JPH107839A - Thermoplastic resin composition, molding and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition useful in the field of automobile parts, electronic parts, etc., requiring antistatic properties, capable of providing an acrylonitrile/butadiene/styrene based resin with heat resistance and antistatic properties, comprising a specific copolymer composition and an antistatic agent. SOLUTION: This composition has <=20,000 poise melt viscosity at 260 deg.C at 60 ±5sec<-1> shear rate, and comprises (A) a maleimide copolymer such as a material obtained, for example, by copolymerizing a mixture of an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride and then reacting the copolymer with a primary amine to imidate the acid anhydride group, (B) an acrylonitrile/styrene-based copolymer, (C) an acrylonitrile/butadiene/styrene based graft copolymer and (D) an antistatic agent such as a polyoxyethylene nonyl phenyl ether in the ratio of 0-40wt.% of the component A, 10-95wt.% of the component B, 0-40wt.% of the component C and 5-30wt.% of the component D based on 100wt.% of the total of the components A+B+C+D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition, a thermoplastic resin molded article using the same, and a method for producing the same. In particular, it is a specific thermoplastic resin composition essentially comprising an AS copolymer and an antistatic agent capable of imparting excellent antistatic properties to an ABS resin. Further, a thermoplastic resin molded article having excellent heat resistance and antistatic properties obtained by a method in which the thermoplastic resin composition and the ABS resin are simultaneously supplied to a molding machine and molded (hereinafter, referred to as direct molding). And a method of manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a mixture of styrene and acrylonitrile was graft-copolymerized to a rubber-like polymer.
So-called ABS resins are used for various applications because of their excellent impact resistance, moldability and good surface gloss. However, these resins have high electrical insulation properties and are easily charged by friction or the like, so that there is a problem that dust and dirt adhere to the resin and impair the appearance of molded articles, sheets, films and the like. Recently, video, computer, O
Along with the remarkable development of electronic products using the same resin, such as A equipment, noise caused by static electricity, failure of instruments due to spark, malfunction of IC, memory Antistatic properties are also required to prevent the destruction of flammable organic solvents, explosion and fire of flammable organic solvents, discomfort to the human body, and decrease in commercial value due to inhalation of dust.

[0003] For this reason, a method of applying an antistatic agent to the surface of an ABS resin molded product to improve the antistatic property has been used. However, the coating process is costly and environmental pollution due to the solvent for the coating is reduced. There's a problem.

Although a method of kneading an antistatic agent into an ABS resin is widely known, there is a drawback that the effect is not exhibited unless a large amount of the antistatic agent is added. In addition, in this method, in order to obtain molded articles having various levels of physical properties of various antistatic agents, there is a complicated quality control in that different resin pellets are required according to the required physical property levels. Furthermore, in order to obtain resin pellets corresponding to the respective physical property levels, kneading operations are individually performed, so that the ABS resin is particularly liable to be deteriorated, resulting in a decrease in impact strength. Furthermore, the kneading operation involves a large cost, which is economically disadvantageous.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is to provide an AB
Provided is a thermoplastic resin composition capable of imparting excellent heat resistance and antistatic property to an S-based resin, and further solves the problems caused when obtaining the above-mentioned molded article, and further provides a thermoplastic resin of the present invention. The composition, heat resistance comprising an ABS resin, a thermoplastic resin molded article excellent in antistatic properties, particularly heat resistance obtained by directly molding the thermoplastic resin composition of the present invention and the ABS resin, An object of the present invention is to provide a thermoplastic resin molded article having excellent antistatic properties or a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found the following thermoplastic resin composition, and have found this thermoplastic resin composition and ABS resin. It has been found that the object can be achieved by directly molding a thermoplastic resin molded body composed of the following, in particular, a thermoplastic resin composition and an ABS resin. That is, in the present invention, component (A): 0 to 40% by weight of a maleimide-based copolymer, component (B): 10 to 95% by weight of an AS-based copolymer,
(C) Component: A thermoplastic resin composition comprising 0 to 40% by weight of an ABS-based graft copolymer, and (D) component: 5 to 30% by weight of an antistatic agent [However, the total of (A) to (D) is 100.
% By weight] of the thermoplastic resin composition
The melt viscosity at ℃ is 60 ± 5 (sec ^-1 )
Is a thermoplastic resin composition of not more than 20,000 poise.

Further, the present invention relates to a thermoplastic resin molded product comprising 4 to 50% by weight of the above-mentioned thermoplastic resin composition and 50 to 96% by weight of an ABS-based resin, particularly to a thermoplastic resin composition of 4 to 50% by weight.
A thermoplastic resin molded article obtained by supplying 50% by weight and 50 to 96% by weight of an ABS-based resin to a molding machine and molding,
Further, it is a production method for obtaining the thermoplastic resin molded article.

