JP2688237B2 - Resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent mechanical properties, heat resistance and moldability. More specifically, a thermoplastic resin composition comprising a polyamide, a specific maleimide-based copolymer, and an inorganic filler, which has improved hygroscopicity, heat resistance and molding processability of polyamide, and gives a molded article excellent in rigidity. Regarding things.

[Conventional technology]

Polyamide has excellent properties such as mechanical properties, chemical resistance, abrasion resistance, and electrical properties, but has low impact resistance (with notch) and low heat resistance, and has a large molding shrinkage. It has the drawback that defects such as sink marks and warpage are likely to occur. Furthermore, it is known that due to its high hygroscopicity, not only the appearance of the molded product tends to be defective during the molding process, but also the size or shape of the molded product is greatly changed, and the mechanical properties of the molded product are also easily changed. ing. In addition, the viscosity of the molten resin is low, and the drooling phenomenon in which the molten resin flows out like a string from the nozzle of the molding machine during injection molding easily occurs,
There is a disadvantage that the molding operation is complicated.

In order to improve such disadvantages of polyamide, attempts have been made to mix or react various kinds of polymer substances with polyamide. For example, a styrene resin such as polystyrene or a styrene-acrylonitrile copolymer was melt-mixed (Japanese Patent Publication No. Sho 38-23476, the same publication).
40-7380, U.S. Pat.Nos. 3,243,478 and 3,243,479,
West German Laid-Open Patent No. 2,403,889), because these resins have poor compatibility with polyamides, a layered peeling phenomenon was observed in a molded article made of the obtained composition, and mechanical properties were also poor. An attempt was made to mix a copolymer of styrene and an unsaturated dicarboxylic acid anhydride monomer with polyamide (JP-A-56-50931), but the resulting composition had poor thermal stability. . For the purpose of improving the compatibility, a copolymer of styrene and an unsaturated dicarboxylic acid anhydride monomer is used as a compatibilizing agent for a styrene resin and a polyamide, and a three-component composition is known. But (Japanese Patent Laid-Open No. 60
No. 195157), the resulting composition has improved compatibility and thermal stability, but its effect was insufficient. A copolymer in which both polymer chains are bonded is known, which is produced by melt-mixing a copolymer containing an imide compound of an unsaturated dicarboxylic acid and a polyamide (Japanese Patent Laid-Open No. 57-57719).
No. 57-141426), the properties of the obtained copolymer are easily affected by the production conditions of the melt mixer, which is industrially disadvantageous. Furthermore, the heat resistance and impact resistance of the obtained copolymer were not always sufficient. A composition comprising an unsaturated dicarboxylic acid anhydride monomer, an aromatic vinyl copolymer, a polyamide and a modified polyolefin is also known (Japanese Patent Laid-Open No. 61-171751), but these are excellent in heat resistance and heat stability. Is insufficient. As an improvement on this, a three-component composition comprising a copolymer of a maleimide monomer, a polyamide and a modified polyolefin is known (JP-A-62-59647).
No. 62-179546), a molded product made of the obtained composition has a defective phenomenon on the surface in the vicinity of the gate, has delamination, and is insufficient in terms of balance of impact value, elongation, rigidity, etc. Met.

[Problems to be solved by the invention]

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

The intent of the present invention is to provide a polyamide resin composition having excellent heat resistance and impact resistance and excellent rigidity.

[Means for solving the problem]

That is, in the present invention, 30 to 70 mol% of (A) aromatic vinyl monomer group, 30 to 50 mol% of maleimide monomer group, 3 to 20 mol% of unsaturated dicarboxylic acid anhydride monomer group and other Maleimide copolymer 10 to 50% by weight consisting of copolymerizable monomer group 0 to 50% by mole, polyamide 40 to 80% by weight, unsaturated dicarboxylic acid anhydride monomer group and / or unsaturated carboxylic acid A thermoplastic resin composition comprising 0 to 40% by weight of a modified polyolefin polymer modified with 0.1 to 10% by weight of a monomer group, and 50 to 98% by weight of a thermoplastic resin composition and 2 to 50% by weight of an inorganic filler. It was found that the composition is a thermoplastic resin composition having good heat resistance and impact resistance, excellent rigidity, moldability, and low hygroscopicity.

The method for producing the maleimide-based copolymer used in the present invention is not particularly limited. For example, aromatic vinyl monomers, maleimide-based monomers, unsaturated dicarboxylic anhydride monomers and other copolymerizable monomers can be used. It can be produced by radical copolymerization of a monomer.

