JPH1135760A - Thermoplastic resin composition, molded article and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give molded products improved in chemical resistance and impact resistance by mixing an unsaturated dicarboxylic acid copolymer with a vinyl copolymer, a graft copolymer, a polyamide resin, an elastomer copolymer and an acrylic rubber polymer having specified properties. SOLUTION: This composition comprises 0.25-46 wt.% copolymer comprising 40-80 wt.% aromatic vinyl monomer, at most 20 wt.% unsaturated dicarboxylic acid anhydride, 0-60 wt.% unsaturated dicarboxylic acid imide, etc., 1.0-76.5 wt.% vinyl copolymer comprising 60-80 wt.% aromatic vinyl monomer, 20-40 wt.% vinyl cyanide monomer, etc., 10.1-5-46 wt.% copolymer obtained by grafting 35-65 pts.wt. mixture containing 50-80 wt.% aromatic vinyl monomer, etc., onto 35-65 pts.wt. rubbery polymer, 1.5-15 wt.% polyamide resin, 1.0-10 wt.% ethylene/α-olefin elastomer copolymer containing an unsaturated dicarboxylic acid and 2.0-20 wt.% acrylic rubbery polymer having a glass transition temperature of 0 deg.C or below and a gel fraction of 70 wt.% or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition having excellent chemical resistance, a molded article, and a method for producing the molded article. More specifically, thermoplastics composed of a specific unsaturated dicarboxylic acid copolymer, vinyl copolymer, graft copolymer, polyamide resin, elastomer copolymer composed of ethylene-α-olefin, and acrylic rubber-like polymer Resin composition. In particular, the present invention relates to a specific polyamide-containing resin and a specific acrylic rubber-like polymer-containing resin capable of imparting excellent chemical resistance to an ABS resin, and
The present invention relates to a thermoplastic resin composition comprising a BS resin and a thermoplastic resin molded article obtained by simultaneously supplying a three-component resin to a molding machine and molding (hereinafter, referred to as a direct molding method), and a method for producing the same. The molded article of the present invention can be preferably used for automobile parts, electric and electronic parts, office equipment parts, heating appliances, tableware, refrigerator parts, bathtub parts, shower parts, water purifier parts, toilet seats and the like.

[0002]

2. Description of the Related Art ABS resins are excellent in high impact strength and rigidity, moldability, gloss, and appearance, and are widely used in industrial parts and household electric appliances. On the other hand, in these applications,
There are many opportunities to come into contact with various chemicals and detergents, and cracks may occur in the ABS resin molded article. In order to prevent this, it is required to impart chemical resistance to the ABS resin.

In order to improve the chemical resistance of the ABS resin, a method of increasing the molecular weight of the AS resin constituting the resin component of the ABS resin, or the composition ratio of acrylonitrile, which is a polar monomer constituting the AS resin, Are known, but these methods impair the processability of the ABS resin and have insufficient chemical resistance.

Further, a composition comprising a mixture of a rubber-containing styrene resin and an acrylate polymer has also been proposed (Japanese Patent Publication No. 63-22222), and it is known that the chemical resistance is remarkably improved. ing. However, in this method, the effect of improving the chemical resistance may not be sufficiently obtained depending on the type of the chemical.

Further, a composition comprising a maleimide-based ABS resin, a polyamide and a modified ethylene-α-olefin-based elastomer has been proposed (JP-A-7-316381).
It is known that the chemical resistance is improved.

It is also known that an ABS resin and a polyamide-containing resin are simultaneously supplied to a molding machine to obtain a molded article having excellent chemical resistance (Japanese Patent Application Laid-Open No. 8-148976). However, even with these methods, depending on the type of chemical, improvement in chemical resistance may not be sufficient.

Further, in order to produce molded articles corresponding to various chemical resistance levels and other requirements of mechanical properties in these methods, it is necessary to use many kinds (resin pellets) corresponding to the characteristic levels and their types. In order to obtain a variety, a very complicated operation such as a kneading operation is required, and there are disadvantages such as a large cost. Furthermore, since a kneading operation is performed to obtain the varieties, especially the ABS resin is deteriorated, and the impact strength is reduced.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks at the same time.
An object of the present invention is to provide a thermoplastic resin composition and a thermoplastic resin molded article which are excellent in chemical resistance while maintaining excellent impact strength, rigidity, moldability, gloss, and appearance, which are advantages of a system resin. According to the method of the present invention, the chemical resistance can be significantly improved as compared with the conventional method for improving the chemical resistance. Another object of the present invention is to solve the above-described variety of products, complicated operations, disadvantages in economical efficiency, and a decrease in impact strength, which are caused when obtaining a molded body corresponding to the characteristic level.

[0009]

Means for Solving the Problems The present inventors have proposed A
As a result of intensive studies for the purpose of developing a thermoplastic resin composition in which the chemical resistance of the BS resin (I) has been dramatically improved, a specific unsaturated dicarboxylic acid copolymer, vinyl copolymer,
The purpose can be achieved by using a thermoplastic resin composition comprising a graft copolymer, a polyamide resin, an elastomer copolymer composed of ethylene-α-olefin, and an acrylic rubbery polymer, and in particular, an ABS resin (I) To
A copolymer containing a specific proportion of unsaturated dicarboxylic anhydride monomer residues, a graft copolymer, a polyamide resin,
An ethylene-α-olefin-based elastomer having an unsaturated dicarboxylic acid and / or an anhydride group in a specific ratio,
And a polyamide-containing resin (II) containing a vinyl copolymer in a specific ratio as required, an acrylic rubber-like polymer, an aromatic vinyl monomer, a vinyl cyanide monomer, and a copolymer thereof. It has been found that the above-mentioned problems can be solved by blending an acrylic rubber-like polymer-containing resin (III) composed of a vinyl copolymer obtained by polymerizing a polymerizable vinyl monomer, and the present invention has been achieved.