Hereinafter, the present invention will be described in detail. The maleimide-based copolymer of the component (A) that can be used in the thermoplastic resin composition of the present invention will be described. As a method for producing the maleimide-based copolymer (A), the first method is to prepare an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative and, if necessary, in the presence or absence of a rubbery polymer. Thus, a maleimide-based copolymer can be obtained by a method of copolymerizing a mixture of vinyl monomers copolymerizable therewith.

As a second production method, an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride and, if necessary, a vinyl monomer copolymerizable therewith in the presence or absence of a rubbery polymer. And then reacting ammonia and / or a primary amine to convert an acid anhydride group into an imide group. Any method can provide a maleimide-based copolymer. it can.

[0010] The rubbery polymer which can be used in the first production method and the second production method is a polymer rubber comprising butadiene alone or a vinyl monomer copolymerizable therewith, ethylene-butadiene.
Examples thereof include propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, and a polymer rubber composed of an acrylic ester alone or a vinyl monomer copolymerizable therewith.

The aromatic vinyl monomer used in the first production method and the second production method is at least one kind of styrene selected from styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like. A styrene monomer and a substituted monomer thereof, of which styrene is particularly preferred.

The unsaturated dicarboxylic imide derivative used in the first production method includes at least one maleimide derivative selected from maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide and the like. Of these, N-phenylmaleimide is preferred.

The copolymerizable vinyl monomers which can be used in the first production method include maleic anhydride, itaconic anhydride, citraconic anhydride, aconitic anhydride, methyl acrylate, ethyl acrylate Examples thereof include at least one selected from acrylates such as acid esters and butyl acrylates, and methacrylates such as methyl methacrylate and ethyl methacrylate.

The unsaturated dicarboxylic anhydride used in the second production method is at least one selected from anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid.
The species is maleic anhydride, particularly preferred.

Examples of the copolymerizable vinyl monomer which can be used in the second production method include acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, and ethyl methacrylate. At least one selected from methacrylic esters such as methacrylic esters is exemplified.

Ammonia and primary amine used in the imidation reaction of the second production method may be either anhydrous or in an aqueous solution. Examples of the primary amine include methylamine, ethylamine, cyclohexylamine and the like. Examples thereof include alkylamines and / or aromatic amines such as aniline, toluidine, and naphthylamine.

When the imidization reaction of the second production method is carried out in a solution state or a suspension state, it is preferable to use a usual reaction vessel, for example, an autoclave. Alternatively, an extruder may be used. The temperature of the imidization reaction is about 80-350 ° C, preferably 100-300 ° C. If the temperature is lower than 80 ° C., the reaction rate is low and the reaction requires a long time, which is not practical. 3
If the temperature exceeds 50 ° C., the physical properties of the polymer decrease due to thermal decomposition. A catalyst may be used at the time of the imidization reaction, and in that case, a tertiary amine such as triethylamine is preferably used.

The rubbery polymer constituting the maleimide copolymer (A), the amount of the aromatic vinyl monomer residue, the amount of the unsaturated dicarboxylic acid imide derivative residue, and the amount of the unsaturated dicarboxylic acid anhydride residue The amount of the vinyl monomer residue copolymerizable therewith is not particularly limited, but is preferably 0 to 40% by weight of a rubbery polymer and 40 to 80% by weight of an aromatic vinyl monomer residue. 10 to 60% by weight of an unsaturated dicarboxylic acid imide derivative residue, 0 to 15% by weight of an unsaturated dicarboxylic anhydride residue and 0 to 15% by weight of a vinyl monomer residue copolymerizable therewith. is there.

The preferred range of the rubbery polymer constituting the component (A) is 0 to 40% by weight, and particularly preferably 0 to 40% by weight.
１５15% by weight. If the amount exceeds 40% by weight, the direct moldability of the thermoplastic resin composition of the present invention with the ABS resin is undesirably reduced.

The preferred range of the amount of the aromatic vinyl monomer residue constituting the component (A) is from 40 to 80% by weight, particularly preferably from 45% by weight to less than 60% by weight. 4
If the amount is less than 0% by weight, the moldability of the thermoplastic resin composition and the ABS resin is reduced, and if it exceeds 80% by weight, the heat resistance of the thermoplastic resin composition is undesirably reduced.