Specific examples of the aromatic vinyl monomer include styrene, α
-Methylstyrene, vinyltoluene, t-butylstyrene and the like, and specific examples of the maleimide-based monomer include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide and N-. There are cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide and the like, and specific examples of the unsaturated dicarboxylic acid anhydride monomer include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride and anhydrous. Examples include ethyl maleic acid and phenyl maleic anhydride, and other copolymerizable monomers include, for example, acrylic monomers. Specific examples of acrylic monomers include methyl (meth) acrylate and ethyl (meth)
Acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, decyl (meth) acrylate, octadecyl (meth) acrylate, hydroxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) There are acrylates and the like, and these can be used alone or in combination. Here, methyl (meth) acrylate means methyl acrylate or methyl methacrylate.

The method for copolymerizing these monomers is not particularly limited, and any known radical copolymerization method can be used.

As another method for producing a maleimide copolymer used in the present invention, a copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic acid anhydride monomer and other copolymerizable monomers may be prepared using ammonia or a copolymer. A method of reacting with a primary amine to imidize an acid anhydride group can be exemplified.
The imidation reaction between a polymer substance having an acid anhydride group in a polymer chain and an amine compound is known, for example,
According to the method disclosed in JP-A-26936 or JP-A-62-8456, a polymer compound and an amine compound can be reacted to produce a maleimide copolymer having a desired imide group.

Examples of the primary amine used in the imidation reaction include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine,
Decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine,
Bromophenylamine, dibromophenylamine and the like.

The imidization reaction is carried out in a solution state using an autoclave,
The reaction can be performed in a bulk molten state or 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.

The solvent used in the solution reaction is arbitrary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, tetrahydrofuran, ethers such as 1,4-dioxane, toluene, aromatic hydrocarbons such as xylene, dimethyl Examples include formamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and the like.

The reaction temperature for imidization is preferably in the range of 50 to 350 ° C.,
A range from 00 to 300 ° C. is particularly preferred.

The imidation reaction does not necessarily require the presence of a catalyst, but if used, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-
Tertiary amines such as diethylaniline are preferred.

The maleimide-based copolymer used in the present invention contains 30 to 70 mol% of an aromatic vinyl monomer group and 30 of a maleimide-based monomer group.
~ 50 mol%, unsaturated dicarboxylic anhydride monomer group 3 ~ 20
Mol% and other copolymerizable monomer groups 0 to 50 mol%
Consists of A more preferred range is an aromatic vinyl monomer group.
50-60 mol%, maleimide monomer group 40-50 mol%, unsaturated dicarboxylic acid anhydride monomer group 3-10 mol% and other copolymerizable monomer group 0-30 mol% . When the aromatic vinyl monomer group is less than 30 mol%, it is difficult to industrially reproducibly produce a polymer having a homogeneous composition, and the maleimide copolymer is mixed with a polyamide and an inorganic filler. The composition obtained in this way is inferior in properties such as thermal stability, moldability and mechanical strength. If the aromatic vinyl monomer group exceeds 70 mol% or the maleimide monomer group is less than 30 mol%, the heat resistance of the obtained composition is poor and the maleimide monomer group is If it exceeds 50 mol%, the moldability of the obtained composition will be poor. If the unsaturated dicarboxylic acid anhydride monomer group is less than 3 mol%, the compatibility with the polyamide and the inorganic filler becomes poor, the particle size of the maleimide copolymer dispersed particles becomes large, and the mechanical strength becomes poor. Moreover, peeling phenomenon is observed in the molded product of the composition. On the other hand, if the content of the unsaturated dicarboxylic acid anhydride monomer group exceeds 20 mol%, the particle size of the maleimide-based copolymer dispersed particles of the composition becomes too small, so that the molding processability is poor and the heat stability of the molded product is poor. The properties may be poor and the surface may be roughened like a shark skin.

The polyamide used in the present invention is not particularly limited, and may be an polyamide obtained from an aliphatic, aromatic or alicyclic dicarboxylic acid and a diamine, a polyamide obtained from an aminocarboxylic acid or a cyclic lactam, or the like. Specific examples include aliphatic polyamides such as nylon 6, nylon 6.6, nylon 6.9, nylon 6.9, nylon 6.6, nylon 4.6, nylon 11, nylon 12, and poly (hexamethylene terephthalate). Lamid), poly (hexamethylene isophthalamide), polyamide containing an aromatic ring such as poly (m-xylylene adipamide), and the like, and these can be used alone or in combination.