Further, the ABS resin (I), the polyamide-containing resin (II) and the acrylic rubbery polymer (II)
It is also possible to simultaneously supply I) to a molding machine to directly obtain an ABS-based resin molded article having excellent chemical resistance, and this method has the effect of eliminating the kneading operation and reducing the product lineup.

That is, the present invention provides the following (A) component:
46% by weight, component (B) 1.0-76.5% by weight,
(C) component 10.15 to 46% by weight, component (D) component 1.5
To 15% by weight, 1.0 to 10% by weight of component (E), and 2.0 to 20% by weight of component (F), wherein each of these components is component (A): aromatic 40 to 80% by weight of vinyl monomer residue, 20% by weight or less of unsaturated dicarboxylic anhydride monomer residue (excluding 0), 0 to less than 60% by weight of unsaturated dicarboxylic acid imide derivative residue And an unsaturated dicarboxylic acid-based copolymer comprising 0 to 20% by weight of a vinyl monomer residue copolymerizable therewith, (B) component: 60 to 80% by weight of an aromatic vinyl monomer residue, cyanide 20 to 40% by weight of vinyl monomer residue and 0 to 30% by weight of vinyl monomer residue copolymerizable therewith
(C) Component: 35 to 65 parts by weight of a rubbery polymer, 50 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer, and A graft copolymer obtained by graft-polymerizing 35 to 65 parts by weight of a monomer mixture composed of 0 to 30% by weight of a vinyl monomer copolymerizable with: (D) component: polyamide resin, (E) component: unsaturated Elastomer copolymer consisting of ethylene-α-olefin containing 5% by weight or less (but not including 0) of dicarboxylic acid monomer residue and / or acid anhydride monomer residue thereof, Component (F): The glass transition temperature is 0 ° C. or less, the gel content is 70% or less, and the solubility parameter is 8.4 or more.
An acrylic rubber-like polymer which is a homopolymer of an acrylate monomer having a ratio of 9.8 (cal / cc) ^1/2 or a copolymer with another copolymerizable monomer.

Further, the thermoplastic resin composition comprises 50 to 90% by weight of the following ABS resin (I), 5 to 25% by weight of a polyamide-containing resin (II), and an acrylic rubbery polymer-containing resin (III). ) Containing 5 to 25% by weight of a thermoplastic resin composition.
The resin (I) comprises 0 to 50% by weight of the unsaturated dicarboxylic acid copolymer (A), 0 to 80% by weight of the vinyl copolymer (B), and the component (C). The resin comprising the graft copolymer 20 to 50% by weight and the polyamide-containing resin (II) are 5 to 20% by weight of the unsaturated dicarboxylic acid type copolymer (A) and the vinyl type (B). 0 to 30% by weight of a copolymer, 3 to 20% by weight of a graft copolymer (C), 30 to 6% of a polyamide resin (D)
A resin composition comprising 0% by weight and 20 to 40% by weight of an ethylene-α-olefin elastomer copolymer (E), and an acrylic rubbery polymer-containing resin (II)
I) is a vinyl copolymer 20 to 6 of the above-mentioned component (B).
0% by weight of the acrylic rubbery polymer of the component (F) 40 to
80% by weight of the resin composition. However, ABS
The components (A), (B), and (C) used in the resin (I), the polyamide-containing resin (II), and the acrylic rubber-like polymer-containing resin (III) must be the same. There is no.

Further, the present invention relates to a resin (II) containing 50 to 90% by weight of the ABS resin (I).
5 to 25% by weight and 5 to 25% by weight of an acrylic rubber-like polymer-containing resin (III) are simultaneously supplied to a molding machine to form a thermoplastic resin molded article. It is a manufacturing method.

Hereinafter, the present invention will be described in detail. The unsaturated dicarboxylic acid-based copolymer as the component (A) used in the present invention will be described. Examples of the aromatic vinyl monomer constituting the component (A) include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Particularly preferred.

Examples of the unsaturated dicarboxylic anhydride include anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, and maleic anhydride is particularly preferred.

Examples of the unsaturated dicarboxylic acid imide derivative include imide monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide and glutarimide. N-phenylmaleimide is particularly preferred.

The vinyl monomers copolymerizable therewith include vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, and acrylic acids such as methyl acrylate, ethyl acrylate and butyl acrylate. Ester monomers, methacrylic acid ester monomers such as methyl methacrylic acid ester and ethyl methacrylic acid ester, vinyl carboxylic acid monomers such as acrylic acid and methacrylic acid, acrylamide, methacrylamide, and N-vinyl Examples thereof include carbazole, and among them, monomers such as acrylonitrile, acrylic ester, methacrylic ester, acrylic acid, and methacrylic acid are particularly preferable.

The copolymer containing an aromatic vinyl monomer and an unsaturated dicarboxylic acid anhydride as essential components includes an unsaturated dicarboxylic acid anhydride, an aromatic vinyl monomer and, if necessary, an unsaturated dicarboxylic acid imide and / or an unsaturated dicarboxylic acid imide. Alternatively, a vinyl monomer copolymerizable therewith is copolymerized. Alternatively, an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride and, if necessary, a vinyl monomer copolymerizable therewith are copolymerized and then reacted with ammonia and / or a primary amine to obtain an imide derivative. It may be.

The component (A) can be polymerized by a general method such as solution polymerization, bulk polymerization, suspension polymerization, or bulk-suspension polymerization.

The ammonia and the primary amine used in the imidization reaction for forming the imide derivative may be either anhydrous or in an aqueous solution. Examples of the primary amine include methylamine, ethylamine, cyclohexyl and the like. Examples thereof include alkylamines such as amines and / or aromatic amines such as aniline, toluidine, and naphthylamine.

When the imidization reaction is carried out in a solution state or a suspension state, it is preferable to use a usual reaction vessel, for example, an autoclave, and when the imidation reaction is carried out in a bulk molten state, an extruder equipped with a devolatilizer is used. You may.

