copolymer and a maleimide-based copolymer.
However, although this thermoplastic resin composition has high heat resistance and high fluidity, it tends to have low surface impact.

[0003]

SUMMARY OF THE INVENTION Under such circumstances,
An object of the present invention is to provide a thermoplastic resin composition having excellent moldability, heat resistance, falling weight strength, and excellent permanent antistatic properties by improving the resin composition without impairing the properties of the styrene resin. To provide.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a maleimide-based copolymer having a specific composition ratio and a vinyl-based graft copolymer having a specific composition ratio have been identified. It has been found that the above-mentioned thermoplastic resin composition can be obtained by blending an elastomer comprising a polyetheresteramide and an ethylene-α-olefin having a specific composition with a resin composition obtained from a vinyl copolymer having a composition ratio of Was.

More specifically, the present invention is summarized as follows: Component (A): 30 to 70% by weight of aromatic vinyl monomer residue, 25 to 55% by weight of unsaturated dicarboxylic acid imide derivative residue, unsaturated dicarboxylic anhydride It is composed of 0 to 25% by weight of a monomer residue and 0 to 40% by weight of a vinyl monomer residue copolymerizable with these monomers, and has a weight average molecular weight of 10%.
5 to 60% by weight of a maleimide copolymer having a molecular weight of 0000 to 180,000; (B) component; 40 to 80% by weight of an aromatic vinyl monomer in 5 to 80 parts by weight of a rubbery polymer; Vinyl monomer 1
10 to 60% by weight of an ABS graft copolymer obtained by graft copolymerizing 20 to 95 parts by weight of a monomer mixture consisting of 5 to 40% by weight and 0 to 40% by weight of a vinyl monomer copolymerizable therewith. Component (C); aromatic vinyl monomer residues 40 to 80% by weight, vinyl cyanide monomer residues 15 to 40% by weight, and vinyl monomer residues 0 to 40 copolymerizable therewith. 0 to 79% by weight of a vinyl copolymer comprising: (D) component: 5 to 20% by weight of polyetheresteramide; (E) component: unsaturated dicarboxylic acid monomer residue and / or acid anhydride thereof Copolymers consisting of ethylene-α-olefins containing 0.1 to 5% by weight of product monomer residues
% By weight of the thermoplastic resin composition.

Hereinafter, the present invention will be described in detail. The weight average molecular weight of the maleimide copolymer (A) used in the present invention is from 100,000 to 180,000. When the weight average molecular weight is less than 100,000, the mechanical properties are not sufficient, and the weight average molecular weight is If it exceeds 180,000, the moldability deteriorates, and defective phenomena such as silver occur in the molded product.

The maleimide copolymer (A) used in the present invention comprises 30 to 70% by weight of aromatic vinyl monomer residues, 25 to 55% by weight of unsaturated dicarboxylic acid imide derivative residues, and unsaturated dicarboxylic anhydride. Monomer residue 0 to 25% by weight, and vinyl monomer residue 0 to 4 copolymerizable with these monomers
Consists of 0% by weight. Preferably, aromatic vinyl monomer residues are 40 to 65% by weight, unsaturated dicarboxylic acid imide derivative residues are 30 to 55% by weight, unsaturated dicarboxylic acid anhydride monomer residues are 0 to 10% by weight, and It is composed of 0 to 20% by weight of a vinyl monomer residue copolymerizable with the monomer. When the content of the aromatic vinyl monomer residue is less than 30% by weight or the content of the unsaturated dicarboxylic acid imide derivative residue is more than 55% by weight, the impact strength becomes low, and a defective product such as silver occurs in the molded product. When the content of the unsaturated dicarboxylic acid imide derivative residue is less than 25% by weight or the content of the aromatic vinyl monomer residue exceeds 70% by weight, the effect of imparting heat resistance is reduced.
Further, when the content of the unsaturated dicarboxylic anhydride monomer residue exceeds 25% by weight, the thermal stability becomes low.

The aromatic vinyl monomer in the maleimide copolymer (A) used in the present invention includes styrene, α-methylstyrene, vinyltoluene, t-butylstyrene,
Examples thereof include styrene monomers such as chlorostyrene and substituted products thereof, among which styrene is particularly preferred. As the unsaturated dicarboxylic acid imide derivative, maleimide, N-
Maleimide monomers such as methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, and the like,
Of these, N-phenylmaleimide is particularly preferred.
Examples of the unsaturated dicarboxylic acid anhydride monomer include anhydrides such as maleic acid, itaconic acid, citraconic acid, and aconitic acid, and maleic anhydride is particularly preferable.