In the present invention, a composition obtained by mixing 10 to 50% by weight of a maleimide copolymer, 40 to 80% by weight of a polyamide, and 0 to 40% by weight of a modified polyolefin polymer, if necessary, is a composition of 50 to 98% by weight.
And 2 to 50% by weight of an inorganic filler are mixed to form a composition. When the maleimide-based copolymer is less than 10% by weight or the polyamide exceeds 80% by weight, the heat resistance of the obtained composition, If the degree of improvement in molding processability or hygroscopicity is insufficient and the maleimide copolymer exceeds 50% by weight or the polyamide is less than 40% by weight, the mechanical strength and chemical resistance of the composition Or wear resistance is inferior.

Further, the modified polyolefin-based polymer may be used if necessary for the purpose of improving impact resistance, but if it is 40% by weight or more, the decrease in rigidity is too large.

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

The modified polyolefin polymer refers to a modified olefin monomer polymer or copolymer, and 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
-Hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene and the like. The modified polyolefin-based polymer may be, if necessary, a non-conjugated diene monomer such as 4-ethylidene norbornene or dicyclopentadiene;
Acrylic monomers and the like already exemplified as copolymerizable monomers that can constitute the maleimide-based copolymer may be copolymerized within a range showing rubber-like elasticity. A preferred composition range is exemplified by 20 to 90 mol% of ethylene, 10 to 80 mol% of an α-olefin monomer and 0 to 10 mol% of other monomers.
Mol%, and it is particularly preferred that the ethylene content is 50 to 85 mol%. Further, the Tg of these modified polyolefin-based polymers is -10C or lower, particularly preferably -30C or lower.

As the unsaturated dicarboxylic acid anhydride monomer constituting the modified polyolefin-based polymer, those already exemplified as the monomer capable of constituting the maleimide-based copolymer can be used, but maleic anhydride is particularly preferable, and unsaturated. Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, fumaric acid and maleic acid.

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

The modification referred to in the present invention is a monomer group used for modification in the main chain or side chain of the polyolefin-based polymer, for example,
This indicates that a maleic anhydride group is present, and can be modified by known techniques such as random copolymerization and graft polymerization. The modification method is not particularly limited, and for example, the methods disclosed in Japanese Patent Publication Nos. 39-6810, 52-43677, 53-5716, 56-9925, and 58-445. Denaturation can be carried out according to Further, those which are modified as grafts rather than being introduced into the main chain are preferable in terms of low-temperature impact value and the like. Furthermore, the residual amount of unreacted monomer is 0.5
The smaller the content is by weight, the more preferable.

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 300,000, from the balance of impact resistance and moldability.

Commercially available modified polyolefin polymers include:
There is Tuffmer MP-0620 (Mitsui Petrochemical).

In the composition of the present invention, the maleimide-based copolymer forms dispersed particles, and the particle size of the dispersed particles is 0.01 to 1.0.
It is preferably micron. A particularly preferred particle size is 0.04 to 0.5 micron. More preferably, 0.05
~ 0.3 microns. However, the particle size of the dispersed particles is a value measured by observing an ultrathin section cut from a sample treated with hydrazine monohydrate and then stained with osmic acid using a transmission electron microscope. If the dispersed particle size is too small, the composition obtained by mixing the polyamide and the inorganic filler has a high melt viscosity, and a shark-skin-like defect phenomenon occurs on the surface of the molded product. If the dispersed particle size is too large, the mechanical strength of the composition becomes poor.

When a modified polyolefin-based polymer is used, the coarse polymer also forms dispersed particles and has an independent amorphous shape.
It is desirable that they are dispersed almost uniformly.

According to the findings of the present inventors, when the same polyamide is used in the same amount, the one that is particularly important as a factor that determines the dispersed particle size in the composition is the unsaturated dicarboxylic acid in the maleimide-based copolymer. 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. Also, when using a modified polyolefin-based polymer, the content of the organic acid group in the polymer is similarly important, and the unsaturated dicarboxylic acid anhydride monomer group in the imidized resin copolymer Similar effects are shown.

Next, as the inorganic filler used in the present invention, talc, silica, clay, mica, calcium carbonate, titanium oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, potassium titanate, calcium silicate,
Barium sulfate is a preferred example. These inorganic fillers may be used alone or in combination of two or more.

