JPH09328590A - Thermoplastic resin composition, molded product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which can give excellent chemical resistance to an ABS resin by mixing five components including a specified copolymer and a resin. SOLUTION: This composition comprises 3-50 pts.wt. maleimide copolymer (A) comprising residues of an aromatic vinyl monomer, residues of an unsaturated dicarboxylic acid anhydride, residues of an unsaturated dicarboxylic acid imide derivative, etc., 0-50 pts.wt. vinyl copolymer (B) comprising residues of an aromatic vinyl monomer, residues of a vinyl cyanide monomer, etc., 3-50 pts.wt. graft copolymer (C) prepared by grafting a monomer mixture comprising an aromatic vinyl monomer, a vinyl cyanide monomer, etc., onto a rubbery polymer, 20-56 pts.wt. polyamide resin (D) and 12-40 pts.wt. elastomer copolymer (E) comprising an ethylene/α-olefin copolymer containing residues of an unsaturated dicarboxylic acid monomer and/or residues of its acid anhydride monomer (the total of components A to E is 100 pts.wt.).

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, the present invention is a maleimide-based copolymer, a rubbery polymer and an aromatic vinyl monomer which require unsaturated dicarboxylic acid anhydride monomer residues and unsaturated dicarboxylic acid imide monomer residues in a specific ratio. Ethylene-containing graft copolymer, polyamide resin, unsaturated dicarboxylic acid monomer residue and / or anhydride monomer residue thereof, in which a monomer residue and a vinyl cyanide monomer residue are essential A thermoplastic resin composition containing an elastomer composed of an α-olefin as an essential component, which is capable of imparting excellent chemical resistance to an ABS resin. Further, a thermoplastic resin molded product comprising the thermoplastic resin composition and an ABS resin having heat resistance and chemical resistance, particularly, the thermoplastic resin composition and the ABS resin are simultaneously supplied to a molding machine for molding. The present invention relates to a thermoplastic resin molded article having excellent impact resistance, heat resistance and chemical resistance obtained by the method (hereinafter referred to as direct molding).

[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 in various applications because of their excellent impact resistance, moldability and good surface gloss. On the other hand, materials having chemical resistance are also desired depending on the application, especially automobile parts, electric / electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts that come into contact with chemicals such as detergents, oils or organic solvents. , Bathtub parts, shower parts, water purifier parts, toilet seats, etc.
Chemical resistance is required for durability reasons.

Conventionally, as a method of improving the chemical resistance of the ABS resin, a method of blending an acrylic rubber polymer or a polyamide resin with the ABS resin is known.

However, although the ABS resin containing the acrylic rubber-like polymer has high chemical resistance and high impact resistance,
There is a problem that heat resistance and heat stability are low. In addition, although the resin composition obtained by blending the polyamide resin with the ABS resin has improved chemical resistance, the compatibility between the blended resins is not sufficient, and peeling may occur when formed into a molded article, and impact resistance may be increased. There is a drawback that it is difficult to balance the chemical resistance and chemical resistance.

When the acrylic rubber-like polymer or polyamide resin is kneaded and mixed with the ABS resin, they are mixed using a kneading machine such as a single screw extruder, a twin screw extruder or a Banbury mixer to obtain a desired chemical resistance. To obtain a resin pellet having properties and other physical properties, and shape the obtained resin pellet by means such as injection molding to produce a molded body.

[0006] In these conventional methods, in order to obtain a molded product having various physical properties such as chemical resistance and heat resistance, different resin pellets are required depending on the required physical property level. Was complicated.

Further, in order to obtain resin pellets corresponding to each physical property level, the kneading operation is performed individually, so that the ABS resin is apt to be deteriorated and the impact strength is lowered. In addition, the kneading operation requires a large cost and is economically disadvantageous.

[0008]

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 chemical resistance to an S-based resin, further solving the problems occurring when obtaining the above-mentioned molded body, and the thermoplastic resin composition of the present invention. , An ABS resin, and a thermoplastic resin molded article having excellent chemical resistance, particularly the thermoplastic resin composition of the present invention, and AB
Impact resistance and heat resistance obtained by directly molding with S-based resin,
It is intended to provide a thermoplastic resin molded article having excellent chemical resistance or a method for producing the same.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention have
As a result of extensive studies aimed at developing a thermoplastic resin composition capable of imparting chemical resistance to a molded product during injection molding of a BS resin, as a result, unsaturated dicarboxylic acid anhydride monomer residues and unsaturated dicarboxylic acid in a specific ratio Maleimide-based copolymers containing acid imide monomer residues, graft copolymers, polyamide resins, unsaturated dicarboxylic acid monomer residues in specific proportions and /
Or ethylene-α-containing an acid anhydride monomer residue
Achieving the above object when an olefin elastomer and, if necessary, an aromatic vinyl monomer residue and a vinyl-based copolymer that essentially contains a vinyl cyanide monomer residue are blended in a specific ratio. The inventors have found what can be done and have reached the present invention.