The vinyl monomers copolymerizable with the above monomers include acrylonitrile, methacrylonitrile, α
-Vinyl cyanide monomers such as chloroacrylonitrile,
Acrylic ester monomers such as methyl acrylate, ethyl acrylate and butyl acrylate; methacrylic ester monomers such as methyl methacrylate and ethyl methacrylate; vinyl carboxylic acids such as acrylic acid and methacrylic acid Acid monomers, acrylamide, methacrylamide and the like.

The method for producing the maleimide-based copolymer used in the present invention includes an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride monomer used as necessary, The monomer and the copolymerizable vinyl monomer may be directly copolymerized by a known method, or the unsaturated dicarboxylic anhydride monomer may be an aromatic vinyl monomer,
And copolymerizing with a vinyl monomer copolymerizable with these monomers, and then reacting with ammonia and / or a primary amine to obtain an unsaturated dicarboxylic acid imide derivative. However, as a method for producing these copolymers, the latter, that is, an unsaturated dicarboxylic anhydride monomer was copolymerized with an aromatic vinyl monomer, and a vinyl monomer copolymerizable with these monomers The method of imidization later is more preferable in terms of copolymerizability and economy. The primary amine used in the imidization reaction is methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline,
Toluidine, naphthylamine, chlorophenylamine,
Examples include dichlorophenylamine, bromophenylamine, dibromophenylamine and the like.

The imidation reaction can be carried out in a solution state, bulk state or suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder. The solvent used for the solution reaction in imidation is arbitrary,
For example, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and N-methyl-2- Examples include pyrrolidone and the like.

The reaction temperature for imidization is preferably in the range of 50 to 350 ° C, particularly preferably in the range of 100 to 300 ° C. The imidation reaction does not necessarily require the presence of a catalyst, but if used, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline,
Tertiary amines such as N, N-diethylaniline are preferred.

The maleimide-based copolymer of the present invention can be prepared by a conventionally known emulsion polymerization method, suspension polymerization method, bulk polymerization method,
It may be obtained by any of the solution polymerization methods, or may be a method obtained by combining these polymerization methods, but is preferably a solution polymerization method.
Further, any of batch polymerization and continuous polymerization may be used.

The (B) ABS-based graft copolymer used in the present invention comprises 40 to 80% by weight of an aromatic vinyl monomer, 15 to 80% by weight of a rubbery polymer, and 15 to 15% by weight of a vinyl cyanide monomer.
To 40% by weight and a vinyl monomer copolymerizable therewith 0
It is obtained by graft copolymerizing 20 to 95 parts by weight of a monomer mixture of about 40% by weight. When the amount of the rubbery polymer is less than 5 parts by weight, that is, when the amount of the monomer mixture exceeds 95 parts by weight, the impact resistance is reduced. When the amount of the monomeric mixture is less than 20 parts by weight, that is, when the amount of the rubbery polymer exceeds 80 parts by weight, heat resistance is reduced. And moldability are reduced. On the other hand, if the amount of the aromatic vinyl monomer in the monomer mixture is less than 40% by weight, the moldability deteriorates.
If the amount is more than 10% by weight, the heat resistance is reduced. Further, when the vinyl cyanide monomer in the monomer mixture is less than 15% by weight or more than 40% by weight, the compatibility with the component (A) decreases,
This causes delamination of the heat-resistant thermoplastic resin composition and a reduction in impact strength.

As the aromatic vinyl monomer in the ABS graft copolymer (B) used in the present invention, styrene, α-methylstyrene, vinyltoluene, t-
Examples thereof include styrene monomers such as butylstyrene and chlorostyrene and substituted products thereof, and among them, styrene is particularly preferred. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and among these, acrylonitrile is particularly preferred.

The vinyl monomers copolymerizable with the above monomers include the same methyl (meth) acrylate as described above,
Ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate,
There are octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like, and these can be used alone or in combination.
Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

Specific examples of the rubbery polymer include a butadiene polymer, a copolymer of butadiene with a copolymerizable vinyl monomer, an ethylene-propylene copolymer, and an ethylene-propylene copolymer.
A propylene-diene copolymer, a block copolymer of butadiene and aromatic vinyl, an acrylate polymer, and a copolymer of an acrylate ester and a vinyl monomer copolymerizable therewith are used.