The preferred range of the amount of the unsaturated dicarboxylic imide derivative residue constituting the component (A) is 10 to 60% by weight.
However, it is particularly preferably 40 to 55% by weight. 1
If the amount is less than 0% by weight, the heat resistance of the thermoplastic resin composition is not sufficiently improved, and if it exceeds 60% by weight, the impact resistance of the thermoplastic resin composition tends to be significantly reduced, which is not preferable.

The preferred range of the amount of the unsaturated dicarboxylic anhydride residue constituting the component (A) is 0 to 15% by weight, particularly preferably 10% by weight or less (however, 0 is not included).
It is. If the amount exceeds 15% by weight, the heat resistance of the thermoplastic resin composition decreases, which is not preferable.

The preferred range of the amount of the copolymerizable vinyl monomer residue constituting the component (A) is 0 to 15% by weight, particularly preferably 0 to 10% by weight. 15% by weight
When the ratio exceeds the above, the compatibility with other components is reduced, and the impact resistance of the thermoplastic resin composition tends to be reduced. When a molded article made of the thermoplastic resin composition and the ABS resin is formed, delamination may occur. More likely to occur.

As the polymerization method of the component (A), in the first production method, any known polymerization method such as suspension polymerization, emulsion polymerization, solution polymerization and bulk polymerization can be used. In the case of the second production method, bulk-suspension polymerization, solution polymerization, bulk polymerization, and the like can be suitably employed.

Next, the AS copolymer (B) used in the thermoplastic resin composition of the present invention will be described.
The AS copolymer is a copolymer comprising an aromatic vinyl monomer, a vinyl cyanide monomer, and a vinyl monomer copolymerizable therewith.

The aromatic vinyl monomer constituting the component (B) includes at least one styrene monomer selected from styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like. Styrene is particularly preferred as the substituted monomer.

The vinyl cyanide monomer constituting the component (B) includes acrylonitrile, methacrylonitrile,
It is at least one selected from α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferred.

The copolymerizable vinyl monomer constituting the component (B) includes acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, and ethyl methacrylate. Methacrylic acid ester monomers such as esters, acrylic acid, vinyl carboxylic acid monomers such as methacrylic acid, acrylamide, methacrylamide, and N
And at least one selected from vinyl carbazole and the like. Among them, monomers such as acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferred.

The amount of the aromatic vinyl monomer residue, the amount of the vinyl cyanide monomer residue, and the amount of the vinyl monomer residue copolymerizable therewith, which constitute the component (B) AS copolymer. The content of is not particularly limited, but preferably the amount of the aromatic vinyl monomer residue is 60 to 80% by weight, and 65 to 75% by weight.
% By weight is particularly preferred. If it is less than 60% by weight, the moldability of the thermoplastic resin composition tends to decrease, and if it exceeds 80% by weight, the heat resistance of the thermoplastic resin composition tends to decrease.
The amount of the vinyl cyanide monomer residue is preferably from 20 to 40% by weight, particularly preferably from 25 to 35% by weight. 20% by weight
If the amount is less than 40% by weight or more than 40% by weight, the compatibility with other components is liable to be lowered, and it is easy to cause delamination of the thermoplastic resin composition and decrease in impact strength. Further, the preferable range of the amount of the vinyl monomer residue copolymerizable with these is 0 to 20% by weight, and particularly preferably 0 to 10% by weight. If it exceeds 20% by weight, the compatibility with other components tends to decrease, and the impact resistance of the thermoplastic resin composition tends to decrease. Delamination is likely to occur.

The polymerization method of the component (B) can be produced by a usual polymerization method, and for example, a polymerization method such as suspension polymerization, solution polymerization and emulsion polymerization can be adopted.

Next, the ABS-based graft copolymer (C) which can be used in the thermoplastic resin composition of the present invention will be described. The ABS graft copolymer is obtained by graft-polymerizing a monomer mixture of an aromatic vinyl monomer, a vinyl cyanide monomer and a vinyl monomer copolymerizable therewith in the presence of a rubbery polymer. It is a thing.

The rubbery polymer used for the component (C) is
Polymer rubber consisting of butadiene alone or a vinyl monomer copolymerizable therewith, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, or vinyl acrylate alone or copolymerizable therewith At least one selected from polymer rubbers composed of monomers
Seeds.

The aromatic vinyl monomer used for the component (C) is styrene, α-methylstyrene, vinyltoluene,
At least one styrene monomer selected from t-butylstyrene, chlorostyrene and the like, and styrene is particularly preferred.

The vinyl cyanide monomer used for the component (C) is at least one selected from acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferred.

The copolymerizable vinyl monomer used for the component (C) includes acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate, and ethyl methacrylate. Examples include at least one selected from methacrylic acid ester monomers such as esters, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylamide, and N-vinylcarbazole.