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. On the other hand, when the temperature exceeds 350 ° 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 amount of the aromatic vinyl monomer residue used in the component (A) is 40 to 80% by weight, but 45 to 60% by weight.
Is particularly preferred. If the amount is less than 40% by weight, the moldability decreases. If the amount exceeds 80% by weight, the heat resistance of the thermoplastic resin composition decreases, which is not preferable. Unsaturated dicarboxylic anhydride monomer residue is 20% by weight or less (however, 0 is not included),
Particularly, 0.5 to 15% by weight is preferable. If no unsaturated dicarboxylic anhydride residue is contained, the compatibility between the component (A) and the polyamide resin is reduced, which not only causes delamination of the molded product but also lowers the impact strength. If it exceeds 20% by weight, crosslinking with the terminal amino group in the polyamide resin proceeds, and MF
Not only does R significantly decrease and the surface appearance is impaired,
Moldability also decreases. The amount of the unsaturated dicarboxylic acid imide derivative residue is 0 to 60% by weight, and if it exceeds 60% by weight, the compatibility of the thermoplastic resin composition is inferior and the impact resistance is greatly reduced.

Next, the vinyl copolymer (B) will be described. The aromatic vinyl monomer used in the component (B) of the present invention is a styrene monomer such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene, and styrene is particularly preferred. . Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferable.

The vinyl monomers copolymerizable therewith include acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate, methyl methacrylate and ethyl methacrylate. Methacrylic acid ester monomers such as acrylic acid, vinyl carboxylic acid monomers such as methacrylic acid, acrylamide, methacrylamide, and N
-Vinyl carbazole and the like. Of these, monomers such as methacrylic acid esters, acrylic acid, and methacrylic acid are particularly preferred.

The component (B) can also be produced by a usual polymerization method,
For example, polymerization methods such as suspension polymerization, solution polymerization, and emulsion polymerization can be adopted.

The aromatic vinyl monomer residue in the component (B) is 60 to 80% by weight, preferably 68 to 78% by weight.
It is. If it is less than 60% by weight or more than 80% by weight, the moldability is reduced. Further, the amount of the vinyl cyanide monomer residue is from 20 to 40% by weight, particularly preferably from 22 to 32% by weight. If it is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) is reduced, which causes delamination of the molded product and a reduction in impact strength.

Next, the graft copolymer of the component (C) of the present invention will be described. The rubbery polymer used as the component (C) is a butadiene polymer, a copolymer of a butadiene and a copolymerizable vinyl monomer, for example, a butadiene-styrene copolymer, an ethylene-propylene copolymer, and an ethylene-polymer. Examples thereof include a propylene-diene copolymer, an acrylate polymer, and a copolymer of an acrylate ester and a copolymerizable vinyl monomer.

The aromatic vinyl monomer used for the component (C) includes styrene monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Is preferred. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like, and acrylonitrile is particularly preferable.

The vinyl monomers copolymerizable therewith include acrylate monomers 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
-Vinyl carbazole and the like, among which acrylic acid esters, methacrylic acid esters, acrylic acid,
Monomers such as methacrylic acid are particularly preferred.

In the production of the graft polymer, any known polymerization techniques can be employed, for example, aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization, and poor solvent for the produced polymer. And a combination thereof.

The rubber particle size of the graft copolymer is from 0.1 to
The range of 0.6 μm is preferable from the viewpoint of impact resistance. When the graft ratio is 20 to 80% and the weight-average molecular weight of the ungrafted copolymer is in the range of 50,000 to 200,000, the balance between impact resistance and moldability is good.

The component (C) is composed of 50 to 80% by weight of an aromatic vinyl monomer in the presence of 35 to 65 parts by weight of a rubbery polymer,
It is obtained by graft polymerization of 35 to 65 parts by weight of a monomer mixture consisting of 20 to 40% by weight of a vinyl cyanide monomer and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. Particularly, 65 to 70% by weight of an aromatic vinyl monomer, 22 to 32% by weight of a vinyl cyanide monomer, and 3 to 13% by weight of a vinyl monomer copolymerizable therewith are preferred. If the amount of the aromatic vinyl monomer is less than 50% by weight, the moldability decreases,
If it exceeds 80% by weight, the heat resistance decreases. Also,
If the amount of the vinyl cyanide monomer is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) is reduced, which causes delamination of the molded article and a reduction in impact strength. When the amount of the rubbery polymer is less than 35 parts by weight, the impact resistance is reduced, and when it exceeds 65 parts by weight, the heat resistance and the moldability are reduced.

Next, the polyamide resin (D) of the present invention will be described. Examples of the polyamide resin (D) include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-12, nylon-11, and the like. These may be used alone or in combination. It can also be used.

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 containing the unsaturated dicarboxylic acid monomer residue and / or the acid anhydride monomer residue of the component has a number average molecular weight of 10,000 to
In the range of 1,000,000 and an ethylene content of 5
Those having 0 to 80 mol% are preferred. As the α-olefin, propylene, 1-butene and 1-pentene can be used, and propylene is particularly preferable.

As the unsaturated dicarboxylic acid and / or its anhydride used for the modification as the functional group of the component (E),
There are maleic acid, itaconic acid, citraconic acid, aconitic acid, and their acid anhydrides, with maleic anhydride being particularly preferred.

The content of unsaturated dicarboxylic acid and / or anhydride thereof is 5% by weight or less (however, 0 is not included),
Preferably it is 0.5 to 5% by weight, and if it exceeds 5% by weight, a gel or the like is generated in the composition. If it is less than 0.5% by weight, the compatibility of the composition is insufficient, causing delamination, and no impact strength is exhibited. The modified ethylene-α-olefin elastomer can be obtained by using the production method of Example 1 disclosed in Japanese Patent Publication No. 58-445.