The method for producing the (B) ABS-based graft copolymer used in the present invention is not particularly limited, and examples thereof include an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith. It can be produced by graft-polymerizing a monomer mixture consisting of a polymer to a rubber-like polymer. Specifically, those obtained by any of the conventionally known emulsion polymerization method, suspension polymerization method, bulk polymerization method, solution polymerization method and the like may be used, or these polymerization methods may be used. Combination technology may be used. still,
The (B) ABS-based graft copolymer obtained by graft-polymerizing the above monomer mixture to a rubber-like polymer may contain an ungrafted copolymer.

The vinyl copolymer (C) of the thermoplastic resin composition of the present invention is not essential, but can be contained in an amount of 79% by weight or less in consideration of the balance of physical properties. (C) The vinyl copolymer is composed of 40 to 80% by weight of an aromatic vinyl monomer, 15 to 40% by weight of a vinyl cyanide monomer and 0 to 40% by weight of a vinyl monomer copolymerizable therewith. Become. If the amount of the aromatic vinyl monomer is less than 40% by weight, the moldability decreases, and if it exceeds 80% by weight, the heat resistance decreases. Further, when the amount of the vinyl cyanide monomer is less than 15% by weight or more than 40% by weight, the compatibility with the component (A) decreases,
This causes delamination of the thermoplastic resin composition and a reduction in impact strength.

The aromatic vinyl monomer in the vinyl copolymer (C) used in the present invention includes the same styrene as described above,
Styrene monomers such as α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like and substituted products thereof are exemplified, and among them, styrene is particularly preferred.
Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like as described above, and among them, acrylonitrile is particularly preferable.

The vinyl monomers copolymerizable with the above-mentioned monomers include the same methyl (meth) acrylate as described above,
Ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate,
There are octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate and the like, and these can be used alone or in combination.
Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate. The method for producing the vinyl copolymer (C) used in the present invention is not particularly limited, and for example, a polymerization method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method can be employed.

The component (D) used in the present invention is a polyetheresteramide, preferably the polyetheresteramide has a polyether as a soft segment,
It is a block copolymer having a polyamide having carboxyl groups at both ends as a hard segment, and can be produced by a known method. Polyamide (d-1) having carboxyl groups at both terminals constituting polyester amide of component D
Are (1) a lactam ring-opening polymer, (2) a polycondensate of an aminocarboxylic acid and / or (3) a polycondensate of a dicarboxylic acid and a diamine, and as the lactam of (1), caprolactam, enantholactam, Laurolactam, undecanolactam and the like. As the aminocarboxylic acid (2), ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω
-Aminocapric acid, 11-aminoundecanoic acid, 12
-Aminododecanoic acid. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and isophthalic acid. Diamines include hexamethylene diamine, heptamethylene diamine, decamethylene diamine, and octamethylene. Diamines and the like can be mentioned. Two or more of the above-mentioned amide-forming monomers may be used in combination. Preferred among these are caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

The polyamide (d-1) having carboxyl groups at both ends uses a dicarboxylic acid having 4 to 20 carbon atoms as a molecular weight regulator, and in the presence of the diamide, the above amide-forming monomer is ring-opened by a conventional method. It is obtained by polymerization or polycondensation. Examples of the dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Aliphatic dicarboxylic acids such as undecandioic acid and dodecandioic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and dicyclohexyl-4,4 ′
Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids. Of these, preferred are aliphatic dicarboxylic acids, and particularly preferred is adipic acid.

The number average molecular weight of the polyamide component (d-1) is from 500 to 5,000, preferably from 500 to 3,
000. If it is less than 500, the heat resistance of the polyetheresteramide itself decreases, and if it exceeds 5,000, a great amount of time is required for producing the polyetheresteramide.

Examples of the polyether (d-2) component include alkylene oxide adducts of alcohols and phenols. As alcohol, ethylene glycol,
Examples thereof include aliphatic, alicyclic, and aromatic group-containing glycols such as propylene glycol, butanediol, cyclohexanediol, and xylylene glycol. Examples of phenols include hydroquinone, bisphenol A, dihydroxydiphenyl ether and the like. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. Preferred is ethylene oxide.