The content of the rubbery polymer constituting the ABS graft copolymer of the component (C) is not particularly limited, but is preferably 35 to 65 parts by weight of the rubbery polymer and 45 to 55 parts by weight. Parts are particularly preferred. If the amount is less than 35 parts by weight, the impact resistance is low, and if it exceeds 65 parts by weight, the moldability in forming a molded article, and the heat resistance of the thermoplastic resin composition of the present invention and the molded article tend to be reduced. Also, (C)
The amount of the aromatic vinyl monomer residue, the amount of the vinyl cyanide monomer residue, and the total amount of the vinyl monomer residue copolymerizable with these, which constitute the ABS-based graft copolymer of the components, are as follows. Although not particularly limited, it is preferably 35 to 65 parts by weight, and particularly preferably 45 to 55 parts by weight. Further, the ratio of these residues is not particularly limited, but the amount of aromatic vinyl monomer residue, the amount of vinyl cyanide monomer residue, and the amount of vinyl monomer residue copolymerizable therewith. The preferred range of the amount of the aromatic vinyl monomer residue is 50 to 80% by weight, and particularly preferably 55 to 75% by weight, based on the total amount of 100% by weight. If the amount is less than 50% by weight, the molding processability when the thermoplastic resin composition is formed into a molded body is apt to decrease, and if it exceeds 80% by weight, the impact resistance of the thermoplastic resin composition of the present invention and the molded body thereof is reduced. There is a tendency. The preferred range of the amount of the vinyl cyanide monomer residue is 20 to 50% by weight, and particularly preferably 25 to 45% by weight. If the amount is less than 20% by weight or more than 50% by weight, the compatibility with the maleimide-based copolymer of the component (A) is apt to decrease, and the impact resistance of the thermoplastic resin composition of the present invention and the molded article thereof is significantly reduced. Tend.
Further, the preferred range of the amount of the vinyl monomer residue copolymerizable therewith is 0 to 20% by weight, particularly 0 to 10% by weight.
Is preferred. If it exceeds 20% by weight, the compatibility of the thermoplastic resin composition tends to decrease, and the impact resistance of the molded article tends to decrease.

The rubber particle size, graft ratio, and weight-average molecular weight of the ungrafted copolymer of the ABS graft copolymer (C) are not particularly limited, but the rubber particle size is preferably in the range of 0.1 to 0.6 μm. It is preferable from the viewpoint of the impact resistance of the thermoplastic resin composition of the present invention and the molded article thereof. When the graft ratio is 20 to 80% and the weight-average molecular weight of the ungrafted copolymer is in the range of 50 to 200,000, the balance between impact resistance and moldability is good, which is preferable.

As the polymerization method of the component (C), any known polymerization techniques can be employed, and examples thereof include aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and poor polymerization of the resulting polymer. Heterogeneous precipitation polymerization in a solvent and the like and combinations thereof.

Next, the component (D) used in the thermoplastic resin composition of the present invention will be described. Examples of the antistatic agent include cationic antistatic agents such as primary alkylamine salts, tertiary alkylamine salts, and quaternary alkylammonium salts, alkyl sulfonates, alkyl sulfates, alkyl phosphates, and monovalent fatty acids. Metal salts, anionic antistatic agents such as sulfates of fatty alcohols, ethylene oxide adducts of alkyl phenols, ethylene oxide adducts of partial fatty acid esters of polyhydric alcohols, glycerin fatty acid esters, sorbitan fatty acid esters, poly (oxyethylene Non-a) such as alkylamines, poly (oxyethylene) alkylamides, poly (oxyethylene) monoalkyl ethers, poly (oxyethylene) dialkyl ethers, poly (oxyethylene) alkylphenyl ethers, polyethylene glycols, etc. Emissions antistatic agents, alkyl betaines,
Examples include at least one selected from amphoteric antistatic agents such as alkylimidazoline type and alkylalanine type, polyvinylbenzyl type cations, and polyacrylic acid type cationic conductive resin antistatic agents. Preferred are polyoxyethylene nonylphenyl ether and N, N'-bis- (2-hydroxyethyl) alkylamine.

The thermoplastic resin composition of the present invention comprises 0 to 40% by weight of the maleimide copolymer (A), 10 to 95% by weight of the AS copolymer (B), and ABS (C).
It is composed of 0 to 40% by weight of the system graft copolymer and 5 to 30% by weight of the antistatic agent of the component (D). Further, 0 to 30% by weight of the maleimide copolymer (A) and the AS (B)
A thermoplastic resin composition comprising 10 to 80% by weight of a copolymer, 0 to 35% by weight of an ABS graft copolymer (C), and 10 to 25% by weight of an antistatic agent (D) is preferable. .