That is, the present invention comprises (A) component: aromatic vinyl monomer residue 40 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 20% by weight or less (however, 0 is not included), Unsaturated dicarboxylic acid imide derivative residue 10% by weight or more and less than 60% by weight and vinyl monomer residue 0 copolymerizable therewith
3 to 50 parts by weight of maleimide-based copolymer consisting of 20 to 20% by weight, component (B): aromatic vinyl monomer residue 60 to 80
% By weight, 20 to 40% by weight of vinyl cyanide monomer residue,
And 0 to 50 parts by weight of a vinyl-based copolymer comprising 0 to 20% by weight of a vinyl monomer residue copolymerizable therewith, (C) component: 35 to 65 parts by weight of a rubber-like polymer, and aromatic vinyl. Graft polymerization of 35 to 65 parts by weight of a monomer mixture consisting of 50 to 80% by weight of a monomer, 20 to 40% by weight of a vinyl cyanide monomer and 0 to 30% by weight of a vinyl monomer copolymerizable therewith. 3 to 50 parts by weight of the graft copolymer, (D) component: more than 20 parts by weight and not more than 56 parts by weight of polyamide resin, (E) component: unsaturated dicarboxylic acid monomer residue and / or its acid anhydride A thermoplastic resin composition comprising an elastomeric copolymer of ethylene-α-olefin containing 5% by weight or less (not including 0) of a monomer residue in an amount of more than 12 parts by weight and 40 parts by weight or less, 265 of thermoplastic resin composition , Melt in 10kg load flow rate (MFR) of the thermoplastic resin composition is 3~40g / 10 min (wherein (total 100 parts by weight of A) ~ (E)).

The advantage of the thermoplastic resin composition of the present invention is that it is simple and low-cost without significantly deteriorating physical properties such as heat resistance and impact resistance of the base ABS resin when formed into a molded body. It is a point of imparting chemical resistance.

The maleimide copolymer (A) component used in the thermoplastic resin composition of the present invention will now be described. As the aromatic vinyl monomer constituting the component (A), styrene, α-methylstyrene, vinyltoluene,
It is at least one monomer selected from styrene-based monomers such as t-butylstyrene and chlorostyrene, and among these, styrene is particularly preferable.

A copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic acid imide derivative, an unsaturated dicarboxylic acid anhydride, and a vinyl monomer which is copolymerizable with any of these, if necessary, is an unsaturated dicarboxylic acid. The anhydride is copolymerized with an aromatic vinyl monomer, and optionally with a copolymerizable vinyl monomer, and then reacted with ammonia and / or a primary amine to form an unsaturated dicarboxylic acid anhydride monomer. Quantum residue,
It may be a maleimide copolymer having an unsaturated dicarboxylic acid imide monomer residue, or maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-naphthylmaleimide, At least one imide monomer selected from glutarimide and the like is used as a direct aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride monomer, and a vinyl monomer copolymerizable therewith, which is optionally used. May be copolymerized to give a maleimide-based copolymer. The unsaturated dicarboxylic acid anhydride is at least one selected from anhydrides such as maleic acid, itaconic acid, citraconic acid and aconitic acid, and maleic anhydride is particularly preferable.

Ammonia and primary amines used in the imidization reaction may be in an anhydrous or aqueous solution, and examples of primary amines include alkylamines such as methylamine, ethylamine and cyclohexylamine, and
At least one selected from aromatic amines such as aniline, toluidine, and naphthylamine.

When the imidation reaction is carried out in a solution state or a suspension state, it is preferable to use an ordinary reaction vessel, for example, an autoclave, and when it is carried out in a bulk molten state, an extruder equipped with a devolatilization device is used. May be.

The temperature of the imidization reaction is about 80 to 350 ° C, preferably 100 to 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 are deteriorated due to thermal decomposition of the polymer. A catalyst may be used during the imidization reaction, and in this case, a tertiary amine such as triethylamine is preferably used.

