JP2782518B2 - Resin composition - Google Patents

Description

The present invention relates to a thermoplastic resin composition having excellent mechanical properties, moldability and appearance of a molded product. More specifically, the present invention relates to a thermoplastic resin composition comprising a polyamide and a specific maleimide-based copolymer, which has improved hygroscopicity, heat resistance, and moldability, and provides a molded article having an excellent appearance.

[Prior art] Polyamide has excellent properties such as mechanical properties, chemical resistance, abrasion resistance, and electrical properties, but has low impact resistance (with a notch), low heat resistance, and low molding shrinkage. It is large and has the disadvantage that defects such as sink marks and warpage are likely to occur in the molded product. 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, melt mixing of styrene resins such as polyethylene or styrene-acrylonitrile copolymer has been performed (Japanese Patent Publication No. 38-23476,
No. 40-7380, U.S. Pat. Nos. 3,243,478, 3,24
No. 3,479, West German Published Patent No. 2,403,889), because these resins are inferior in compatibility with polyamide, a laminar exfoliation phenomenon of a molded article comprising the obtained composition was observed, Inferior in properties. Attempts have been made to mix a copolymer of styrene and an unsaturated dicarboxylic anhydride monomer with polyamide (JP-A-56-50931), but the resulting composition has poor thermal stability. . For the purpose of improving compatibility, a three-component composition using a copolymer of styrene and an unsaturated dicarboxylic anhydride monomer as a compatibilizer between a styrene resin and a polyamide is known. (JP-A-60-195157), the resulting composition is compatible,
Although the thermal stability has been improved, its effect has been insufficient. Produced by melt-mixing a copolymer containing an imide compound of an unsaturated dicarboxylic acid and a polyamide,
Copolymers in which both polymer chains are bonded are known (JP-A-57-57719 and JP-A-57-141426), but the properties of the obtained copolymer are influenced by the production conditions of a melt mixer. Easy to receive,
Industrially disadvantaged. Furthermore, the heat resistance and impact resistance of the obtained copolymer were not always sufficient. A composition comprising an unsaturated dicarboxylic anhydride monomer, an aromatic vinyl copolymer, a polyamide and a modified polyolefin is also known (Japanese Patent Application Laid-Open No. 1717151/1986). Not enough. As this improvement, a ternary composition comprising a copolymer of a maleimide-based monomer, a polyamide and a modified polyolefin is known (Japanese Patent Application Laid-Open Nos. 62-59647 and 62-179546). The molded article made of the composition had a poor phenomenon on the surface near the gate, had delamination properties, and was insufficient in terms of balance of impact value, elongation, rigidity, and the like.

[Problems to be Solved by the Invention] As described above, many attempts have been made to improve various properties of polyamide, but all of the effects have been practically insufficient.

An object of the present invention is to provide a polyamide resin composition having good heat resistance and impact resistance, a good balance of elongation and rigidity, and giving a beautiful appearance.

[Means for Solving the Problems] That is, in the present invention, 30 to 67 mol% of an aromatic vinyl monomer group,
10 to 50% by weight of a maleimide-based copolymer comprising 30 to 50% by mole of a maleimide-based monomer group, 3 to 20% by mole of an unsaturated dicarboxylic anhydride monomer group and 0 to 37% by mole of an acrylic-based monomer group % And polyamide 40 to 80% by weight, unsaturated dicarboxylic anhydride monomer group and / or unsaturated carboxylic acid monomer group
A composition comprising 3 to 40% by weight of a modified polyolefin polymer modified at 0.1 to 10% by weight, wherein the maleimide-based copolymer is a composition forming dispersed particles, and the particle size of the dispersed particles is 0.01 to 0.01%. ~ 1.0 micron in the thermoplastic resin composition characterized by the impact resistance, elongation, rigidity, good balance of heat resistance, etc.,
It has been found that it has excellent moldability and low hygroscopicity, and that the molded product gives a beautiful appearance. Further, in the present invention, it is preferable that the modified polyolefin-based polymer is also dispersed as dispersed particles in an independent amorphous form having a size of several μm or less and substantially uniformly.

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

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, N- Cyclohexylmaleimide, N-phenylmaleimide, N-tolylmaleimide and the like, specific examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethylmaleic anhydride, There are ethyl maleic acid, phenyl maleic anhydride and the like. Specific examples of the acrylic monomer include methyl (meth) acrylate, 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) acrylate, etc. These can be used alone or in combination. Here, (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.