The maleimide copolymer of the component (A) contains 40
If the amount exceeds the weight percentage, the thermoplastic resin composition of the present invention and ABS
It is not preferable because the impact resistance of a molded product obtained by directly molding a resin is reduced.

10% by weight of the AS copolymer of the component (B)
If it is less than 1, the mixing of the thermoplastic resin composition of the present invention and the ABS resin is insufficient, and the impact resistance of a molded article obtained by directly molding the thermoplastic resin composition and the ABS resin is not preferable. If it exceeds 95% by weight, the effect of imparting antistatic properties is not sufficient.

When the content of the ABS graft copolymer (C) exceeds 40% by weight, the thermoplastic resin composition of the present invention and A
It is not preferable because the mixing property of the BS resin becomes insufficient and the impact resistance of the molded article obtained by directly molding the thermoplastic resin composition of the present invention and the ABS resin decreases.

When the amount of the antistatic agent (D) is less than 5% by weight, the antistatic effect of the thermoplastic resin molded article comprising the thermoplastic resin composition of the present invention and an ABS resin is low, and is 30% by weight.
If it exceeds, the heat resistance of the thermoplastic resin composition itself decreases,
There is a problem that the raw material pellets are fused at the time of drying when producing a thermoplastic resin molded body with an ABS resin, which is not preferable.

The thermoplastic resin composition of the present invention has a temperature of 26.
Melt viscosity at 0 ° C. is 20,000 poise or less, preferably 15,000 poise or less, 5000 poise
It is necessary to be above. In the range exceeding 20,000 poise, the dispersion becomes poor, and the antistatic property of the molded article obtained by directly molding the thermoplastic resin composition of the present invention and the ABS resin is lowered, which is undesirable. There is a problem that it is unstable, surging (pulsation) occurs in the molding machine, and the plasticization time becomes constant, making it difficult.

The temperature 220 of the thermoplastic resin composition of the present invention
° C, melt flow rate at 10 kg load (MF
R) is not particularly limited, but is preferably 3 to 100 g /
It is 10 minutes, particularly preferably 35 to 80 g / 10 minutes.
If it is less than 3 g / 10 minutes, the molded article obtained by directly molding with an ABS resin tends to have a low antistatic property, and
If the heating time exceeds / 10 minutes, the heat resistance and impact resistance of the molded body are likely to decrease.

The method of mixing the components (A), (B), (C) and (D) during the production of the thermoplastic resin composition of the present invention is not particularly limited, and any known means can be used. be able to. For example, a Banbury mixer,
Examples include a tumbler mixer, a mixing roll, a single-screw or twin-screw extruder. As a mixing form, there is a method of obtaining a composition from ordinary melt mixing and blending in a solution.

The ABS resin which can be used at the time of direct molding with the thermoplastic resin composition of the present invention is not particularly limited. Specifically, ABS (acrylonitrile-butadiene-styrene) resin, α-methyl Styrene-based heat-resistant ABS (acrylonitrile-butadiene-α-
Methyl styrene) resin, maleimide-based heat-resistant ABS (acrylonitrile-butadiene-styrene-N-phenylmaleimide) resin, AES (acrylonitrile-EPDM)
-Styrene) resin, AAS (acrylonitrile-acrylate-styrene) resin, MBS (methyl methacrylate-butadiene-styrene) resin, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) resin, and the like. Those having a combined content of less than 35% by weight are used.

The thermoplastic resin composition of the present invention may contain an ABS resin in a range that does not deviate from the object of the present invention, specifically, in a range of 0 to 20%.

Melt flow rate (MFR) of thermoplastic resin composition and ABS resin usable in the present invention
Is not particularly limited, but is preferably 1/1 to 10 /
It is one. If the ratio is less than 1/1, dispersion tends to be poor, and the antistatic property tends to be poor. If the ratio exceeds 10/1, slip tends to occur during molding plasticization, and molding is difficult.

The mixing ratio of the thermoplastic resin composition of the present invention to the ABS resin is not particularly limited, but preferably 4 to 50% by weight of the thermoplastic resin composition and 50 to 50% of the ABS resin.
96% by weight, and more preferably 5 to 5%.
The content is 40% by weight and 60 to 95% by weight of the ABS resin, particularly preferably 5 to 20% by weight of the thermoplastic resin composition and 80 to 95% by weight of the ABS resin. When the amount of the thermoplastic resin composition is less than 4% by weight, the molded article obtained by directly molding with the ABS resin has insufficient antistatic properties, and when it exceeds 50% by weight, the direct molding with the ABS resin is insufficient. Properties tend to decrease.