The aromatic vinyl monomer residue used in the component (A) is 40 to 80% by weight, but 45 to 60% by weight.
Are particularly preferred. If it is less than 40% by weight, the moldability is lowered, and if it exceeds 80% by weight, the heat resistance of the thermoplastic resin composition is lowered, which is not preferable. The unsaturated dicarboxylic acid imide derivative residue used in the component (A) is 10% by weight or more and less than 60% by weight, less than 10% by weight, or 60% by weight.
In the above case, the compatibility of the thermoplastic resin composition is poor, and the impact resistance is significantly reduced. The unsaturated dicarboxylic acid imide derivative residue is particularly preferably 25 to 55% by weight.
In addition, the unsaturated dicarboxylic acid anhydride monomer residue is 20% by weight.
Below (however, 0 is not included), and 0.5 to 15% by weight is particularly preferable. If the unsaturated dicarboxylic acid anhydride residue is not contained, the compatibility of the maleimide copolymer of the component (A) and the polyamide resin of the component (D) will be reduced, and this will only cause delamination of the molded body. No impact strength is reduced. When it exceeds 20% by weight, crosslinking with the terminal amino groups in the polyamide resin as the component (D) proceeds, resulting in fluidity (melt florate:
MFR) is lowered, and not only the surface appearance is impaired,
Moldability is also reduced. Further, the copolymerizable vinyl monomer residue is 0 to 20% by weight, and 0 to 10% by weight is particularly preferable. If it exceeds 20% by weight, the compatibility with other components is lowered, the impact resistance is lowered, and layer peeling is likely to occur when the molded body is formed.

The weight average molecular weight of the maleimide copolymer as the component (A) is not particularly limited, but it is preferably 70,000 to 160,000, particularly preferably 80,000 to 150,000.

Next, the vinyl copolymer (B) used in the thermoplastic resin composition of the present invention will be described. The aromatic vinyl monomer used in the component (B) of the present invention is at least one selected from styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene. Yes, styrene is particularly preferred. The vinyl cyanide monomer includes at least one selected from acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.

Further, as vinyl monomers copolymerizable with these, acrylic acid esters such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, etc., methyl methacrylic acid ester, ethyl methacrylic acid ester, etc. Methacrylic acid ester monomer, acrylic acid, vinylcarboxylic acid monomer such as methacrylic acid,
At least one selected from acrylic acid amide, methacrylic acid amide, N-vinylcarbazol and the like can be mentioned. Among these, monomers such as methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.

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 exceeds 80% by weight, moldability will be deteriorated. 20 vinyl cyanide monomer residues
-40% by weight, particularly 22-32% by weight is desirable. When it is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) is lowered, which causes delamination of the molded article and a reduction in impact strength. The copolymerizable vinyl monomer residue is 0 to
It is 20% by weight, but 0 to 10% by weight is particularly suitable. If it exceeds 20% by weight, the compatibility with other components is lowered, the impact resistance is lowered, and layer peeling is likely to occur when the molded body is formed.

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

Next, the graft copolymer of the component (C) used in the thermoplastic resin composition of the present invention will be described.
The rubber-like polymer used as the component (C) is a butadiene polymer, a copolymer of a vinyl monomer copolymerizable with butadiene, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer, or the like. At least one kind selected can be mentioned.

The aromatic vinyl monomer used as the component (C) is at least one selected from styrene-based monomers such as styrene, α-methylstyrene, vinyltoluene, t-butylstyrene and chlorostyrene. And styrene is particularly preferable. The vinyl cyanide monomer includes at least one selected from acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and the like, and acrylonitrile is particularly preferable.

Further, as vinyl monomers copolymerizable with these, acrylic acid ester monomers such as methyl acrylic acid ester, ethyl acrylic acid ester, butyl acrylic acid ester, methyl methacrylic acid ester, ethyl methacrylic acid are used. Methacrylic acid ester monomers such as ester, acrylic acid, vinylcarboxylic acid monomers such as methacrylic acid, acrylic acid amide, methacrylic acid amide, and
At least one kind selected from N-vinylcarbazole and the like can be mentioned, and of these, monomers such as acrylic acid ester, methacrylic acid ester, acrylic acid and methacrylic acid are particularly preferable.

Any known polymerization technique can be adopted for producing the graft polymer as the component (C). For example, aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization, solution polymerization and production weight. Examples include precipitation heterogeneous polymerization in a poor solvent of the combination, and combinations thereof.

The rubber particle size of the graft copolymer as the component (C), the graft ratio and the weight average molecular weight of the ungrafted copolymer are not particularly specified, but the rubber particle size is 0.1 to 0.
The range of 6 μm is preferable from the viewpoint of impact resistance. The graft ratio is 20 to 80%, particularly preferably 30 to 50%.
And the weight average molecular weight of the ungrafted copolymer is 50,000 to 2
The range of 0,000, particularly preferably 60,000 to 100,000, is preferable since the balance between impact resistance and moldability is good.