Next, the acrylic rubbery polymer as the component (F) of the present invention will be described. Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, cyclohexyl acrylate, octyl acrylate, hydroxyethyl acrylate, and methoxyethyl acrylate, with butyl acrylate being particularly preferred.

As other copolymerizable monomers, styrene,
styrene monomers such as α-methylstyrene and t-butylstyrene, vinyl cyanide monomers such as acrylonitrile and methacrylonitrile, methacrylate monomers such as methyl methacrylate and butyl methacrylate, ethylene, propylene, -Olefin monomers such as butene, isobutylene and 2-butene, and vinyl ether monomers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether, and the like, with methyl methacrylate being particularly preferred.

Further, divinylbenzene, ethylene glycol dimethacrylate, 1,3
-Butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, propylene glycol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, trimethylolpropane trimethacrylate, allyl acrylate, vinyl acrylate,
Examples include polyfunctional vinyl monomers such as vinyl methacrylate, glycidyl acrylate, and glycidyl methacrylate, and ethylene glycol methacrylate is particularly preferred.

It is essential that the component (F) has an acrylate monomer residue. Further, a mixture of two or more types of the component (F) can also be used.

The component (F) of the present invention has a glass transition temperature of 0.
C. or lower, the gel content is 70% or lower, and the solubility parameter is 8.4 to 9.8 (cal / cc) ^1/2 . When the glass transition temperature exceeds 0 ° C., the impact strength of the thermoplastic resin composition decreases, and the chemical resistance becomes insufficient.

On the other hand, if the gel content exceeds 70%, the thermoplastic resin composition and the molded product obtained by direct molding have insufficient chemical resistance. The gel content of the component (F) of the present invention is determined by completely removing the methyl ethyl ketone solution of the component (F) at a temperature of 30 ° C. for 24 hours and then filtering through a 200-mesh stainless steel wire mesh to completely remove the filtration residue. Dry,
{(Filtration residue weight) / ((A) component weight)} × 100%
Asked.

Further, the solubility parameter is 8.4-9.
If the ratio is out of the range of 8 (cal / cc) ^1/2 , the chemical resistance of the thermoplastic resin composition and the molded product obtained by direct molding are not sufficient.

The solubility parameter is John
"Polymer Handbook" published by Wiley & Son
(1989, Third Edition, Section VII Nos. 519-5
59), and the solubility parameter δ _T of the copolymer was determined to be additive in terms of weight fraction. That is, the solubility parameter [delta] _n of a homopolymer of each (meth) acrylate monomer constituting the copolymer made of m types of (meth) acrylic acid ester monomer, the weight fraction W _n Is calculated from equation (1) by using equation (1).

[0046]

(Equation 1)

For example, normal butyl acrylate 70
The solubility parameter of the acrylic rubbery polymer composed of 30% by weight of methyl methacrylate and 30% by weight of methyl methacrylate is 8.8 (ca)
1 / cc) ^1/2 and the solubility parameter of methyl methacrylate 9.5 (cal / cc) ^1/2
To obtain 9.0 (cal / cc) ^1/2 .

The method for producing the component (F) is not particularly limited, but production by an emulsion polymerization method is industrially advantageous, and a known technique of the emulsion polymerization method can be applied as it is.

In the present invention, the component (A), the component (B),
The compounding ratio of the component (C), the component (D), the component (E), and the component (F) is as follows: component (A) 0.25 to 46% by weight;
Component 1.0 to 76.5% by weight, component (C) 10.15 to
46% by weight, 1.5 to 15% by weight of component (D), 1.0 to 10% by weight of component (E), and 2.0 to 20% by weight of component (F). If it is less than 25% by weight, the compatibility with the component (D) is not sufficient, and if it exceeds 46% by weight, the impact resistance and moldability of the resin composition deteriorate.
If the component (B) content is less than 1.0% by weight, the moldability decreases, and
If it exceeds 6.5% by weight, the impact resistance decreases. If the content of the component (C) is less than 10.15% by weight, the impact resistance is lowered, and
If the amount is more than 10% by weight, the moldability decreases. If the component (D) is less than 1.5% by weight, the chemical resistance is not sufficient, and if it exceeds 15% by weight, the dimensional stability decreases. The component (E) is 1.
If it is less than 0% by weight, the impact resistance is not sufficient, and if it exceeds 10% by weight, the moldability is reduced. (F) component is 2.0% by weight
If it is less than 10%, the chemical resistance is not sufficient, and if it exceeds 20% by weight, the appearance becomes poor.

Further, the present invention is a thermoplastic resin composition comprising the above-mentioned components (A) to (F), and when these are mixed, the following ABS resin (I) 50 to 90% by weight,
5 to 25% by weight of a polyamide-containing resin (II) and 5 to 25% by weight of an acrylic rubbery polymer-containing resin (III)
Is preferably mixed. ABS resin (I)
0 to 50% by weight of an unsaturated dicarboxylic acid-based copolymer as the component (A), 0 to 80% by weight of a vinyl-based copolymer as the component (B),
And a graft copolymer (C) of 20 to 50% by weight, and specific examples thereof include ABS (acrylonitrile-butadiene-styrene) resin and α-methylstyrene-based heat-resistant ABS (acrylonitrile-butadiene-α). -Methylstyrene; acrylonitrile-butadiene-α-methylstyrene-styrene) resin, maleimide-based heat-resistant ABS (acrylonitrile-butadiene-N-phenylmaleimide-styrene) resin, AES (acrylonitrile-EPDM-styrene) resin, AAS (acrylonitrile-acrylate) -Styrene) resin, MBS (methyl methacrylate-butadiene-styrene; methyl methacrylate-acrylonitrile-butadiene-styrene) resin, and the like.