Further, the thermoplastic resin composition of the present invention further comprises an antioxidant, a stabilizer, an ultraviolet absorber, a flame retardant, a plasticizer, a lubricant, a colorant, talc, silica, clay, mica,
It is also possible to add at least one selected from fillers such as calcium carbonate. When the thermoplastic resin composition and the ABS resin of the present invention are supplied to a molding machine, these additives can be supplied simultaneously.

Coloring agents which can be generally used for ABS resins include titanium oxide, iron oxide (petal oxide), ultramarine, phthalocyanine blue, carbon black, titanium yellow, cobalt blue, perinone red, perylene red, and quinacridone red. And anthraquinone red are preferred.

As a method of supplying the thermoplastic resin composition of the present invention and the ABS resin to a molding machine, a method of supplying a preblended material using a known device such as a tumbler mixer or a V blender, a method of supplying a molding machine, And a method in which the two materials are separately and quantitatively supplied to the hopper described above, or a method in which the thermoplastic resin composition and the ABS resin are melt-kneaded in advance into pellets and then supplied to a molding machine. It is not particular about the supply method. Further, a colorant or a colorant masterbatch can be simultaneously supplied according to the purpose.

Examples of the molding machine used in the present invention include an injection molding machine, a sheet molding machine, a blow molding machine and an injection blow molding machine. The optimum value for the cylinder set temperature of the molding machine is determined by the types of the thermoplastic resin composition and the ABS resin. Specifically, in the case of the present invention, 220 ° C. to 280 ° C.
Is preferred.

Further, in the case of injection molding, by installing a known static mixer, for example, a Toray type, a through type, a Kenix type, etc., between the molding machine cylinder and the nozzle, a more excellent antistatic effect can be obtained. A molded article having properties can be obtained.

Further, as the screw of the injection molding machine, a full-flight screw having the highest versatility can be used, but a dalmage type, pin type or Maddock type screw having higher kneading properties can also be used.

[0058]

EXAMPLES The present invention will be further described with reference to the following examples.
The present invention is not limited to the following examples as long as the gist is not exceeded. All parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

Maleimide Copolymer as Component (A) Experimental Example 1 Production of Maleimide Copolymer (SMI-1) In an autoclave equipped with a stirrer, 60 parts of styrene, α
-Charge 0.05 parts of methylstyrene dimer and 100 parts of methyl ethyl ketone, purge the system with nitrogen gas, raise the temperature to 85 ° C, and add 40 parts of maleic anhydride and 0.15 part of benzoyl peroxide to methyl ethyl ketone 20.
The solution dissolved in 0 parts was added continuously over 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.
Then, the mixture was 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-based copolymer. C-13 NMR analysis revealed that the conversion of the acid anhydride group to the imide group was 93 mol%. This maleimide-based copolymer was a copolymer containing 51% of N-phenylmaleimide units and was designated as copolymer SMI-1. The gel permeation chromatography (GPC) analysis revealed that the weight average molecular weight was 145,000. For GPC measurement, "SHOdex GPC" manufactured by Showa Denko KK
The weight average molecular weight in terms of polystyrene was determined using "SYSTEM-21" and a calibration curve prepared using polystyrene having a standard molecular weight. Table 1 shows the composition ratio of the maleimide-based copolymer (SMI-1) used above and the weight average molecular weight determined by gel permeation chromatography (GPC).

[0060]

[Table 1]

AS copolymer of component (B) Experimental example 2 Production of AS copolymer (AS-1) In a reaction vessel equipped with a stirrer, 75 parts of styrene, 25 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, 0.5 parts of t-dodecylmercaptan, 0.5 parts of benzoyl peroxide 0 .2 parts and water 250 parts were charged, and the temperature was raised to 70 ° C. to start polymerization. After 7 hours from the start of polymerization, the temperature was raised to 75 ° C.
And kept for 3 hours to complete the polymerization. The polymerization rate is 97
% Has been reached. 200 parts of a 5% hydrochloric acid aqueous solution was added to the obtained reaction solution to cause precipitation, dehydration and drying, and a white bead-like copolymer was obtained. This was designated as AS-1.

Experimental Example 3 Production of AS Copolymer (AS-2) In a reaction vessel equipped with a stirrer, 75 parts of styrene, 25 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, 0.3 parts of t-dodecylmercaptan, 0.3 parts of benzoyl peroxide 0 .2 parts and water 250 parts were charged, and the temperature was raised to 70 ° C. to start polymerization. After 7 hours from the start of polymerization, the temperature was raised to 75 ° C.
And kept for 3 hours to complete the polymerization. The polymerization rate is 97
% Has been reached. 200 parts of a 5% hydrochloric acid aqueous solution was added to the obtained reaction solution to cause precipitation, dehydration and drying, and a white bead-like copolymer was obtained. This was designated as copolymer AS-2.