Another method for producing the maleimide copolymer used in the present invention is to prepare a copolymer of an aromatic vinyl monomer, an unsaturated dicarboxylic anhydride monomer and an acrylic monomer with ammonia or a primary amine. And a method of imidizing an acid anhydride group by reacting with the above. The imidation reaction between a polymer having an acid anhydride group in a polymer chain and an amine compound is known, for example, according to the method disclosed in JP-B-61-26936 or JP-B-62-8456.
By reacting a polymer substance with an amine compound, a maleimide-based copolymer having an intended imide group can be produced.

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.

Melting used for the melting reaction is arbitrary, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, tetrahydrofuran, ethers of 1,4-dioxane, aromatic hydrocarbons such as toluene and xylene, dimethylformamide , Dimethylsulfoxide, 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 imidization reaction does not necessarily require the presence of a catalyzer, 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 67 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 0 to 37 mol% of acrylic monomer groups. A more preferred range is from 50 to 60 aromatic vinyl monomer groups.
Mol%, 40-50 mol% of a maleimide monomer group, 3-10 mol% of an unsaturated dicarboxylic anhydride monomer group, and 0-30 mol% of an acrylic monomer group. When the amount of the aromatic vinyl monomer group is less than 30 mol%, it is difficult to produce a polymer having a homogeneous composition with good industrial reproducibility, and it is obtained by mixing the maleimide-based copolymer with a polyamide. Inferior properties such as thermal stability, moldability and mechanical strength of the resulting composition.
When the content of the aromatic vinyl monomer group exceeds 67 mol% or the content of the maleimide monomer group is less than 30 mol%, the heat resistance of the obtained composition is inferior, and
If it exceeds 50 mol%, the moldability of the obtained composition will be poor. When the content of the unsaturated dicarboxylic acid anhydride monomer group is less than 3 mol%, the compatibility of the composition obtained by mixing with the polyamide is poor, and the particle diameter of the miremid-based copolymer-dispersed particles becomes large. And the peeling phenomenon is observed in a molded product of the composition. Further, when the unsaturated dicarboxylic anhydride monomer group exceeds 20 mol%, the particle size of the maleimide-based 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 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, 10 to 50% by weight of a maleimide-based copolymer, 40 to 80% by weight of a polyamide, and a modified polyolefin-based polymer 3
When the amount of the maleimide-based copolymer is less than 10% by weight or the amount of the polyamide is more than 80% by weight, the resulting composition is heat-resistant, moldable, or hygroscopic. If the degree of improvement is insufficient and the maleimide-based copolymer exceeds 50% by weight or the polyamide is less than 40% by weight, the mechanical strength, chemical resistance or abrasion resistance of the composition is inferior. .

If the modified polyolefin polymer is less than 3% by weight, the effect of improving the impact resistance is low, and if it is 40% by weight or more, the decrease in rigidity is too large.

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 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. In addition, the modified polyolefin-based polymer is already exemplified, if necessary, as a non-conjugated diene monomer such as 4-ethylidene norbornene, dicyclopetadiene, or a copolymerizable monomer capable of forming a maleimide-based copolymer. The acrylic monomer or the like may be copolymerized within a range showing rubber-like elasticity. A preferred composition range is, for example, 20 to 90 mol% of ethylene, 10 to 80 mol% of an α-olefin monomer and 0 to 10 mol% of other monomers, and the ethylene content is 50 to 85 mol%. Is particularly preferred. Further, the Tg of these modified polyolefin-based polymers is -10C or lower, particularly preferably -30C or lower.

As the unsaturated dicarboxylic 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 preferred, and unsaturated maleic anhydride is preferred. 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 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. For example, JP-B-39-6810, JP-B-52-43677, and JP-B-53-5716.
The denaturation can be carried out according to the methods disclosed in JP-B-56-9925 and JP-B-58-445. 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. Further, it is preferable that the residual amount of the unreacted monomer is smaller by 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 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 needs to be microns. Particularly preferred particle sizes are between 0.04 and 0.5 microns. More preferably 0.05 to 0.3
Micron. 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 less than 0.01 micron, the composition obtained by mixing with the polyamide 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 exceeds 1.0 micron, the mechanical strength of the composition becomes poor.