The polyamide-containing resin (II) contains 5 to 20% by weight of the unsaturated dicarboxylic acid copolymer (A), 0 to 30% by weight of the vinyl copolymer (B),
(C) 3 to 20% by weight of the graft copolymer of the component, (D)
A resin composition comprising 30 to 60% by weight of a polyamide resin as a component and 20 to 40% by weight of an ethylene-α-olefin-based elastomer copolymer as a component (E). If the solubility is not sufficient and exceeds 20% by weight, the impact resistance and moldability of the composition are significantly reduced. If the component (B) exceeds 30% by weight, there is a problem that the impact resistance is reduced. If the amount of the component (C) is less than 3% by weight, the impact resistance is reduced, and if it exceeds 20% by weight, the moldability is reduced. If the component (D) is less than 30% by weight, the chemical resistance is not sufficient, and if it exceeds 60% by weight, the dimensional stability decreases.
If the component (E) is less than 20% by weight, the impact resistance is not sufficient, and if it exceeds 40% by weight, the moldability decreases.

In order to obtain the polyamide-containing resin (II) of the present invention, the method of mixing the components (A) to (E) 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 composition from a blend in a multi-stage molten mixture using ordinary contact mixing, master pellets and the like. Particularly, when the components (D) and (E) are melt-mixed in advance and then mixed with the remaining components (A) to (C), the chemical resistance, impact resistance and moldability of the molded product are further improved. .

Next, the acrylic rubber-like polymer-containing resin (III) of the present invention comprises 20 to 60% by weight of the vinyl copolymer (B) and the acrylic rubber-like polymer (F). A resin comprising 40 to 80% by weight of the resin, preferably 25 to 50% by weight of the vinyl copolymer (B) and 50 to 75% by weight of the acrylic rubbery polymer (F).
Consists of

If the vinyl copolymer of the component (B) is less than 20% by weight, the component (F) will agglomerate and the molded article will have poor appearance. On the other hand, if the content is more than 60% by weight, the impact strength of the molded article decreases.

If the acrylic rubbery polymer as the component (F) is less than 40% by weight, a large amount must be blended in order to obtain a desired molded article having chemical resistance, which is economically disadvantageous. In addition, the impact strength is reduced. Also, 80
When the content is more than the weight percentage, the acrylic rubber-like polymer aggregates, and the molded article has poor appearance.

The vinyl copolymer of the component (B) has the aromatic vinyl monomer residues 60 to 8 as described above.
0% by weight, 20 to 40% by weight of a vinyl cyanide monomer residue, and 0 to 3 of a vinyl monomer residue copolymerizable therewith.
0% by weight. If the ratio is outside this range, the compatibility with the component (F) will be poor, and the impact strength of the thermoplastic resin composition and the molded product obtained by direct molding will decrease.

The method of mixing the components (B) and (F) during the production of the acrylic rubbery polymer-containing resin (III) of the present invention is not particularly limited, and any known means can be used. Examples of the means include a Banbury mixer, a mixing roll, and an extruder such as a single-screw or twin-screw extruder. When both the component (B) and the component (F) are produced by an emulsion polymerization method, the component (B) latex and the component (F)
It is preferable to blend a predetermined amount of the component latex, use it after dehydration and drying.

When the thermoplastic resin composition of the present invention comprises an ABS resin (I), a polyamide-containing resin (II), and an acrylic rubber-like polymer-containing resin (III), AB
S-based resin (I) is 50 to 90% by weight, preferably 6% by weight.
0 to 80% by weight. If the content of the ABS resin (I) is less than 50% by weight, the moldability and dimensional stability are undesirably reduced.
On the other hand, if the content of the ABS resin (I) exceeds 90% by weight, the chemical resistance is undesirably lowered. Polyamide-containing resin (I
I) is from 5 to 25% by weight, preferably from 10 to 20% by weight. If it is less than 5% by weight, the chemical resistance decreases, and if it exceeds 25% by weight, the moldability decreases, which is not preferable. The acrylic rubber-like polymer-containing resin (III) is 5 to 25% by weight, preferably 10 to 20% by weight. If it is less than 5% by weight, the chemical resistance is reduced. It is not preferable because it decreases.

The method for mixing the components (I) to (III) 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.

The ABS resin (I), the polyamide-containing resin (II), and the acrylic rubber-like polymer-containing resin (III) are used as stabilizers, plasticizers, lubricants, ultraviolet absorbers, and colorants. It is also possible to mix the components according to the formula (1), and further, they can be added when the components (I) to (III) are mixed.

Further, the thermoplastic resin molded article can be directly obtained by supplying the components (I) to (III) of the present invention to a molding machine.

Examples of the molding machine used in the direct molding method include, but are not limited to, an injection molding machine, a sheet molding machine, a blow molding machine, and an injection-blow molding machine.

As a method of supplying the components (I) to (III) to the molding machine by the direct molding method, a tumbler mixer,
A method of supplying a pre-blended material using a known device such as a V blender or a method of separately and quantitatively supplying both materials to a supply port of a molding machine can also be adopted. It is not particular about the supply method.

The optimum temperature of the cylinder of the molding machine is determined by the composition of the thermoplastic resin composition. Specifically, in the case of the present invention, the temperature is preferably 240 ° C. to 280 ° C.

In the case of injection molding, a higher-quality molded product is obtained by installing a known static mixer, for example, a sluser type or a Kenix type, between a molding machine cylinder and a nozzle. I can do it.

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.

Hereinafter, the present invention will be further described with reference to examples. However, 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.

[0068]

【Example】

(1) ABS resin (I) A commercially available ABS resin “GT” as a general ABS resin that satisfies the monomer component of the ABS resin (I) and each copolymer composition.
-R (manufactured by Denki Kagaku Kogyo Co., Ltd.) "(hereinafter referred to as ABS-1
) Is commercially available as heat-resistant ABS resin "K-0
90 (manufactured by Denki Kagaku Kogyo Co., Ltd.) "(hereinafter referred to as ABS-2
) Was used.

(2) Polyamide-containing resin (II) (A) Production of unsaturated dicarboxylic acid copolymer (A) component-1 (A-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 a temperature of 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 92 mol%. This maleimide-based copolymer was a copolymer containing 51% of an N-phenylmaleimide unit as an unsaturated dicarboxylic acid imide derivative, and was referred to as copolymer A-1.