The graft copolymer as the component (C) comprises 50 to 80% by weight of an aromatic vinyl monomer and 20 to 40% by weight of a vinyl cyanide monomer in the presence of 35 to 65 parts by weight of a rubbery polymer. , And vinyl monomers 0 to 30 copolymerizable therewith
It is obtained by graft-polymerizing 35 to 65 parts by weight of a monomer mixture consisting of wt% (however, the total amount of the rubber-like polymer and the monomer mixture is 100 parts by weight). In particular, 65 to 72% by weight of the aromatic vinyl monomer, 22 to 32% by weight of the vinyl cyanide monomer, and 0 to 13% by weight of the vinyl monomer copolymerizable therewith are preferable. When the amount of the aromatic vinyl monomer is less than 50% by weight, the direct moldability between the thermoplastic resin composition of the present invention and the ABS resin is lowered, and when it exceeds 80% by weight, the heat resistance of the thermoplastic resin composition of the present invention is low. Will decrease. On the other hand, if the vinyl cyanide monomer is less than 20% by weight or more than 40% by weight, the compatibility with the component (A) is lowered, and the thermoplastic resin composition of the present invention and the ABS resin are delaminated. It also causes a drop in impact strength. If the copolymerizable vinyl monomer residue exceeds 30% by weight, the compatibility with other components is reduced and the impact resistance is reduced, and layer peeling is likely to occur when a molded product is formed. When the amount of the rubber-like polymer as the component (C) is less than 35 parts by weight, the impact resistance of the thermoplastic resin composition of the present invention decreases, and when it exceeds 65 parts by weight, the heat resistance of the thermoplastic resin composition of the present invention is low. And the thermoplastic resin composition of the present invention and ABS
It is not preferable because the direct moldability with the resin is lowered.

In the graft polymerization, it is usually difficult to graft the entire amount of the monomer onto the rubbery polymer, and an ungrafted copolymer is produced as a by-product. In the present invention, not only the true graft copolymer in which the ungrafted copolymer is positively separated and removed, but also the graft polymerization in which the ungrafted copolymer is contained may be used. It can be handled.

Next, the polyamide resin of the component (D) used in the thermoplastic resin composition of the present invention will be described.
Examples of the polyamide resin as the component (D) include nylon-6, nylon-6,6, nylon-4,6, nylon-6,10, nylon-12, nylon-11, etc., which may be used alone or in combination. Can also be used.

Next, the elastomer (E) composed of ethylene-α-olefin used in the thermoplastic resin composition of the present invention will be described. Ethylene-α-containing unsaturated dicarboxylic acid and / or its anhydride as component (E)
The olefin elastomer has a number average molecular weight in the range of 10,000 to 1,000,000,
The ethylene content is preferably 50 to 80 mol%.
As the α-olefin, at least one selected from propylene, 1-butene and 1-pentene can be used, and propylene is particularly preferable.

As the unsaturated dicarboxylic acid monomer residue and / or its anhydride monomer residue used for modification as the functional group of the component (E), maleic acid, itaconic acid, citraconic acid, aconitic acid and There is at least one selected from these acid anhydride monomers, and maleic anhydride is particularly preferable.

The content of the unsaturated dicarboxylic acid monomer residue and / or its anhydride monomer residue is 5% by weight or less (excluding 0), preferably 0.5 to 5% by weight. Yes, if it exceeds 5% by weight, gel or the like is generated in the composition.
On the other hand, if it is less than 0.5% by weight, the compatibility of the thermoplastic resin composition is insufficient, which may cause delamination when formed into a molded article,
Impact strength does not develop. This modified ethylene-α-
Elastomers consisting of olefins are available in Japanese Patent Publication Sho-45-445
It can be obtained by using the manufacturing method of Example 1 disclosed in the publication.