It is also desirable that the modified polyolefin-based polymer forms dispersed particles, and is dispersed in an independent amorphous form and 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 for determining the dispersed particle size in the composition is the unsaturated dicarboxylic anhydride in the maleimide-based copolymer. The content is the content of the monomer group. When the content is low, the particle size is large, and when the content is high, the particle size is small. The content of the organic acid group 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 a metal salt of an organic acid and / or a fatty acid amide compound. When these compounds are contained, there is an advantage that the impact strength of the obtained composition is improved.

The organic acid metal salt used in the present invention includes lauric acid,
Fatty acids such as myristylic acid, palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, ricinoleic acid, and hydroxystearic acid; aromatic carboxylic acids such as phthalic acid; and sodium, potassium, lithium magnesium, calcium, strontium, and barium And salts with metals such as zinc, cadmium, aluminum, tin and lead. Magnesium, calcium, barium, zinc, etc.
Divalent metal salts are preferred.

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.

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 0.05 to 5% by weight.
In the range of 2% by weight, more preferably 0.2 to 1% by weight. If less than 0.01% by weight, the effect of addition is not recognized,
If it exceeds 5% by weight, properties such as heat resistance and rigidity may be reduced, and the effect of improving the impact value may be small.

Particularly preferably, these organic acid metal salts and fatty acid amides are used in combination.
Near is preferred.

It is also possible to contain an antioxidant, and the use of a phenolic antioxidant is preferred from the viewpoint of discoloration and the like. As a phenolic antioxidant, octadecyl-3- (3.
5-di-t-butyl-4-hydroxyphenyl) propionate (for example, Irganox 1076), N-N'hexamethylenebis (3.5-di-t-butyl-4-hydroxycinnamamide (for example, 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'-butylidenebis-6-t-
Butyl-m-cresol, 2,6-bis (2'-hydroxy-3'-tert-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'-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-tert-butyl-4-hydroxyphenyl) propionate] methane, 2.2'-thiodiethylbis- [3- (3.5-di-t-butyl-4-
Hydroxyphenyl) -propionate], N-lauroyl-p-aminophenol and N-stearoyl-
There are p-aminophenol and the like, and it is more 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 another factor, the dispersed particle size also depends on the method of mixing the maleimide-based copolymer with the polyamide or the modified polyolefin-based polymer.

The mixing of the maleimide-based copolymer and the polyamide, the modified polyolefin-based polymer can be carried out using a usual melt-kneading apparatus, but as a melt-kneading apparatus that can be suitably used, a screw extruder, a Banbury mixer, a co-kneader, There are mixing rolls and the like.

The composition of the present invention can be made into a composition by adding other additives or modifiers depending on the application.Specifically, glass fibers, carbon fibers, reinforcing fibers such as aramid fibers, There are fillers such as talc, silica, clay, mica, calcium carbonate, etc., ultraviolet absorbers, flame retardants, lubricants, coloring agents and the like.

[Examples] 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 on a weight basis. 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
Stained for 24 hours. 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: Heat distortion temperature (HDT) was measured under a load of 18.6 kg / cm ² using an injection molded product having a thickness of 1/4 ″ according to ASTM D-648.

(No annealing) Impact strength: Notched Izod was measured using a 1/4 "thick injection molded product according to ASTM D-256. The ambient temperature was 23 ° C.

Flowability: 265 ° C, load according to ASTM D-1238
The melt flow rate was measured at 10 kg.

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

(1) Polyamide (B) The following nylon 6, nylon 12, and nylon 66 obtained by a melt polymerization method are used.

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

b-2) Nylon 12; Nylon 12 having a relative viscosity of 2.40 and a concentrated sulfuric acid obtained from 12-aminododecanoic acid.

b-3) Nylon 66: Nylon 66 with concentrated sulfuric acid having a relative viscosity of 2.55 obtained from equimolar salts of hexamethylenediamine and adipic acid.

(2) Maleimide-based copolymer (A) The maleimide-based 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 alline were added and reacted at 130 ° C. for 7 hours. The reaction solution was cooled to a greenhouse and vigorously stirred methanol 30
0 parts, filtered and dried to obtain a maleimide-based copolymer (a
-3) was obtained. Other maleimide-based copolymers were similarly prepared. These are shown in Table 1.