(B) Production of unsaturated dicarboxylic acid copolymer (A) component-2 (A-2) 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and nitrogen gas was introduced into the system. After the replacement, the temperature was raised to 85 ° C., and the mixture was sufficiently stirred while maintaining the temperature at 85 ° C. A-2 was produced in the same manner as in A-1, except that 1 part of α-methylstyrene dimer was added thereto.

(C) Production of unsaturated dicarboxylic acid copolymer (A) component-3 (A-3) 80 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, and nitrogen gas was introduced into the system. After the substitution, the temperature was raised to 85 ° C, and maleic anhydride 10
Of acrylonitrile and 0.15 part of benzoyl peroxide in 200 parts of methyl ethyl ketone were continuously added over 8 hours. After the addition, the temperature was kept at 85 ° C. for a further 3 hours. The reaction solution is supplied to a vented twin-screw extruder, devolatilized, and unsaturated dicarboxylic acid-based copolymer A-3
I got Table 1 shows the composition analysis results and characteristic analysis of A-1 to A-3.

[0072]

[Table 1]

In Table 1, St is styrene, NPMI is N-phenylmaleimide, MAH is maleic anhydride, A
N represents acrylonitrile.

In the copolymer composition, styrene, acrylonitrile and maleic anhydride were determined by analyzing unreacted monomers in the reaction solution by gas chromatography.
For phenylmaleimide, the copolymer was analyzed by C-13 NMR to determine the conversion of maleic anhydride.

The GPC measurement for calculating the weight average molecular weight shown in Table 1 was carried out by using "SHOD" manufactured by Showa Denko KK.
The weight average molecular weight in terms of polystyrene was determined by using "EX GPC SYSTEM-21" and a calibration curve prepared using polystyrene having a standard molecular weight.

(D) Production of vinyl copolymer (B) component-1 (B-1) 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, and t in a reaction vessel equipped with a stirrer. -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 B-1.

(E) Production of Graft Copolymer (C) Component (C-1) Polybutadiene latex 1 was placed in a reaction vessel equipped with a stirrer.
43 parts (solid content 35%, weight average particle diameter 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetylic acid 0.03
Parts, 0.003 parts of ferrous sulfate and 150 parts of pure water were heated to a temperature of 50 ° C., and 50 parts of a monomer mixture composed of 70% of styrene and 30% of acrylonitrile, 0.2 parts of t-dodecyl mercaptan 0.2 And 0.15 part of kimene hydroperoxide were continuously added over 6 hours, and after the addition, the temperature was raised to 65 ° C. and polymerization was carried out for 2 hours. The conversion reached 97%. After adding an antioxidant to the obtained latex,
After coagulation with calcium chloride, washing and drying, a graft copolymer was obtained as a white powder. This was designated as copolymer C-1.

Next, in order to determine the graft ratio of C-1 and the molecular weight of the ungrafted copolymer, 3 g of C-1 was swelled in a methyl ethyl ketone solution, and the ungrafted styrene-styrene in the supernatant solution was centrifuged. When the molecular weight of the acrylonitrile copolymer was measured by gel permeation chromatography, the weight average molecular weight was 82,000. The composition of the gel component (graft copolymer and polybutadiene rubber) precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the weight of the graft copolymer was determined from the amounts of styrene and acrylonitrile. The polybutadiene rubber was analyzed by the bromine addition method, and the weight of the polybutadiene rubber was determined. From the weight of the graft copolymer thus obtained and the weight of the polybutadiene rubber, the graft ratio was determined from the following formula (2).
3%.

[0079]

(Equation 2)

(F) Polyamide resin (D component) As the polyamide resin (D), nylon-6; ε-
Relative viscosity 2.6 obtained by condensation polymerization of caprolactam
Nylon-6 (CM-1017 manufactured by Toray Industries, Inc.) of 5 (concentrated sulfuric acid as a solvent, the concentration was 0.5 g / 100 ml, and the temperature was measured at 25 ° C.) was used.

(G) Modified ethylene-α-olefin-based elastomer copolymer (component E) Ethylene-propylene having a number average molecular weight of 500,000 according to the production method (according to Examples) described in JP-A-52-49289. The copolymer (MFR at a temperature of 230 ° C. under a load of 10 kg is 0.1%).
1.3 g of maleic anhydride was grafted onto 5 g / 10 min of EPR and used.

(H) Mixing of (D) component and (E) component 60% of (D) component and 40% of (E) component are blended, and the blend is co-rotating twin-screw extruder equipped with a 35 mm devolatilizer. At 280 ° C. and pelletized to obtain a resin composition H-1.

(I) Production of polyamide-containing resin (II) The components (A), (B), (C) and H-1 [(D) + (E)] are shown in Table 2. Blend at the indicated ratios, extruded at a temperature of 280 ° C. with a co-rotating twin-screw extruder equipped with a 35 mm devolatilizer, pelletized, and X-1 to X-
5 was created. These melt flow rates (MFR)
Was measured and shown in Table 2.

[0084]

[Table 2]

(3) Resin containing acrylic rubber-like polymer (III) (a) Production of vinyl copolymer (B) component-2 (B-
2) 150 parts of pure water and 2 parts of potassium stearate were charged into an autoclave, and heated to 50 ° C. while stirring. Here, 0.005 part of ferrous sulfate / heptahydrate, 0.01 part of tetrasodium ethylenediaminetetraacetate / dihydrate, and 0.3 part of sodium formaldehyde sulfoxylate / dihydrate were added to 10 parts of pure water. The dissolved aqueous solution was injected. Subsequently, 100 parts of a mixed solution consisting of 75% of styrene and 25% of acrylonitrile and α-methylstyrene dimer 1.
0 parts were continuously added over 4 hours. After completion of the addition of the monomer mixture, tertiary butyl peroxyacetate was added.
One part was added, the temperature of the reaction solution was raised to 70 ° C., and the mixture was further stirred for 2 hours to terminate the polymerization, thereby obtaining a latex of a vinyl copolymer B-2. The weight average molecular weight of this vinyl copolymer B-2 was 225,000.