Table 2 shows the component composition ratio of the AS copolymer used above and the weight average molecular weight measured by GPC.

[0064]

[Table 2]

(A) ABS Graft Copolymer of Component (C) Production of ABS Graft Copolymer (GF-1) 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%), 1 part of sodium stearate, 0.1 part of sodium formaldehyde sulfoxylate, tetrasodium ethylenediamine tetraacetic acid 0.0
3 parts, ferrous sulfate 0.003 part, and pure water 150 parts
The mixture was heated to 0 ° C., and 50 parts of a monomer mixture composed of 75% of styrene and 25% of acrylonitrile, 0.2 parts of t-dodecyl mercaptan, and 0.15 parts of cumene hydroperoxide were continuously added thereto over 6 hours. 65 ° C after further addition
And polymerized for 2 hours. The conversion reached 97%. An antioxidant (Irganox 107) was added to the obtained latex.
6) After adding 0.3 parts, 300 parts of a 5% calcium chloride aqueous solution was added, and the mixture was coagulated, washed with water and dried to obtain a graft copolymer (GF-1) as a white powder.

Experimental Example 5 ABS-based graft copolymer (G
Production of F-2) In the production of GF-1 shown in Experimental Example 4, a graft copolymer (GF-2) was obtained in the same manner as in Experimental Example 4 except that 0.2 parts of t-dodecylmercaptan was not used. Was.

Table 3 shows the composition ratio of the ABS-based graft copolymer used, the graft ratio, and the weight-average molecular weight of the ungrafted copolymer.

These values are obtained by setting a fixed amount of a sample at a temperature of 25 ° C.
After swelling in a solvent methyl ethyl ketone (MEK) for 24 hours, the supernatant solution obtained by centrifugation was used as an ungrafted copolymer, and the weight-average molecular weight by GPC measurement and the composition analysis by Kjeldahl nitrogen quantitative analysis were performed. The MEK-insoluble matter precipitated by centrifugation was taken out, and the solvent was completely dried and removed. Then, the weight of the rubbery polymer was determined by a halogen addition method, and the graft ratio was determined by the following equation.

Graft ratio = [(weight of MEK insoluble matter−weight of rubbery polymer) / weight of rubbery polymer] × 100 (%)

[0070]

[Table 3]

As the antistatic agent of the component (D), polyoxyethylene nonylphenyl ether (Nonion NS-220 manufactured by NOF: hereinafter referred to as D-1) and N, N'-bis- (2-hydroxyethyl) alkyl An amine (Miyocol 324 manufactured by Miyoshi Oil &Fat; hereinafter, referred to as D-2) was used.

Experimental Example 6 Manufacture of thermoplastic resin composition The kneading and mixing for preparing the thermoplastic resin composition is carried out by a twin screw extruder TEM-35B manufactured by Toshiba Machine Co. (screw diameter: 37 m
m, L / D = 32), cylinder temperature setting 280
° C, screw rotation speed 250 rpm, discharge rate 20 kg /
The operation was performed under the conditions of hr.

Tables 4 and 5 show the mixing ratios of the prepared thermoplastic resin compositions. The prepared thermoplastic resin compositions were referred to as MB-1 to MB-10, respectively.

[0074]

[Table 4]

[0075]

[Table 5]

ASTM D-12 is used as an ABS resin.
A commercially available ABS resin “QF (manufactured by Denki Kagaku Kogyo Co., Ltd.)” having a melt flow rate of 40 g / 10 minutes measured at a temperature of 220 ° C. and a load of 10 kg according to A.38 (A
A commercially available maleimide-based ABS resin “K-090 (manufactured by Denki Kagaku Kogyo Co., Ltd.)” having a melt flow rate of 13 g / 10 minutes under the same conditions as in the case of BS-1) (ABS-
2).

Examples 1 to 10 and Comparative Examples 1 to 6 A thermoplastic resin composition and an ABS resin were molded at the compounding ratios shown in Tables 6 to 8, and the IZOD impact strength and thermal deformation at that time were obtained. The results of the temperature (HDT) and the surface resistivity were also shown. The thermoplastic resin composition and the ABS resin of the present invention are dried at a temperature of 80 ° C. for 3 hours, and then dried with a tumbler mixer.
The mixture was mixed for minutes and fed to an injection molding machine. The injection molding was performed by using an injection molding machine K-125 manufactured by Kawaguchi Iron Works. The molding conditions are as follows. Cylinder set temperature: 260 ° C. Injection speed: 70% Mold temperature: 60 ° C. Screw: full flight type In Comparative Example 1, the thermoplastic resin composition was fused during drying and could not be molded. The results are shown in Tables 6 to 8.