The number average molecular weight of the polyether component (d-2) is from 500 to 5,000. If it is less than 500, the antistatic property is insufficient, and if it exceeds 5,000, the reactivity is reduced, so that a great amount of time is required in producing the polyetheresteramide.

If the component (D) is less than 5% by weight, no antistatic property is exhibited, and if it exceeds 20% by weight, heat resistance and rigidity are undesirably reduced.

Next, ethylene-α of the component (E) of the present invention is used.
-The olefin elastomer will be described. (E)
The ethylene-α-olefin-based elastomer having an unsaturated dicarboxylic acid and / or an anhydride residue thereof as a component has a number average molecular weight of 10,000 to 1,000,000.
Those having an ethylene content in the range of 0 to 50 to 80 mol% are preferred. As the α-olefin, propylene, 1-butene and 1-pentene can be used, and propylene is particularly preferable. The unsaturated dicarboxylic acid used for the modification as the functional group of the component (E) and / or
Or as its anhydride, maleic acid, itaconic acid,
There are citraconic acid, aconitic acid and their anhydrides, with maleic anhydride being particularly preferred.

The content of the unsaturated dicarboxylic acid and / or anhydride thereof is 0.1 to 5% by weight, preferably 0.5 to 5% by weight, and if it exceeds 5% by weight, the thermoplastic resin composition Gels and the like are generated. If the amount is less than 0.1% by weight, the compatibility between the resins in the thermoplastic resin composition is insufficient, causing delamination, and the chemical resistance and impact strength are not improved. The modified ethylene-α-olefin elastomer can be obtained by using the production method of Example 1 disclosed in JP-B-58-445.

When the component (E) is less than 1% by weight, there is no effect of improving the falling weight strength, and when it exceeds 4% by weight, although the falling weight strength is improved, the antistatic property is lowered. This is (E)
Since the component interacts with the component (D), it is presumed that when added in a large amount, the dispersibility of the component (D) decreases. Therefore, only when the component (E) is added in an amount of 1 to 4% by weight, the effect of high falling weight strength and high antistatic property can be obtained.

The thermoplastic resin composition of the present invention comprises (A) 5 to 60% by weight of the component, (B) 10 to 60% by weight of the component,
Component (C) is 0 to 79% by weight, component (D) is 5 to 20% by weight, and component (E) is 1 to 4% by weight. Preferably (A)
Component 10 to 50% by weight, component (B) 15 to 50 parts by weight,
Component (C) is 20 to 50% by weight, component (D) is 5 to 15% by weight, and component (E) is 2 to 3% by weight. If the component (A) is less than 5% by weight, heat resistance is not sufficient, and if it exceeds 60% by weight, the impact resistance and moldability of the composition are significantly reduced. If the component (B) is less than 10% by weight, impact resistance is not exhibited, and if it exceeds 60% by weight, there is a problem that heat resistance is reduced. If the content of the component (C) exceeds 79% by weight, there is a problem that the impact resistance is reduced. If the component (D) is less than 5% by weight, the antistatic property is not sufficient, and if it exceeds 20% by weight, there is a problem that heat resistance is reduced. If the content of the component (E) is less than 1% by weight, the improvement of the surface impact is not sufficient, and if it exceeds 4% by weight, there is a problem that the antistatic property is lowered due to the interaction with the polyamide part of the component (D). .

The thermoplastic resin composition of the present invention is used for cassette halves, communication equipment housings such as portable telephones, housings for home electric appliances, copiers, fax parts, ventilation fan parts and the like.

The method of mixing the components (A) to (E) to obtain the thermoplastic resin composition of the present invention is not particularly limited, and any known means can be used. Examples of the means include a Banbury mixer, a tumbler mixer, a mixing roll, a single screw or twin screw extruder, and the like. As a mixing form, there is a method of obtaining a thermoplastic resin composition by ordinary contact mixing, multi-stage melt mixing using a master pellet, blending in a solution, and the like.

Further, a stabilizer, a flame retardant, a plasticizer, a lubricant, an ultraviolet absorber, a colorant and a filler such as talc, silica, clay, mica, calcium carbonate, etc. are further added to the thermoplastic resin composition of the present invention. It is also possible. Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. All parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

[0035]

The present invention will be described in more detail with reference to the following examples. These are all examples and do not limit the content of the present invention.