(B) Production of vinyl copolymer (B) component-3 (B-3) The amount of styrene and acrylonitrile was adjusted to 100 parts of a mixed liquid composed of 85% styrene and 15% acrylonitrile, and α
-The vinyl copolymer B- was produced in the same manner as in the above (A) except that the methylstyrene dimer was changed to 0.7 part.
3 latex was obtained. The weight average molecular weight of this vinyl copolymer B-3 was 243,000. The weight-average molecular weights of B-2 and B-3 were determined by using a sample obtained by extracting a part of the emulsion of the component (B) polymer and depositing methanol to obtain a solid sample, "SHODEX GPC" manufactured by Showa Denko KK. SY
The weight average molecular weight in terms of polystyrene was determined using a calibration curve prepared using polystyrene having a standard molecular weight using "STEM-21".

(C) Production of acrylic rubbery polymer (F) (F-1 to F-4) 120 parts of pure water and 4 parts of sodium alkyldiphenyl ether disulfonate were charged into an autoclave, and stirred at a temperature of 65 ° C. Heated. Here, 0.005 part of ferrous sulfate heptahydrate, 0.01 part of tetrasodium ethylenediaminetetraacetate dihydrate and 0.3 part of sodium formaldehyde sulfoxylate dihydrate are dissolved in 10 parts of pure water. The diluted aqueous solution was injected. Next, a mixture 100 of monomers constituting the acrylic rubbery polymer (F) shown in Table 3 was used.
20 parts of the autoclave were injected into the autoclave and the remaining 80
To the solution, 0.05 part of potassium persulfate was added evenly and continuously over 6 hours together with an aqueous solution of 20 parts of pure water.
After the addition was completed, the mixture was cooled, and the acrylic rubbery polymer F-1 to A-1 was added.
A latex of F-4 was obtained. Table 3 also shows the physical property values of these acrylic rubbery polymers.

[0088]

[Table 3]

In Table 3, n-BA is n-butyl acrylate, MMA is methyl methacrylate, EGdGM
A represents ethylene glycol dimethacrylate, and AN represents acrylonitrile.

(D) Preparation of resin (III) containing acrylic rubbery polymer A predetermined amount of a latex of vinyl copolymer (B) and acrylic rubbery polymer (F) is blended, and an aqueous solution of calcium chloride is added. Then, the precipitate deposited at a temperature of 90 ° C. was filtered and dehydrated. After this was dried, it was pelletized with a single screw extruder to obtain a resin composition (G). Table 4 shows the composition ratio.

[0091]

[Table 4]

Examples 1 to 9 Components (I) to (III) were blended at the ratios shown in Tables 5 to 6, and the blend was heated at a temperature of 35 mm with a co-rotating twin-screw extruder equipped with a devolatilizer. Extruded at 250 ° C. and pelletized. Using the pellets, test pieces for measuring physical properties were prepared at a temperature of 250 ° C. by an injection molding machine, and various physical properties were measured. The results are shown in Tables 5 and 6. Table 6 also shows various physical property values of ABS-1 as Reference Example 1 and ABS-2 alone as Reference Example 2.

[0093]

[Table 5]

[0094]

[Table 6]

Examples 10 to 15 Components (I) to (III) were blended at the ratios shown in Table 7 and supplied directly to an injection molding machine to form test pieces. The molding was performed by attaching a static kneader (mixing nozzle) TMN-16-06 manufactured by Toray Engineering Co., Ltd. to an injection molding machine K-125 manufactured by Kawaguchi Iron Works Co., Ltd. Other molding conditions are as follows. Cylinder setting temperature: 260 ° C Injection pressure: Minimum filling pressure + 5kg / cm ² G Injection speed: 70% Mold temperature: 60 ° C Screw: Full flight type

[0096]

[Table 7]

Comparative Examples 1 to 18 ABS resins (I), polyamide-containing resins (II), and acrylic rubber-like polymer-containing resins (III) were listed in Tables 8 to 10.
Examples 1 to 9 except that blending was carried out at the ratios shown in Table 10.
The results were shown in the same manner as in the above.

[0098]

[Table 8]

[0099]

[Table 9]

[0100]

[Table 10]

Comparative Examples 19 to 22 Components (I) to (III) were blended at the ratios shown in Table 11 and directly supplied to an injection molding machine to form test pieces.
The molding was performed by attaching a static kneader (mixing nozzle) TMN-16-06 manufactured by Toray Engineering Co., Ltd. to an injection molding machine K-125 manufactured by Kawaguchi Iron Works Co., Ltd. Other molding conditions are as follows. Cylinder setting temperature: 260 ° C Injection pressure: Minimum filling pressure + 5kg / cm ² G Injection speed: 70% Mold temperature: 60 ° C Screw: Full flight type

[0102]

[Table 11]

Physical property measurement test method 1) Izod impact strength: Measured according to ASTM-D256 using a 1/4 inch thick notched test piece. 2) HDT (thermal deformation temperature): A at a load of 18.6 kg / cm ²
It was measured according to STM D-648. 3) MFR: temperature 265 ° C, load 10kg, ASTM
It measured according to D-6874. 4) Critical strain (chemical resistance): specimen shape 330 mm x 2
0mm x 2mm, major radius 300mm, minor radius 100mm
The critical strain amount after 24 hours at a temperature of 23 ° C. was measured by the 楕 円 ellipse method. The test piece was prepared by press-forming a pellet at a temperature of 270 ° C. in order to eliminate the influence of molding distortion. The chemical was performed using brake oil. 5) Dimensional stability: Dimensional changes in the longitudinal direction of the dumbbell before and after immersing ASTM D-638 No. 1 dumbbell in hot water at a temperature of 80 ° C for 24 hours were measured. The case where the dimensional change rate was 0.5% or less was evaluated as ○, and the case where it exceeded 0.5% was evaluated as ×. 6) Surface appearance: 127 mm long, 127 mm wide, 2 m thick
m was molded with side gates (two points) under the above-mentioned injection molding conditions, and the appearance of the molded product was visually observed and judged according to the following criteria. ：: No defect phenomenon (flow mark, silver stripe, flash) occurred on the surface. ×: A defect phenomenon (flow mark, silver stripe, flash) has occurred on the surface.