The content of the inorganic filler in the composition of the present invention is 2 to 50% by weight. Preferably in the range of 5 to 45% by weight, 2% by weight
If it is less than 50, the effect of improving rigidity and heat resistance is insufficient, and 50
If it exceeds 5% by weight, impact resistance may be remarkably deteriorated and the surface condition of the molded product may be poor. In addition, the inorganic filler,
It may be surface-treated.

In addition, a lubricant, an antioxidant, an ultraviolet absorber, a flame retardant, a colorant, etc. may be added to the above resin composition of the present invention depending on the application. For example, as a lubricant
Organic acid metal salts and fatty acid amides can be used, and organic acid metal salts are fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, and hydroxystearic acid. , A salt of an aromatic carboxylic acid such as phthalic acid and a metal such as sodium, potassium, lithium, magnesium, calcium, strontium, barium, zinc, cadmium, aluminum, tin and lead. A divalent metal salt such as magnesium, calcium, barium or zinc is preferable.

The fatty acid amide is a primary amide or a secondary amide of the above-mentioned fatty acid, and the secondary amide may be a bisamide such as methylenebisstearylamide and ethylenebisstearylamide.

As the antioxidant, it is preferable to use a phenolic antioxidant because of discoloration. As a phenolic antioxidant, octadecyl-3- (3.5-di-t-butyl-4-
Hydroxyphenyl) propionate (eg Irganox 1076), N-N'hexamethylenebis (3.5-
Di-t-butyl-4-hydroxycinnamamide (eg Irganox 1098), 3.5-di-t-butyl-4
-Hydroxytoluene, 2.2'-methylenebis- (4
-Methyl-6-t-butylphenol), 4,4'-methylenebis (2.6-di-t-butylphenol), 4
4'-butylidene bis-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), 1.1.1.1
-Tetrakis [methyl-3- (3.5-di-t-butyl-
4-hydroxyphenyl) propionate] methane, 2
.2'-thiodiethylbis- [3- (3.5-di-t-
Butyl-4-hydroxyphenyl) -propionate], N-lauroyl-p-aminophenol and N
-Stearoyl-p-aminophenol and the like, and it is preferable to use a combination of general nylon and olefin. It is of course possible to use a copper chelate-based antioxidant for nylon.

As a method for obtaining the composition of the present invention, a usual melt mixing method can be used. Examples of melt-kneading devices that can be suitably used include a screw extruder, a roll mixer, a Banbury mixer, and a cokneader.

The order of melt-mixing may be such that all the components may be melt-mixed at the same time, or a method in which two or three types of components are melt-mixed in advance, a maleimide-based copolymer and a polyamide, and optionally a modified polyolefin-based polymer. It is possible to use a method in which the above are melt-mixed in advance and then the inorganic filler is kneaded.

Further other polymers in the resin composition of the present invention, for example, polyolefin polymers such as polypropylene and polyethylene, polystyrene, styrene resins such as ABS, PET, PBT.
Polyester resin such as PPE resin, PPS resin and the like can be mixed in an amount that does not impair the characteristics of the composition of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but all parts and percentages used in Examples and Comparative Examples are by weight. These are all examples and do not limit the content of the present invention.

 In addition, the measuring method of various properties is as follows.

Dispersion particle size in the composition: A sample previously trimmed was immersed in hydrazine monohydrate 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 to stain. Ultrathin sections were cut out from the stained samples, and transmission electron micrographs were taken. The obtained image was analyzed to determine the particle size.

Heat resistance: According to ASTM D-648, the heat distortion temperature (HDT) was measured with a load of 18.6 kg / cm ² using an injection molded product with a thickness of 1/4 ". (Without annealing) Impact strength: ASTM D- According to 256, the notched Izod was measured with a 1/4 "thick injection molded product. Ambient temperature is 23
° C.

Flowability: According to ASTM D-1238, temperature 265 ℃, load 10kg
Was used to measure the melt flow rate (MFR).

Appearance: A molded article having a boss and ribs on the back surface and having an opening was molded using a 5 oz injection molding machine, and the appearance of the molded article was visually judged. The molding temperature is 260 ° C.

Tensile strength: ASTM D-638 Flexural strength: ASTM D-790 Flexural modulus: ASTM D-790 (1) Polyamide (B) The following nylon 6, nylon 12, and nylon 66 obtained by the melt polymerization method are used.

b-1) Nylon 6; Nylon 6 having a relative viscosity of concentrated sulfuric acid of 2.65 obtained from ε-caprolactam.

b-2) Nylon 12; Concentrated sulfuric acid relative viscosity 2.40 nylon 12 obtained from 12-aminododecanoic acid.

b-3) Nylon 66; nylon with concentrated sulfuric acid relative viscosity 2.55 obtained from equimolar salt of hexamethylenediamine and adipic acid
66.