The component (A), the component (B), the component (C), the component (D) and the component (E) in the thermoplastic resin composition of the present invention are mixed in a proportion of 3 to 50 parts by weight of the component (A). ,
(B) component 0 to 50 parts by weight, (C) component 3 to 50 parts by weight, (D) component over 20 parts by weight and 56 parts by weight or less,
The amount of the component (E) is more than 12 parts by weight and 40 parts by weight or less, particularly preferably 5 to 30 parts by weight of the component (A), 0 to 30 parts by weight of the component (B), 5 to 20 parts by weight of the component (C), The component (D) is 30 to 50 parts by weight and the component (E) is 20 to 40 parts by weight (however, the total of (A) to (E) is 100 parts by weight).
When the amount of the component (A) is less than 3 parts by weight, the compatibility is insufficient,
If it exceeds 50 parts by weight, the impact resistance of the thermoplastic resin composition,
Moldability is significantly reduced. Further, if the amount of the component (B) exceeds 50 parts by weight, there is a problem that the moldability is lowered. If the amount of the component (C) is less than 3 parts by weight, the impact resistance will decrease, and if it exceeds 50 parts by weight, the moldability will decrease. If the amount of component (D) is 20 parts by weight or less, the chemical resistance is insufficient, and if it exceeds 56 parts by weight, the dimensional stability deteriorates. When the amount of the component (E) is 12 parts by weight or less, the impact resistance is not sufficient, and when it exceeds 40 parts by weight,
Moldability decreases. The ratio of the component (D) to the component (E) in the thermoplastic resin composition of the present invention is not particularly limited, but is preferably (E) / (D) = 30/70 by weight.
５０50/50.

The method of mixing the components (A) to (E) in order to obtain the thermoplastic resin composition of the present invention is not particularly limited,
Known means can be used. Examples of such means include Banbury mixers, tumbler mixers, and mixing rolls.
And a single-screw or twin-screw extruder. As a mixing form, there are a usual contact mixing, a multi-stage melt mixing using a master pellet or the like, and a method of obtaining a composition by blending in a solution. In particular, the components (D) and (E) may be melt-mixed in advance and then mixed with the remaining components (A) to (C). In particular, a resin composition comprising the component (D) and the component (E) is melt-mixed in advance, and the ratio of the component (A), the component (B), and the component (C) is [(A) + (B) by weight]. +
(C)] / [(D) + (E)] = 60/40 to 20/8
0, particularly preferably 40/60 to 20/80 are mixed to form a thermoplastic resin composition, and then directly molded with an ABS resin to obtain heat resistance and chemical resistance of the obtained molded product. Impact resistance and moldability are further improved. Further, the melt fluorate (MFR) of the thermoplastic resin composition of the present invention
Is required to be in the range of 3 to 40, preferably 3 to 25, and particularly preferably 3 to 10. If it is less than 3, the surface appearance of the molded product obtained by directly molding with the ABS resin is inferior, and if it exceeds 40, the impact strength and heat resistance of the molded product tend to be lowered.

Further, the thermoplastic resin composition of the present invention may be further blended with a stabilizer, a plasticizer, a lubricant, an ultraviolet absorber and a colorant according to the purpose.

When the thermoplastic resin composition of the present invention and the ABS resin are supplied to the injection molding machine, these additives may be supplied at the same time. Specific examples of the ABS resin used in the present invention include ABS (acrylonitrile-butadiene-styrene) resin, α-methylstyrene heat-resistant ABS (acrylonitrile-butadiene-α-methylstyrene) resin, and maleimide heat-resistant ABS (acrylonitrile). -Butadiene-N-phenylmaleimide) resin, A
ES (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 are mentioned, but they are not particularly limited.

The mixing ratio of the thermoplastic resin composition of the present invention and the ABS resin is not particularly limited, but preferably 10 to 50% by weight of the thermoplastic resin composition and 50 to 50 of the ABS resin.
90% by weight, preferably thermoplastic resin composition 15-40
% By weight, 60 to 85% by weight of ABS resin, particularly preferably 15 to 30% by weight of the thermoplastic resin composition and 70 to 85% by weight of ABS resin.

When the thermoplastic resin composition is less than 10% by weight, the chemical resistance of the molded product obtained by directly molding it with the ABS resin is not sufficient. On the other hand, if it exceeds 50% by weight, the direct formability with the ABS resin is deteriorated.

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

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

The thermoplastic resin composition of the present invention and the ABS resin may be supplied to a molding machine by preblending using a known device such as a tumbler mixer or a V blender, or molding. It is possible to employ a method in which both materials are separately quantitatively supplied to the supply port of the machine, or a method in which the thermoplastic resin composition and the ABS resin are melt-kneaded in advance into pellets and then supplied to the molding machine. There is no particular focus on the supply method.

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

In the case of injection molding, a known static mixer such as Sulzer type, Kenix type or Toray type is installed between the molding machine cylinder and the nozzle to obtain higher quality molding. You can get a body.

Further, as the screw of the injection molding machine, the most versatile full flight screw can be used, but it is also possible to use the dullage type, pin type, or maddock type screw having higher kneadability.