[0104]

As shown in Examples of Tables 5 and 6, the thermoplastic resin composition of the present invention has excellent chemical resistance, and also has excellent impact strength and appearance. On the other hand, as shown in the comparative examples of Tables 8 to 10, a thermoplastic resin composition deviating from the scope of the present invention cannot maintain these excellent qualities. Therefore, as shown in Tables 5 and 6, the thermoplastic resin composition of the present invention has excellent chemical resistance and is extremely useful in a wide range of fields such as industrial parts and household electric parts.

Further, as shown in the examples of Table 7, the ABS resin (I), the polyamide-containing resin (II) and the acrylic rubber-like polymer-containing resin (III) of the present invention were directly molded, A molded article having chemical resistance, high quality appearance, and impact resistance can be obtained without deteriorating various physical properties of the base ABS resin.

On the other hand, as shown in Comparative Examples in Table 11, the polyamide-containing resin (I
When the resin (I) and the acrylic rubbery polymer-containing resin (III) are used, a molded article having these excellent qualities cannot be obtained.

As described above, the thermoplastic resin composition of the present invention has excellent chemical resistance, and the impact resistance, heat resistance and high appearance of the ABS resin have not been reduced. Moreover, the present invention can be directly molded with the ABS resin and the chemical resistance-imparting component, and the molded product has excellent chemical resistance, and does not deteriorate the various physical properties of the base ABS resin, and has good moldability. Is also excellent. In addition, because it is possible to adopt the economically superior process of direct molding, automotive parts, electric and electronic parts, office equipment parts, heating appliances, tableware, refrigerator parts, bathtub parts, shower parts, water purifier parts, toilet seats The industrial utility value of these materials is extremely high.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 35/00 C08L 35/00

Claims (4)

[Claims] 1. The following component (A) 0.25 to 46% by weight, component (B) 1.0 to 76.5% by weight, component (C) 1
0.15 to 46% by weight, component (D) 1.5 to 15% by weight, component (E) 1.0 to 10% by weight, and component (F) 2.0 to 20% by weight. Thermoplastic resin composition. Component (A): 40 to 80% by weight of aromatic vinyl monomer residue, 20% by weight or less of unsaturated dicarboxylic acid anhydride monomer residue (however, 0 is not included), and unsaturated dicarboxylic acid imide derivative residue An unsaturated dicarboxylic acid copolymer comprising 0 to less than 60% by weight of a group and 0 to 20% by weight of a vinyl monomer residue copolymerizable therewith; (B) component: an aromatic vinyl monomer residue 60 to 80% by weight, 20 to 40% by weight of a vinyl cyanide monomer residue, and 0 to 30% by weight of a vinyl monomer residue copolymerizable therewith.
(C) Component: 35 to 65 parts by weight of a rubbery polymer, 50 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer, and A graft copolymer obtained by graft-polymerizing 35 to 65 parts by weight of a monomer mixture composed of 0 to 30% by weight of a vinyl monomer copolymerizable with: (D) component: polyamide resin, (E) component: unsaturated Elastomer copolymer consisting of ethylene-α-olefin containing 5% by weight or less (but not including 0) of dicarboxylic acid monomer residue and / or acid anhydride monomer residue thereof, Component (F): The glass transition temperature is 0 ° C. or less, the gel content is 70% or less, and the solubility parameter is 8.4 or more.
An acrylic rubber-like polymer which is a homopolymer of an acrylate monomer having a ratio of 9.8 (cal / cc) ^1/2 or a copolymer with another copolymerizable monomer. 2. The following ABS-based resin (I): 50 to 90% by weight, polyamide-containing resin (II): 5 to 25% by weight, and acrylic rubber-like polymer-containing resin (III): 5 to 25
2. The thermoplastic resin composition according to claim 1, wherein the ABS resin (I) is an unsaturated dicarboxylic acid copolymer of component (A) according to claim 1.
% By weight, 0 to 80% by weight of the vinyl copolymer (B)
And a polyamide-containing resin (II), which is a resin comprising the graft copolymer (C) and 20 to 50% by weight of the component (C).
The unsaturated dicarboxylic acid copolymer 5 of the component (A)
20% by weight, 0 to 30% by weight of the vinyl copolymer (B), 3 to 20% by weight of the graft copolymer (C),
A resin composition comprising 30 to 60% by weight of the polyamide resin (D) and 20 to 40% by weight of the ethylene-α-olefin-based elastomer copolymer (E), and a resin containing an acrylic rubbery polymer ( III) is 20 to 60% by weight of the vinyl copolymer of the component (B) according to claim 1;
And an acrylic rubber-like polymer (F) of 40 to 80% by weight. 3. The ABS resin (I) 50 according to claim 2.
To 90% by weight, polyamide-containing resin (II) 5 to 25% by weight, and acrylic rubber-like polymer-containing resin (III)
A thermoplastic resin molded product obtained by simultaneously supplying 5 to 25% by weight to a molding machine and molding. 4. The ABS resin (I) 50 according to claim 2,
To 90% by weight, polyamide-containing resin (II) 5 to 25% by weight, and acrylic rubber-like polymer-containing resin (III)
A method for producing a thermoplastic resin molded article, comprising simultaneously supplying 5 to 25% by weight to a molding machine and molding.