(2) Maleimide Copolymer (A) The maleimide copolymer was prepared by charging 100 parts of styrene into an autoclave equipped with a stirrer, replacing the system with nitrogen gas, and then heating to 80 ° C. To this was added a solution prepared by dissolving 67 parts of maleic anhydride and 0.2 part of benzoin peroxide in 300 parts of methyl ethyl ketone over 8 hours. After the addition, the temperature was kept at 80 ° C. for a further 4 hours.

To the above copolymer, 1.2 parts of triethylamine and 38.1 parts of aniline were added and reacted at 130 ° C. for 7 hours. The reaction solution was cooled to room temperature and stirred vigorously.
Pour 0 parts, filter, and dry to obtain maleimide copolymer (a-
1) got. Other maleimide-based copolymers were similarly prepared. These are shown in Table 1.

(3) Modified polyolefin polymer (C) 10 kg of ethylene / α-olefin copolymer pellets having an ethylene content of 80 mol%, 120 g of powdered maleic anhydride,
.5-dimethyl-2.5-di (t-butylperoxy)
Hexane-3 10.0 g was charged into a 20-liter Henschel mixer in which nitrogen was passed, and the mixture was stirred for 5 minutes and blended uniformly, and this was a 40 mmφ extruder (nitrogen passed, L / D-28, Dalmage type).
Then, make pellets. The cylinder temperature was adjusted so that the polymer temperature was 240 ° C, and the graft reaction product (c
-1) was obtained (the amount of maleic anhydride introduced into the copolymer was
0.9% by weight).

(4) Inorganic filler (D) d-1) Toncal (Shiroishi Calcium Co., Ltd., trade name Whiteton SB) d-2) Calcium Silicate (Kinsei Kogyo Co., Ltd., trade name FPW # 5000) d- 3) Magnesium hydroxide (Kyowa Chemical Industry Co., Ltd., trade name Kisuma 5B) Example 1 10 kg of nylon-6 (b-1) above was blended with 0.05% by weight of barium stearate in 20 L Henschel to give 40 m
Extruded at 240 ℃ with mφ extruder and pelletized 4.0k
g, 20l Henschel, blended with 0.5% by weight of ethylenebisstearyl amide, maleimide copolymer resin (a-1) 3.0 kg, modified polyolefin polymer (c-1) 1.5
kg, tankar 1.5kg, antioxidant (octadecyl-3-
Add 0.25% by weight of (3.5-di-t-butyl) -hydroxyphenyl-propionate and 0.5% by weight of N.N'-hexamethylenebis (3.5-di-t-butyl) -hydroxy-hydrocinnamamide. After blending, the mixture was extruded with a 40 mmφ extruder equipped with CTM (Kobe Steel Co., Ltd.) at 290 ° C. and pelletized. The dispersed particle size of the maleimide-based copolymer in the obtained composition was 0.1 μm. The state of the dispersed particles of the modified polyolefin polymer is also good. Using the pellets, a test mold for measuring physical properties was prepared using an injection molding machine, and various physical properties were measured. The results are shown in Table 2. Similarly, Examples 2 to 7 and Comparative Examples 1 to 3 were performed.

The molding temperature was set at 270 ° C. as a standard, and was slightly modified depending on the condition of the molded product.

From Table 2, the composition of the present invention has rigidity, impact strength, heat resistance,
It is recognized that the balance of fluidity is excellent.

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Claims (2)

(57) [Claims] 1. (A) 30 to 70 mol% of aromatic vinyl monomer group, 30 to 50 mol% of maleimide monomer group, 3 to 20 mol% of unsaturated dicarboxylic acid anhydride monomer group and others 10 to 50% by weight of a maleimide-based copolymer consisting of 0 to 50% by mole of a copolymerizable monomer group, (B) a polyamide 40 to 80% by weight, and (C) an unsaturated dicarboxylic acid anhydride monomer group And / or 50 to 98% by weight of a thermoplastic resin composition consisting of 0 to 40% by weight of a modified polyolefin polymer modified with 0.1 to 10% by weight of an unsaturated carboxylic acid monomer group, and an inorganic filler of 2 to 50% A thermoplastic resin composition containing 100% by weight. 2. The resin composition according to claim 1, wherein the maleimide-based copolymer forms dispersed particles of 0.01 to 1.0 micron.