Reference Example 1 Maleimide copolymer (A) component (A-
1) 150 parts by weight of methyl ethyl ketone, 60 parts by weight of styrene, and 0.05 part by weight of α-methylstyrene dimer were charged into an autoclave equipped with a stirrer, and the system was purged with nitrogen gas, and then heated to a temperature of 85 ° C. To this, 40 parts by weight of maleic anhydride, 0.15 of benzoyl peroxide
A solution in which 200 parts by weight of methyl ethyl ketone was dissolved in 200 parts by weight was continuously added for 8 hours. After the addition, the temperature was kept at 85 ° C. for a further 3 hours. 38 parts of aniline and 0.6 parts of triethylamine were added to the obtained copolymer solution and reacted at 140 ° C. for 7 hours. The reaction solution was supplied to a twin-screw extruder equipped with a vent, and devolatilized to obtain a maleimide copolymer. Each monomer residue was measured by C-13 NMR analysis. This was designated as copolymer A-1.

[0036]

Reference Example 2 Maleimide copolymer (A) component (A-
2) In an autoclave equipped with a stirrer, 150 parts by weight of methyl ethyl ketone and 60 parts by weight of styrene were charged, and after the inside of the system was replaced with nitrogen gas, the temperature was raised to 85 ° C, and sufficient stirring was performed while maintaining the temperature. A maleimide-based copolymer A-2 was produced in the same manner as in A-1 except that 1 part of α-methylstyrene dimer was added thereto. Molecular weight and molecular weight distribution: determined by GPC (gel permeation chromatography) in terms of polystyrene. Tg (glass transition temperature): Measured by a DSC (differential scanning calorimetry) device according to JIS K-7121.
Table 1 shows the composition analysis results and characteristic analysis of A-1 to A-2.

[0037]

[Table 1]

[0038]

[Reference Example 3] (B) ABS-based graft copolymer Polybutadiene latex 1 was placed in a reaction vessel equipped with a stirrer.
43 parts (solid content 35%, weight average particle size 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0 .03
Parts, 0.003 parts of ferrous sulfate and 150 parts of pure water.
The mixture was heated to 0 ° C., and 50 parts of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile, 0.2 parts of t-dodecylmercaptan, and 0.15 parts of cumene hydroxide were continuously added over 6 hours. , And 65 after addition
The temperature was raised to ℃, and polymerization was carried out for 2 hours. The conversion reached 97%.
After adding an antioxidant to the obtained latex, it was coagulated with calcium chloride, washed with water and dried to obtain a graft copolymer as a white powder. This was designated as copolymer B-1.

Next, in order to determine the graft ratio of B-1 and the molecular weight of the ungrafted copolymer, 3 g of B-1 was swelled in a methyl ethyl ketone solution, and the ungrafted styrene-acrylonitrile in the supernatant solution was centrifuged. When the molecular weight of the copolymer was measured by gel permission chromatography, the weight average molecular weight was 82,000. Further, the composition of the gel component precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis, pyrolysis gas chromatography and bromine addition method, and the graft ratio was determined by the following formula. The graft ratio was 33%.

[0040]

Reference Example 4 Production of Component (C) In a reaction vessel equipped with a stirrer, 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, t-
0.5 part of dodecyl mercaptan, 0.2 part of benzoyl peroxide and 250 parts of water were charged, and the temperature was raised to 70 ° C. to initiate polymerization. After 7 hours from the start of the polymerization,
The temperature was raised to 5 ° C and kept for 3 hours to complete the polymerization. The conversion reached 97%. The obtained reaction solution was neutralized with hydrochloric acid, dehydrated and dried to obtain a white bead-like copolymer. This was designated as copolymer C-1.

[0041]

Reference Example 5 Production of Component (D) In a 3 L stainless steel autoclave, 105 parts of ε-caprolactam, 17.1 parts of adipic acid, and Irganox 10
0.3 parts of 10 (antioxidant Ciba-Geigy) and 6 parts of water
The mixture was purged with nitrogen, and heated and stirred at 220 ° C. for 4 hours while sealing under pressure to obtain an acid value 11 having a carboxyl group at both ends.
117 parts of a polyamide oligomer of No. 0 were obtained. Next, 225 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added,
Polymerization was performed at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours,
A polymer was obtained. Its relative viscosity is 2.20 (0.
5% by weight m-cresol solution at 25 ° C.). This polyetheresteramide is designated as D-1.