The present invention will be further described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Incidentally, the parts in Examples and Comparative Examples,
All percentages are by weight unless otherwise specified.

[0047]

【Example】

Experimental Examples 1-2. Maleimide-based copolymer (A) component (A-
1, A-3) 60 parts of styrene, α in an autoclave equipped with a stirrer
-Methyl styrene dimer (0.05 parts) and methyl ethyl ketone (100 parts) were charged, the system was replaced with nitrogen gas and then the temperature was raised to 85 ° C, and 40 parts of maleic anhydride and 0.15 part of benzoylperoxide were added to methyl ethyl ketone (20).
A solution dissolved in 0 part was continuously added in 8 hours. The temperature was kept at 85 ° C. for a further 3 hours after the addition. 38 parts of aniline and 0.6 parts of triethylamine were added to the copolymer solution obtained here.
Then, the mixture was reacted at 140 ° C. for 7 hours. The reaction liquid was supplied to a twin-screw extruder with a vent and devolatilized to obtain a maleimide copolymer. From C-13 NMR analysis, the conversion rate of acid anhydride groups to imide groups was 92 mol%. This maleimide copolymer was a copolymer containing 52% of N-phenylmaleimide units as an unsaturated dicarboxylic acid imide derivative, and this was designated as copolymer A-1. The maleimide copolymer A-3 was also produced in the same manner as A-1 except that the addition rate of aniline was adjusted to adjust the addition rate of maleic anhydride to the imide group.

Experimental Example 3 Maleimide-based copolymer (A) component (A-2) 60 parts of styrene and 100 parts of methyl ethyl ketone were charged into an autoclave equipped with a stirrer, the system was replaced with nitrogen gas, and then the temperature was raised to 85 ° C. The mixture was sufficiently stirred while maintaining the temperature. Maleimide copolymer A-2 was produced in the same manner as in A-1, except that 1 part of α-methylstyrene dimer was added thereto. Table 1 shows A-1 to A-
The composition analysis result and characteristic analysis of No. 3 are shown.

[0049]

[Table 1]

For the GPC measurement for calculating the weight average molecular weight, "SHODEX GPC SY" manufactured by Showa Denko KK
STEM-21 "was used to determine the polystyrene-equivalent weight average molecular weight using a calibration curve prepared using standard molecular weight polystyrene.

Experimental Example 4. Production of Vinyl Copolymer (B) Component (B-1) 70 parts of styrene, 30 parts of acrylonitrile, 2.5 parts of tribasic calcium phosphate, 0.5 part of t-dodecyl mercaptan, in a reaction can equipped with a stirrer. 0.2 parts of benzoyl peroxide and 250 parts of water 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. The obtained reaction solution is neutralized with hydrochloric acid, dehydrated,
After drying, a white bead-shaped copolymer was obtained. This was designated as copolymer B-1.

Experimental Example 5. Production of Graft Copolymer (C) Component (C-1) Polybutadiene latex 1 in a reaction can equipped with a stirrer
43 parts (solid content 35% weight average particle size 0.25 μm, gel content 90%), sodium stearate 1 part, sodium formaldehyde sulfoxylate 0.1 part, tetrasodium ethylenediamine tetraacetic acid 0 .03
Parts, ferrous sulfate 0.003 parts, and pure water 150 parts 50 parts
The mixture was heated to 0 ° C., and 50 parts of a monomer mixture consisting of 70% styrene and 30% acrylonitrile, 0.2 part of t-dodecyl mercaptan, and 0.15 part of kyuumen hydroperoxide were continuously added thereto over 6 hours, 65 ° C after further addition
And polymerized for 2 hours. The polymerization rate reached 97%. An antioxidant (Irganox 107) was added to the obtained latex.
6) After adding 0.3 parts, coagulation with calcium chloride, washing with water, and drying to obtain a graft copolymer as a white powder. This was designated as copolymer C-1.

Next, in order to measure the grafting ratio of C-1 and the molecular weight of the ungrafted copolymer, 3 g of C-1 was taken, swollen in a methyl ethyl ketone solution, and centrifuged to obtain an ungrafted styrene-containing solution. 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 rubber-like polymer) precipitated by centrifugation was analyzed by Kjeldahl nitrogen quantitative analysis and pyrolysis gas chromatography, and the weight of the graft copolymer was measured from the amounts of styrene and acrylonitrile. The polybutadiene rubber was analyzed by the bromine addition method to determine the weight of the rubber-like polymer. From the weight of the graft copolymer thus obtained and the weight of the rubber-like polymer, the graft ratio was calculated from the following formula, and the graft ratio was 33%. Graft ratio = (weight of graft copolymer / weight of rubber-like polymer) × 100 (%)

As the polyamide resin of the component (D), nylon-6; relative viscosity 2.65 obtained by condensation polymerization of ε-caprolactam (concentrated sulfuric acid as solvent, concentration 0.5 g / 10)
0 ml, temperature measured at 25 ° C) Nylon-6
(CM-1017 manufactured by Toray Industries, Inc.) was used as D-1.

Experimental Example 6. Production of Elastomer (Component E) Consisting of Modified Ethylene-α-Olefin (E-1) Ethylene-propylene copolymer having a number average molecular weight of 500,000 according to the production method (according to the examples) disclosed in JP-A-52-49289. Polymer (230 ° C, MFR of 10 kg is 0.5 g /
10 minutes modified EPR: Mitsui Petrochemical Co., Ltd. Tuffmer M
P-0430) with 1.3% maleic anhydride grafted was used as E-1.

Experimental Example 7. Mixing of (D) component and (E) component 60 parts of (D) component and 40 parts of (E) component are blended, and this blend is extruded at 280 ° C. in a co-rotating twin-screw extruder equipped with a 35 mm devolatilizer. And pelletized to obtain a resin composition F-1. By the same method, a resin composition F-2 comprising 80 parts of component (D) and 20 parts of component (E) was obtained.

Experimental Example 8. Production of thermoplastic resin composition (A) component, (B) component, (C) component, and F-1,
The F-2 component was blended in an amount ratio shown in Table 2 to obtain 35 mm
Thermoplastic resin compositions MB-1 to M are extruded at 280 ° C. in a co-rotating twin-screw extruder equipped with a devolatilizer and pelletized.
B-9 was produced. The melt flow rate (MFR) of this thermoplastic resin composition was measured and is shown in Table 2.

[0058]

[Table 2]

As the ABS resin, a commercially available ABS resin "GT-R (manufactured by Denki Kagaku Kogyo Co., Ltd.)" (hereinafter referred to as AB
S-1) is a heat-resistant ABS resin commercially available as "K-
090 (manufactured by Denki Kagaku Kogyo Co., Ltd.) "(hereinafter, ABS-
2).

Examples 1 to 7 thermoplastic resin compositions MB-2, MB-4, MB-5, M
B-7, MB-8 and ABS resin ABS-1, ABS
-2 was supplied to each of the injection molding machines at a ratio shown in Table 3 with a quantitative feeder to mold a test piece. For molding, injection molding machine K-125 manufactured by Kawaguchi Iron Works Co., Ltd. is added to static kneader (mixing nozzle) TMN- manufactured by Toray Engineer Co., Ltd.
16-06 was attached. Other molding conditions are as follows. Cylinder set temperature: 260 ° C Injection pressure: Minimum filling pressure + 5kg / cm ² G Injection speed: 70% Mold temperature: 60 ° C Screw: Full flight type Various physical properties are measured using the test piece obtained here,
The results are shown in Table 3. In addition, evaluation of ABS-1 and ABS-2 to which the thermoplastic resin composition was not added was set as a reference example in Table 4.

Example 8 20 parts of thermoplastic resin composition MB-2 and ABS resin A
80 parts of BS-2 and 26 parts of 40 mmΦ single screw extruder
It was extruded at 0 ° C to obtain pellets. Using this pellet,
Test pieces were prepared under the same molding conditions as in Example 1. The physical property measurements are shown in Table 3.

[0062]

[Table 3]

[0063]

[Table 4]

Comparative Examples 1 to 8 Thermoplastic Resin Compositions MB-1, MB-3, MB-6, M
B-9, F-1, and ABS resin ABS-1, ABS
-2 was carried out in the same manner as in the example, except that -2 was used in the ratio shown in Table 5.

[0065]

[Table 5]

Test method for measuring physical properties 1) HDT (heat distortion temperature): load 18.6 kg / c
m ² , 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) MFR: 265 ° C, 10 kg load condition, ASTM
It measured according to D-6874. 4) Critical strain (chemical resistance): test piece shape 330 × 20 ×
2 mm, long radius 248 mm, short radius 148 mm 1/4
The critical strain amount after 24 hours at 23 ° C. was measured by the ellipse method. In addition, in order to eliminate the influence of molding strain, the test piece is 2
The pellets were press-molded at 70 ° C. and cut out to manufacture. The chemical was done using salad oil. 5) Dimensional stability: According to ASTM D-638, No. 1 dumbbell was immersed in warm water at 80 ° C. for 24 hours, and the dimensional change in the longitudinal direction of the dumbbell before and after the immersion was measured. When the dimensional change rate was 0.5% or less, it was marked with ◯, and when it exceeded 0.5%, it was marked with x. 6) Appearance: A square plate having a length of 127 mm, a width of 127 mm, and a wall thickness of 2 mm was molded under the above injection molding conditions with side gates (2 points), and the appearance of the molded body was visually observed and judged according to the following criteria. ◯: No defective phenomenon (flow mark, silver strip, flash) on the surface. X: A defective phenomenon (flow mark, silver strip, flash) occurs on the surface.

As shown in the examples of Table 3, by directly molding the thermoplastic resin composition of the present invention and the ABS resin, the chemical resistance and the chemical resistance of the base ABS resin are not lowered. A molded product having a high quality appearance can be obtained. On the other hand, as shown in Comparative Examples in Table 5, when a thermoplastic resin composition deviating from the scope of the present invention is used,
It is not possible to obtain moldings of these excellent qualities.

[0068]

As described above, the molded product obtained by molding the thermoplastic resin composition of the present invention and the ABS resin is excellent in chemical resistance and heat resistance, and in particular, The thermoplastic resin composition can be directly molded with the ABS resin, the molded product has excellent chemical resistance, heat resistance and impact resistance, and further, does not deteriorate the physical properties of the base ABS resin. It also has excellent moldability. According to the direct molding of the present invention, by changing the compounding ratio of the base ABS desired to have chemical resistance and the specific thermoplastic resin composition, the desired ABS resistance can be obtained without lowering the characteristics of the base ABS. A molded article having chemical properties can be easily obtained at low cost. In addition, since it is possible to use an economically superior process called direct molding,
It has an extremely high industrial utility value as a material for electronic parts, office equipment parts, heat appliances, tableware, refrigerator parts, bathtub parts, shower parts, water purifier parts, toilet seats and the like.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08L 77/00 LQS C08L 77/00 LQS

Claims (5)

[Claims] 1. Component (A): aromatic vinyl monomer residue 40
~ 80% by weight, unsaturated dicarboxylic acid anhydride monomer residue 2
Maleimide system consisting of 0% by weight or less (excluding 0), unsaturated dicarboxylic acid imide derivative residues of 10% by weight or more and less than 60% by weight, and vinyl monomer residues of 0 to 20% by weight copolymerizable therewith. Copolymer 3 to 50 parts by weight, component (B): aromatic vinyl monomer residue 60 to 80% by weight, vinyl cyanide monomer residue 20 to 40% by weight, and vinyl copolymerizable therewith 0 to 50 parts by weight of vinyl-based copolymer consisting of 0 to 20% by weight of monomer residue, component (C): 35 to 65 parts by weight of rubber-like polymer, 50 to 80% by weight of aromatic vinyl monomer A graft copolymer 3 to which 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 is graft-polymerized. 50 parts by weight, component (D): polyamide resin 20 Ethylene containing more than 56 parts by weight and more than 5 parts by weight, and (E) component: 5% by weight or less (not including 0) of unsaturated dicarboxylic acid monomer residue and / or acid anhydride monomer residue thereof. In a thermoplastic resin composition comprising more than 12 parts by weight and not more than 40 parts by weight of an elastomeric copolymer composed of -α-olefin, the thermoplastic resin composition has a melt flow rate (MFR) of 3 at 265 ° C and a load of 10 kg. To 40 g / 10 minutes, the thermoplastic resin composition (however, the total of (A) to (E) is 1).
(00 parts by weight). 2. The thermoplastic resin according to claim 1, wherein the weight ratio of the component (D) to the component (E) is (E) / (D) = 30/70 to 50/50. Composition. 3. A composition comprising a component (D) and a component (E) is melt-mixed in advance, and a component (A), a component (B),
The weight ratio of the component (C) is [(A) + (B) +
(C)] / [(D) + (E)] = 60/40 to 20/8
The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin composition is mixed so as to be 0. 4. The thermoplastic resin composition according to claim 1, 2 or 3 and 10 to 50% by weight and the ABS resin 50 to 90% by weight.
A thermoplastic resin molded product obtained by feeding and molding the above into a molding machine. 5. The thermoplastic resin composition according to claim 1, 2 or 3 and 10 to 50% by weight and the ABS resin 50 to 90% by weight.
A method for producing a thermoplastic resin molded article, which comprises simultaneously feeding and molding the same into a molding machine.