Example 11 Ten parts of the thermoplastic resin composition MB-1 and 90 parts of an ABS resin (ABS-1) were extruded at a temperature of 260 ° C. using a 40 mmφ single screw extruder to obtain pellets. Using the pellets, test pieces were prepared under the same molding conditions as in Example 3, and various physical properties were measured. Table 7 shows the results.

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

Comparative Examples 7 to 9 D-1 was blended as an antistatic agent with an ABS resin at a ratio shown in Table 9, and the blend was fed to a co-rotating twin-screw extruder equipped with a 35 m / m devolatilizer. At a temperature of 250 ° C.
Pelletized. Examples 1 to 10 using this pellet
In the same manner as in the above, test pieces for measuring physical properties were prepared at a temperature of 260 ° C. using an injection molding machine, and various physical properties were measured. Table 9 shows the results.

Reference Examples 1 and 2 Test pieces were prepared from the thermoplastic resin composition and ABS resins (ABS-1 and ABS-2) not using an antistatic agent under the same molding conditions as in Example 3. Various physical properties were measured. Table 9 shows the results.

[0084]

[Table 9]

Physical property measurement test method 1) Heat distortion temperature (HDT): load 18.6 kg / cm ²
Was measured according to ASTM D-648. 2) IZOD impact strength: Measured according to ASTM D-256 using a 1/4 inch thick notched test piece. 3) Surface resistivity: The surface resistivity was injection molded 12
The measurement was performed using a 7 × 127 × 2 mm square plate. The square plate immediately after molding is washed in pure water for 1 minute and dried sufficiently.
In accordance with 911, the surface resistivity was adjusted at a temperature of 23 ° C. and a humidity of 50% RH for 24 hours to obtain a surface resistivity of R manufactured by Kawaguchi Electric Works, Ltd.
Measured with a -503 super insulation meter. 4) Melt viscosity: using a capillary rheometer (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a shear rate of 60 [sec ^-1 ] and a cylinder temperature of 260 ° C., a capillary length of 40 m.
m and a diameter of 1 mm were measured according to JIS K-7199. 5) Melt flow rate (MFR): Measured according to JIS K-6874 at a load of 10 kg and a temperature of 220 ° C.

As is clear from the results shown in Tables 6 and 7, the thermoplastic resin molded articles of Examples 1 to 11 were excellent in I
It shows the ZOD impact strength, heat resistance, and surface resistivity.

In Comparative Example 1, since the amount of the antistatic agent in the thermoplastic resin composition exceeded 30%, it could not be molded by fusing during drying.

In Comparative Examples 2 to 6, the viscosity of the thermoplastic resin composition at the time of melting exceeded 20,000 poise, and the thermoplastic resin compositions were not uniformly mixed, so that the IZOD impact strength and the surface resistivity were inferior.

Further, when Comparative Examples 7 to 9 are compared with Examples 1 to 6, the surface resistivity is inferior, and the direct molding method using the thermoplastic resin composition of the present invention is superior. You can see that it is.

[0090]

According to the molding method of the present invention using the thermoplastic resin composition of the present invention, a resin molded article having excellent heat resistance and antistatic properties can be obtained economically and advantageously. The present invention relates to automobile parts, electric and electronic parts, office equipment parts, heating appliances, tableware, refrigerator parts, bathtub parts, shower parts, and water purifier parts, which have conventionally been required to use an ABS resin and have antistatic performance. It can be applied particularly effectively as a material for toilet seats and the like.

Claims (3)

[Claims] (1) Component (A): Maleimide copolymer 0 to 4
0% by weight, (B) component: 10 to 95% by weight of AS copolymer, (C) component: 0 to 40% by weight of ABS graft copolymer, (D) component: 5 to 30% by weight of antistatic agent [Where the total of (A) to (D) is 10
0% by weight], the temperature of the thermoplastic resin composition is 26
When the melt viscosity at 0 ° C. is 60 ± 5 (sec.
(c- ¹ ) a thermoplastic resin composition having a molecular weight of 20,000 poise or less. 2. The thermoplastic resin composition 4 to 5 according to claim 1.
A thermoplastic resin molded article obtained by supplying 0% by weight and 50 to 96% by weight of an ABS resin to a molding machine and molding. 3. The thermoplastic resin composition 4 to 5 according to claim 1.
A method for producing a thermoplastic resin molded article, wherein 0% by weight and 50 to 96% by weight of an ABS resin are simultaneously supplied to a molding machine and molded.