As the component (E), two types of Tuffmer manufactured by Mitsui Chemicals (ethylene-propylene rubber: grade MP-043)
0 and P-0480) were used. The Mooney viscosity was measured according to JIS K6300 at a temperature of 100 ° C., a residual heat of 1 minute, and a rotor rotation time of 4 minutes. The properties are shown in Table 2.

[0043]

[Table 2]

[0044]

Examples 1 to 3 and

Comparative Examples 1 to 7 (A) having the compounding ratio shown in Tables 3 and 4
After blending the components (E) through a Henschel mixer for 3 minutes, the mixture was heated at 250 ° C. for 2 hours using a vented twin screw extruder.
The pellets were extruded at 00 rpm and a discharge rate of 20 kg / hr. Using the pellets, test specimens were prepared by an injection molding machine, and the IZOD impact and Vicat softening point were measured, and the surface impact strength and surface resistivity were evaluated. The results are shown in Tables 3 and 4.

[0045]

[Table 3]

[0046]

[Table 4]

The various evaluation methods shown in Tables 3 and 4 are as follows. Vicat softening point: According to ASTM D-1525, a 3.2 mm thick injection molded product molded at a molding temperature of 250 ° C. was used to measure the Vicat softening point (49 N load). IZOD impact strength: In accordance with ASTM D-256, using a 6.4 mm thick injection molded product molded at a molding temperature of 250 ° C., the notched IZOD impact strength was 50% relative humidity,
The measurement was performed at an ambient temperature of 23 ° C. Surface impact strength: A square plate of 127 × 127 × 2 mm thickness was formed at a forming temperature of 250 ° C., and a 50% breaking height was measured with a 300 g weight at the tip 5R at a relative humidity of 50% and an ambient temperature of 23 ° C. Surface specific resistance: After forming a square plate for measuring the surface impact strength, the plate is washed with an aqueous solution of a detergent (Mama Lemon; manufactured by Lion Corporation), and then sufficiently washed with ion-exchanged water. From 2 to 20 ° C and 65% relative humidity
After standing for 4 hours, the surface resistivity was measured. MFR: according to ASTM D-6874, temperature 220
It measured at 10 degreeC and a load of 10 kg.

[0048]

The composition of the present invention in which the maleimide-based heat-resistant ABS is blended with the polyetheresteramide and the acid-modified elastomer has a higher surface impact strength than the conventional composition in which the maleimide-based ABS is blended with the polyetheresteramide. Excellent heat resistance and antistatic properties.

Claims (2)

[Claims] 1. Component (A): aromatic vinyl monomer residue 30
To 70% by weight, unsaturated dicarboxylic acid imide derivative residue 2
5 to 55% by weight, 0 to 25% by weight of an unsaturated dicarboxylic anhydride monomer residue, and 0 to 40% by weight of a vinyl monomer residue copolymerizable with these monomers. 5 to 60% by weight of a maleimide copolymer having a molecular weight of 100,000 to 180,000; Component (B): 5 to 80 parts by weight of a rubbery polymer; 40 to 80% by weight of an aromatic vinyl monomer; Vinyl cyanide monomer 1
10 to 60% by weight of an ABS graft copolymer obtained by graft copolymerizing 20 to 95 parts by weight of a monomer mixture consisting of 5 to 40% by weight and 0 to 40% by weight of a vinyl monomer copolymerizable therewith. Component (C); aromatic vinyl monomer residues 40 to 80% by weight, vinyl cyanide monomer residues 15 to 40% by weight, and vinyl monomer residues 0 to 40 copolymerizable therewith. 0 to 79% by weight of a vinyl copolymer comprising: (D) component: 5 to 20% by weight of polyetheresteramide; (E) component: unsaturated dicarboxylic acid monomer residue and / or acid anhydride thereof Copolymers consisting of ethylene-α-olefins containing 0.1 to 5% by weight of product monomer residues
% By weight of a thermoplastic resin composition. 2. The component (D) is a polyetheresteramide derived from a polyamide having carboxyl groups at both ends and having a number average molecular weight of 500 to 5,000 and a polyether having a number average molecular weight of 500 to 5,000. The thermoplastic resin composition according to claim 1, wherein: