JPH02311545A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To prepare a thermoplastic resin compsn. which gives a molded article having improved mechanical properties and dimensional stability and an excellent appearance while retaining the chemical resistance inherent in polyamide by blending a polyamide with a specific maleimide copolymer, a polyolefin copolymer modified with an unsatd. carboxylic acid, etc. CONSTITUTION:10 to 50wt.% maleimide copolymer (A) comprising 30 to 70mol% arom. vinyl monomer, 30 to 50mol% maleimide monomer, 3 to 20mol% unsatd. dicarboxylic anhydride, and 0 to 50mol% other copolymerizable monomer; 10 to 60wt.% polyamide (B); 0 to 40wt.% olefin polymer (C) modified with 0.1 to 10wt.% unsatd. dicarboxylic acid (anhydride); and 20 to 80wt.% other thermoplastic resin (D) (e.g. ABS resin, methyl methacrylate-butadiene-styrene copolymer, or polycarbonate) are blended in such a way that component A disperses as particles with diameters of 0.01 to 1.0mum to give a thermoplastic resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic resin composition having excellent mechanical properties, dimensional stability, chemical resistance, and appearance of molded articles. More specifically, it is made of a specific maleimide copolymer, polyamide, modified polyolefin polymer, and other thermoplastic resin, and has improved mechanical properties and dimensional stability while maintaining the chemical resistance of polyamide. Moreover, the present invention relates to a thermoplastic resin composition that provides a molded article with an excellent appearance.

[Conventional technology]

While polyamide has excellent properties such as mechanical properties, chemical resistance, abrasion resistance, and electrical properties, it has poor impact resistance (notched).
, has low heat resistance, high molding shrinkage rate, and tends to cause problems such as sink marks and warpage in molded products. Furthermore, due to its high hygroscopicity, it is known that it not only tends to cause defects in the appearance of the molded product during the molding process, but also tends to cause large changes in the dimensions or shape of the molded product, as well as changes in the mechanical properties of the molded product. ing. In addition, the molten resin has a low viscosity, and a truing phenomenon in which the molten resin flows out of the nozzle of the molding machine as if pulling a string during injection molding is likely to occur, making the molding operation complicated.

In order to improve these drawbacks of polyamide, attempts have been made to mix or react various polymeric substances with polyamide. For example, styrene resins such as polystyrene or styrene-acrylonitrile copolymer were melt-blended (Japanese Patent Publication No. 3B-23476).
No. 40-7380, U.S. Patent No. 3,243.47
No. 8, No. 3,243.479, West German Published Patent No. 2
, No. 403.889), these resins have poor compatibility with polyamide, and therefore, a layered peeling phenomenon was observed in molded products made from the obtained compositions, and the mechanical properties were also poor.

In addition, an attempt was made to mix a copolymer of styrene and an unsaturated dicarboxylic anhydride monomer with polyamide (Japanese Patent Application Laid-open No. 50931/1983), but the resulting composition had poor thermal stability. . For the purpose of improving compatibility, a composition consisting of seven three components is known in which a copolymer of styrene and an unsaturated dicarboxylic acid anhydride monomer is used as a compatibilizer between a styrenic resin and a polyamide. Although it is (Unexamined Japanese Patent Publication No. 60-1
No. 95157), the resulting composition was improved in compatibility and thermal stability, but its effects were insufficient. It is produced by melt-mixing a copolymer containing an imide compound of unsaturated dicarboxylic acid and polyamide. A copolymer in which art dealer molecular chains are bonded is known (Japanese Unexamined Patent Publication No. 57-5
No. 7719, No. 57-141426), the properties of the obtained copolymer were easily influenced by the production conditions using a melt mixer, which was an industrial disadvantage. Furthermore, the heat resistance and impact resistance of the obtained copolymers were not necessarily sufficient. Compositions consisting of unsaturated dicarboxylic anhydride monomers, aromatic vinyl copolymers, polyamides, and modified polyolefins are also known (Japanese Patent Application Laid-open No. 171751/1983), but these have poor heat resistance and thermal stability. Not enough.

As an improvement on this, a three-component composition consisting of a copolymer of a maleimide monomer, a polyamide, and a modified polyolefin is known (JP-A-62-59647 and JP-A-62-179546). In the molded product made from the composition, defective phenomena were observed on the surface near the gate, there was delamination, and the balance of impact value, elongation, rigidity, etc. was insufficient.

[Problem to be solved by the invention]

As mentioned above, many attempts have been made to improve the properties of polyamides, but the effects have all been insufficient for practical use.

An object of the present invention is to provide a polyamide resin composition that has excellent mechanical properties, dimensional stability, chemical resistance, and appearance of molded products.

[Means to solve the problem]

That is, in the present invention, (A): aromatic vinyl monomer group 30
~70 mol%, maleimide monomer group 30-50 mol%
, 10 to 50% by weight of a maleimide copolymer consisting of 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups and 0 to 50 mol% of other copolymerizable monomer groups, (B):
10 to 60% by weight of polyamide, (C): 0 to 10% modified polyolefin polymer modified with 0.1 to 10% by weight of unsaturated dicarboxylic anhydride monomer groups and/or unsaturated carboxylic acid monomer groups 40% by weight, and (D): the above (
Thermoplastic resins other than A), (B) and (C) 20-8
0% by weight, and the maleimide copolymer as component (A) forms dispersed particles of 0.01 to 1.0 microns, the resulting composition has a good balance of mechanical properties such as impact resistance, elongation, and rigidity, and has good dimensional stability due to its low moisture absorption, and its molded products have a beautiful appearance.

There are no particular limitations on the method for producing the maleimide copolymer used in the present invention, and examples include aromatic vinyl monomers, maleimide monomers, unsaturated dicarboxylic acid anhydride monomers, and other copolymerizable monomers. It can be produced by radical copolymerization of polymers.

Specific examples of aromatic vinyl monomers include styrene, α-
There are methylstyrene, vinyltoluene, 1-butylstyrene, etc., and specific examples of maleimide monomers include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide,
N-cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide, etc. Specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride. , ethyl maleic anhydride, phenyl maleic anhydride, etc. Specific examples of other copolymerizable monomers include:
Acrylonitrile, methacrylaterile, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, octadecyl (meth)acrylate,
Examples include hydroxyethyl (meth)acrylate, methoxyethyl (meth)acrylate, and glycidyl (meth)acrylate, and these can be used alone or in combination. However, methyl (meth)acrylate here refers to methyl acrylate or methyl methacrylate.

There are no particular restrictions on the method of copolymerizing these monomers, and any known radical copolymerization method can be employed.

As another method for producing the maleimide copolymer used in the present invention, a copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer, and other copolymerizable monomers is mixed with ammonia or A method of imidizing an acid anhydride group by reacting with a primary amine can be exemplified. The imidization reaction between a polymer substance having an acid anhydride group in the polymer chain and an amine compound is known, for example,
According to the method disclosed in No. 26936 or No. 62-8456, a desired maleimide copolymer having an imide group can be produced by reacting a polymeric substance with an amine compound.

Examples of primary amines used in imidization reactions are:
Examples include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, dibromophenylamine.

The imidization reaction is carried out in a solution state using O, Tocrepe.
The reaction can be carried out in a bulk molten state or in a suspended state. It is also possible to carry out the reaction in a molten state using a melt kneading device such as a screw extruder.

Any solvent can be used in the solution reaction, such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexanone, tetrahydrofuran,
Examples include ethers such as 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethyl sulfoxide, and N-methyl-2-pyrrolidone.

The imidization reaction temperature is preferably in the range of 50 to 350°C, particularly preferably in the range of 100 to 300°C.

Although the imidization reaction does not necessarily require the presence of a catalyst,
If used, trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-
Tertiary amines such as diethylaniline are preferred.

The maleimide copolymer used in the present invention contains 30 to 70 mol% of aromatic vinyl monomer groups, 30 to 50 mol% of maleimide monomer groups, and 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups. Mol% and other copolymerizable monomer groups 0
Consisting of ~50 mol%. Furthermore, preferred ranges include 50 to 60 mol% of aromatic vinyl monomer groups, 40 to 50 mol% of maleimide monomer groups, 3 to 10 mol% of unsaturated dicarboxylic anhydride monomer groups, and other monomer groups. The polymerizable monomer group is 0 to 30 mol%. If the aromatic vinyl monomer group is less than 30 mol%, it is difficult to industrially produce a polymer with a homogeneous composition with good reproducibility, and it is difficult to produce a polymer having a homogeneous composition with good reproducibility. The resulting composition has poor properties such as thermal stability, moldability, and mechanical strength. Also,
If the aromatic vinyl monomer group is more than 70 mol% or the maleimide monomer group is less than 30 mol%, the resulting composition will have poor heat resistance, and if the maleimide monomer group is less than 5 mol%, the resulting composition will have poor heat resistance.
If it exceeds 0 mol %, the moldability of the resulting composition will be poor. If the unsaturated dicarboxylic anhydride monomer group is less than 3 mol%, the compatibility of the composition obtained by mixing with the polyamide will be poor, and the particle size of the maleimide copolymer dispersed particles will become large. The mechanical strength is poor, and a peeling phenomenon is observed in molded products of the composition. Further, if the unsaturated dicarboxylic anhydride monomer group exceeds 20 mol%, the particle size of the maleimide copolymer dispersed particles of the composition becomes too small;
The molding processability is poor, the thermal stability of the molded product is poor, and the surface may become rough like a shark's skin.

The polyamide used in the present invention is not particularly limited, and may be a polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, etc. Specific examples include aliphatic polyamides such as nylon 6, nylon 6/6, nylon 6/9, nylon 6/10, nylon 6/12, nylon 4/61, nylon 11, and nylon 12, and poly(hexamethylene terephthalate). (lamid), poly (hexamethylene isophthalamide), poly
There are polyamides containing aromatic rings such as (m-xylylene adipamide), and these can be used alone or in combination.

The modified polyolefin polymer used in the present invention is a modified polyolefin polymer modified with an unsaturated dicarboxylic anhydride monomer and/or an unsaturated carboxylic acid monomer, and preferably has rubber-like elasticity.

The modified polyolefin polymer refers to a modified product of an olefin monomer polymer or copolymer. Specific examples of the olefin monomer used include ethylene, propylene, 1-butene, isobutylene, and 2-butene. , cyclobutene, 3-methyl-1-butene, 4-methyl-1-butene, 4-methyl-1-pentene, cyclopentene, 1-
Examples include hexene, cyclohexene, 1-octene, 1-decene, and 1-dodecene. In addition, if necessary, the modified polyolefin polymer may be copolymerized with a non-conjugated diene monomer such as 4-ethylidene norbornene or dicyclopentadiene, or an acrylic monomer within a range that exhibits rubber-like elasticity. It's okay to stay.

In addition, thermoplastic resins other than those mentioned above that can be used in the present invention include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, methyl methacrylate-butadiene-styrene copolymer, and polycarbonate. , polyethylene terephthalate, polybutylene terephthalate, polyphenylene oxide, etc.

In the present invention, 10 to 50% by weight of maleimide copolymer, 10 to 60% by weight of polyamide, 0 to 40% by weight of modified polyolefin polymer, and 20 to 8% by weight of other thermoplastic resin.
0% by weight is mixed to form a composition, but the maleimide copolymer is less than 10% by weight or the polyamide is 60% by weight.
If the amount exceeds 50% by weight, the heat resistance, molding processability, or hygroscopicity of the resulting composition will be insufficiently improved. If so, the mechanical strength, chemical resistance, or abrasion resistance of the composition is poor.

Moreover, if the modified polyolefin polymer is 40% by weight or more, the rigidity will decrease too much.

Further, to illustrate a preferred composition range of the modified polyolefin polymer, 20 to 90 mol% of ethylene, 10 to 80 mol% of α-olefin monomer, and 0 to 80 mol% of other monomers.
10 mol%, and the ethylene content is 50 to 85 mol%
It is particularly preferable that Further, the Tg of these modified polyolefin polymers is -10°C or less, particularly preferably -30°C or less.

As the unsaturated dicarboxylic anhydride monomer for modifying the modified polyolefin polymer, those already exemplified as monomers that can constitute the maleimide copolymer can be used, but maleic anhydride is particularly preferred; Examples of carboxylic acid monomers include acrylic acid and methacrylic acid.

The content of unsaturated dicarboxylic anhydride monomer groups or unsaturated carboxylic acid groups in the modified polyolefin polymer is 0.
．． 1 to IO% by weight is preferred, and 0.1 to 5% by weight is particularly preferred. If it is less than 0.1% by weight, the mechanical strength of the resulting composition will be insufficient, and a layered peeling phenomenon may be observed in the molded product, and if it exceeds 10% by weight, the mechanical strength or May impair thermal stability.

Modification in the present invention refers to the presence of a monomer group used for modification, such as a maleic anhydride group, in the main chain or side chain of the polyolefin polymer, and it can be used for random copolymerization, graft polymerization, etc. Modification can be carried out using known techniques such as. There are no particular limitations on the modification method; for example, Japanese Patent Publication No. 39-6810, Japanese Patent Publication No. 52-43677, Japanese Patent Publication No. 5716-1982, Japanese Patent Publication No. 56-9925, Japanese Patent Publication No.
Modification can be carried out according to the method disclosed in No. 8-445 and the like. In addition, those that are modified as a graft form rather than introduced into the main chain are preferable from the viewpoint of low-temperature impact value. Furthermore, the amount of unreacted monomer residues is preferably as low as 0.5% by weight or less.

The molecular weight of the modified polyolefin polymer is not particularly limited, but is preferably from 50,000 to 500,000, particularly preferably from 100,000 to 30,000, in view of the balance between impact resistance and moldability.

These commercially available modified polyolefin polymers include Tafmer MP-0620 (Mitsui Petrochemical).

In the composition of the present invention, the maleimide copolymer forms dispersed particles, and the particle diameter of the dispersed particles is 0.01 to 1.
．． It needs to be 0 micron.

A particularly preferred particle size is 0.04 to 0.5 microns. More preferably, it is 0.05 to 0.3 micron.

However, the particle diameter of the dispersed particles is a value measured by observing an ultrathin section cut from a sample treated with hydrazine hydrate and stained with osminic acid using a transmission electron microscope. If the dispersed particle size is less than 0.01 micron, the melt viscosity of the composition obtained by mixing with polyamide will be high (and a shark-skinned defective phenomenon will occur on the surface of the molded product.
．． If it exceeds 0 micron, the mechanical strength of the composition will be poor.

It is also desirable that the modified polyolefin polymer forms dispersed particles, which are independent, amorphous, and fairly uniformly dispersed.

According to the findings of the present inventors, when the same amount of the same polyamide is used, the unsaturated dicarboxylic acid in the maleimide copolymer is a particularly important factor determining the dispersed particle size in the composition. It is the content of anhydride monomer groups; when the content is low, the particle size is large, and when the content is high, the particle size is small. The content of organic acid groups in the modified polyolefin polymer is also important, and exhibits the same effect as the unsaturated dicarboxylic anhydride monomer group in the imidized resin copolymer.

The composition of the present invention preferably contains an organic acid metal salt and/or a fatty acid amide compound.

Containing these compounds has the advantage of improving the impact strength of the resulting composition.

The organic acid metal salts used in the present invention include fatty acids such as lauric acid, myristylic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, and hydroxystearic acid, and aromatic carboxyl acids such as phthalic acid. Salts of acids and metals such as sodium, potassium, lithium, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, tin, and lead.

Divalent metal salts such as magnesium, calcium, barium, and zinc are preferred.

In addition, fatty acid amide refers to the primary amide of the above-mentioned fatty acid,
The secondary niamide may be a bisamide such as methylene bis stearyl amide or ethylene bis stearyl amide.

The content of the organic acid metal salt and/or fatty acid amide in the composition of the present invention is 0.01 to 5% by weight, preferably 0.01 to 5% by weight.
The amount is in the range of 0.05 to 2% by weight, more preferably 0.2 to 1% by weight. - If the amount is less than 0.01% by weight, no effect will be observed, and if it exceeds 5% by weight, properties such as heat resistance and rigidity may deteriorate, and the effect of improving impact value may be small.

Particularly preferably, these organic acid metal salts and fatty acid amide are used in combination, and the amounts of the organic acid metal salt and fatty acid amide used are as follows:
The ratio is not particularly critical as long as it is within the above-mentioned amount, but it is preferably around 1:1.

It is also possible to contain an antioxidant, and the use of phenolic antioxidants is preferred from the viewpoint of discoloration. As a phenolic antioxidant, octadecyl-3-(3,
5-di-t-butyl-4-hydroxyphenyl)propionate (e.g. Irganox 1076), N-
N'hexamethylenebis(3,5-di-t-butyl-
4-Hydroxycinnamamide (e.g. Irganox 1098), 3, 5-sheet t-7'' thyl-4-hydroxytoluene, 2,2°-methylenebis-(4-methyl-6-t-butylphenol), 4・4"-methylenebis(2,6-di-t-butylphenol), 4.4°
-butylidenebis-6-t-butyl-m-cresol,
2,6-bis(2°-hydroxy-3′-t-butyl-
5°-Methylbenzyl)-4-methylphenol, 1.
1,3-tris(2'-methyl-5'-t-butyl-4
°-Hydroxyphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3°,5'-di-t-butyl-4'-hydroxybenzyl)benzene, 4,4-
Thiobis(2'-methyl-6'-t-butylphenol), 2,2'-thiobis(4'-methyl-6'-t-butylphenol), 4,4"-thiobis(3-methyl-
6-t-butylphenol), 1,1,1-tetrakis[methyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate comethane, 2,2'-thiodiethylbis -(3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate], N-
Examples include lauroyl-p-aminophenol and N-stearoyl-p-aminophenol, and it is preferable to use a combination of those for general nylon and those for olefins. Furthermore, it is of course possible to use a copper chelate type antioxidant for nylon.

As another factor, the dispersed particle size also depends on the method of mixing the maleimide copolymer with polyamide, modified polyolefin polymer, and other thermoplastic resins.

Mixing of the maleimide copolymer, polyamide, modified polyolefin polymer, and other thermoplastic resins can be carried out using a normal melt kneading device, but a suitable melt kneading device is a screw extrusion machine,
There are bread mixers, cornices, mixed rolls, etc.

The composition of the present invention can be made into a composition by adding other additives or modifiers depending on the purpose. Specifically, reinforcing fibers such as glass fiber, carbon fiber, aramid fiber, etc. These include fillers such as talc, silica, clay, mica, and calcium carbonate, ultraviolet absorbers, flame retardants, lubricants, and colorants.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.
All parts and percentages used in the Examples and Comparative Examples are by weight. Further, all of these are illustrative and do not limit the content of the present invention.

The methods for measuring various properties are as follows.

Dispersed particle size in the composition: A pre-trimmed sample was immersed in hydrazine hydrate and left at 60°C for 48 hours. After washing with water, this sample was immersed in a 1% osmic acid aqueous solution and left at room temperature for 24 hours for staining. Ultrathin sections were cut from the stained samples and transmission electron micrographs were taken. The obtained image was analyzed to determine the particle size.

Impact strength: according to ASTM D-256, thickness 1/8
The notched isot was measured using an injection molded product.The ambient temperature was 23°C.

A strip-shaped test piece with a thickness of 2 mm formed by chemical-resistant nibless was placed in a 1/4 oval jig, and dioctyl phthalate was applied to the surface of the test piece at an ambient temperature of 23°C. After being left for 48 hours, the position of crank occurrence was determined. The critical strain was calculated. The maximum strain of the 1 part 4 elliptical jig used is the specimen thickness 2.
In the case of m, it is 1.11.

Dimensional stability: using ASTM D63B No. 2 dumbbells, treated at a humidity of 80% and a temperature of 60°C for 10 days, and then cooled to a product temperature of 23°C, the length and absolute dry state of the dumbbells, 23
The difference in dumbbell length in °C was defined as the dimensional change.

Appearance = 5oz injection molded with boss and ribs on the back,
A molded product having an opening was molded, and the appearance of the molded product was visually evaluated. The molding temperature is 260℃.

(1) Maleimide-based copolymer (A) For the maleimide-based copolymer, 100 parts of styrene was placed in an autoclave equipped with a stirrer, the inside of the system was purged with nitrogen gas, and then heated to a temperature of 80°C.

A solution of 67 parts of maleic anhydride and 0.2 parts of benzoin peroxide dissolved in 300 parts of methyl ethyl ketone was added to this over 8 hours. After the addition, the temperature was increased to 8 for an additional 4 hours.
It was kept at 0°C.

To the above copolymer, 1.2 parts of triethylamine and 38.1 parts of aniline were added, and the reaction solution was reacted at 130°C for 7 hours. The reaction solution was cooled to room temperature and poured into 300 parts of methanol that was vigorously stirred. After filtering and drying, a maleimide copolymer (a-2) was obtained. Other maleimide copolymers were prepared in the same manner. These are shown in Table-1.

Table 1 Unit: Mol% (2) Polyamide (B) The following nylon 6 and nylon 66 obtained by melt polymerization were used.

b-1) Nylon 6; concentrated sulfuric acid obtained from ε-caprolactam; relative viscosity of 2.65; b-2) Nylon 66; concentrated sulfuric acid obtained from equimolar salts of hexamethylene diamine and adipic acid; relative viscosity 2.55 nylon 66° (3) Modified polyolefin polymer (C) 10 kg of ethylene/l-olefin copolymer with 80 mol% ethylene content, 120 g of powdered maleic anhydride, 2.5- 310.0 g of dimethyl-2,5-di(t-butylperoxy)hexane was charged into a 2ON Henschel mixer through which nitrogen was passed, and stirred for 5 minutes to blend uniformly. 24℃
Graft reaction product (C-1) was obtained (the amount of maleic anhydride introduced into the copolymer was 0.9% by weight).

(4) Thermoplastic resins other than these (D) The following thermoplastic resins were used.

d-1) Acrylonitrile-butadiene-styrene copolymer ABS GR-2000 manufactured by Denki Kagaku Co., Ltd.d-2) Polycarbonate Panlite L-1250 manufactured by Kijinsha Examples-1 to 7 and Comparative Examples-1 to 5 Above (D Nylon- 6(b-1) 10kg of barium stearate and 0.05% by weight of barium stearate were blended at Henschel and 240"C0 was produced using a 40wmφ extruder.
After blending 05% by weight, maleimide copolymer resin (a
-2) 3.5 kg, modified polyolefin polymer (C-
1) 1.5 kg, antioxidant (octadecyl-3-(
0.25% of 3,5-di-t-butyl)-hydroxyphenyl-propionate and 0.25% of N.N'-hexamethylenebis(3,5-di-1-butyl)-hydroxy-hydrocinnamamide. 5% by weight), and after blending,
290 using a 40mφ extruder with CTM (manufactured by Kobe Steel)
It was extruded with 'llll' and made into a pellet.

5 kg of the obtained pellets and the above-mentioned ABS manufactured by Denki Kagaku Co., Ltd.
(GR-2000> After blending 5 kg of pellets, C
It was extruded at 270° C. using a 40 Dragon φ extruder equipped with a TM. The dispersed particle size of the maleimide copolymer in the resulting composition was 0.
．． It was IIJm. Further, the condition of the dispersed particles of the modified polyolefin polymer is also good. Using this pellet, a test mold for measuring physical properties was created using an injection molding machine, and various physical properties were measured. The results are shown in the table. Similarly, Example-
Comparative Examples 2 to 7 and Comparative Examples 1 to 5 were also conducted.

The standard molding temperature was 270°C, and slight modifications were made depending on the condition of the molded product.

The following is clear from the results of Examples and Comparative Examples.

From Example-1 and Comparative Example-1, if the unsaturated dicarboxylic anhydride monomer group in the maleimide copolymer is less than 3 mol%, impact strength is not developed; The dispersion of the coalescence was also poor and the dispersed particle system became large.

On the other hand, as in Comparative Example 2, there are too many unsaturated dicarboxylic acid anhydride groups, so the impact value is not improved and the appearance is poor.

Comparative Examples 3 and 4 do not contain component b or component C, but in these cases as well, impact strength is not developed and the critical strain, which is an index of chemical resistance, is small.

When the C component and the d component of Comparative Example 5 are not included, and the b component exceeds 60% by weight, the dimensional change is large and there is a problem in dimensional stability.

In contrast, Examples 1 to 7 have impact strength, dimensional stability,
It can be seen that the chemical resistance and appearance of the molded product are well balanced.

Comparative example

Claims (1)

[Claims] 1. (A): 30 to 70 mol% of aromatic vinyl monomer groups,
A maleimide copolymer consisting of 30 to 50 mol% of maleimide monomer groups, 3 to 20 mol% of unsaturated dicarboxylic anhydride monomer groups, and 0 to 50 mol% of other copolymerizable monomer groups. 10-50% by weight, (B): Polyamide 10
~60% by weight, (C): unsaturated dicarboxylic anhydride monomer group and/or unsaturated carboxylic acid monomer group 0.1~
Modified polyolefin polymer modified with 10% by weight 0
-40% by weight, and (D): 20 to 80% by weight of a thermoplastic resin other than the above (A), (B) and (C), and the maleimide copolymer of the component (A) is 0.01% by weight. ~1
．． A thermoplastic resin composition characterized in that it forms dispersed particles of 0 micron. 2. The thermoplastic resin of component (D) is an acrylonitrile-butadiene-styrene copolymer, an acrylonitrile-butadiene-styrene-α-methylstyrene copolymer, a methyl methacrylate-butadiene-styrene copolymer, and/or a polycarbonate. The thermoplastic resin composition according to claim 1. 3. The thermoplastic resin composition according to claim 1 or 2, containing an organic acid metal salt and/or a fatty acid amide.