(3) Modified polyolefin polymer 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 Henschel mixer through which nitrogen was passed, and stirred for 5 minutes to be uniformly blended.
This is formed into a pellet by a 40 mmφ extruder (flowing nitrogen, L / T-28, dalmage type). The cylinder temperature was adjusted so that the polymer temperature became 240 ° C. to obtain a graft reaction product (c-3) (the amount of maleic anhydride introduced into the copolymer was 0.9% by weight). Other modified polyolefin polymers were prepared in the same manner. These are shown in Table-2.

Examples-1 to 18 and Comparative Examples-1 to 5 0.05% by weight of barium stearate was blended with 10 kg of the nylon-6 (b-1) in 20 Henschel,
Extruded at 240 ° C with a 40mmφ extruder and pelletized
5.0 kg, put into 20 Henschel, after blending 0.5% by weight of ethylene bisstearyl amide, 3.5 kg of maleimide copolymer resin (a-2), 1.5 kg of modified polyolefin polymer (c-3), antioxidant ( Octadecyl-3-
0.25% by weight of (3.5-di-t-butyl) -hydroxyphenyl-propionate and 0.5% by weight of NN'-hexamethylenebis (3.5-di-t-butyl) -hydroxy-hydrocinnamide were added. After blending, the mixture was extruded at 290 ° C. using a 40 mmφ extruder with CTM (manufactured by Kobe Steel) to form pellets. 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 pellet, an injection molding machine was used to prepare a test mold for measuring physical properties, and various physical properties were measured. The results are shown in the table. Similarly, Examples 2 to 15 and Comparative Examples 1 to 5 were performed. In Comparative Examples -1 and 2, the maleic anhydride content in the maleimide-based copolymer was out of the range. In Comparative Example-3, the maleic anhydride content in the modified polyolefin polymer was out of the range. Comparative Example-
In 4 and 5, the content of the modified polyolefin polymer is out of the range.

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

The following is clear from the results of the examples and comparative examples.

From Example 2 and Comparative Example 1, if the maleimide-based copolymer does not have an unsaturated dicarboxylic anhydride monomer group, the effect of improving the impact value is small, the elongation is low, and it is not practical. At this time, the dispersion of the maleimide-based copolymer was also poor, and the dispersed particle size was large.

Further, even when the amount of the unsaturated dicarboxylic anhydride is too large as in Comparative Example-2, the impact value is not improved, and the appearance is poor and the moldability (flow) is reduced.

From Example-2 and Comparative Example 3, it is found that the content of dicarboxylic anhydride in the polyolefin polymer is important, and if not, the effect of improving the impact value is small and the appearance is poor.

As described above, it can be seen that only when both contain an appropriate unsaturated carboxylic acid anhydride (graft, copolymerization), the physical property balance is improved.

Further, as is clear from the examples and comparative examples, it is understood that the dispersion state of the maleimide-based copolymer is also important for the physical properties, and it does not matter whether the particle size is large or small.

Electron micrographs of the resin compositions obtained in Example 2 and Comparative Examples 1 and 3 are shown in FIG. 1, FIG. 2 and FIG.

As can be seen from FIG. 1, the resin composition of the present invention has a maleimide-based copolymer having a particle size of 0.1 μm, and the modified polyolefin-based polymer is almost uniformly dispersed in a semi-continuous layer.

In Comparative Example-1, the dispersed particle size of the maleimide-based copolymer was large, and the dispersed particle size of the modified polyolefin-based copolymer was also poor unlike Example-1.

In Comparative Example-3, the dispersed particle diameter of the maleimide-based copolymer was small, and the dispersion of the modified polyolefin-based polymer was non-uniform.

[Brief description of the drawings]

FIG. 1, FIG. 2 and FIG. 3 show Example-2,
6 is an electron micrograph showing a dispersion state of maleimide-based copolymer particles of the resin compositions obtained in Comparative Examples 1 and 3.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C08L 35/06 C08L 35/06 (56) References JP-A-63-105051 (JP, A) JP-A-62-59647 (JP) JP-A-61-171751 (JP, A) JP-A-57-57719 (JP, A) JP-A-64-79243 (JP, A) JP-A-2-41359 (JP, A)

Claims (3)

(57) [Claims] (A) 30 to 67 mol% of an aromatic vinyl monomer group, 30 to 50 mol% of a maleimide monomer group, 3 to 20 mol% of an unsaturated dicarboxylic anhydride monomer group, and others. 10 to 50% by weight of a maleimide copolymer comprising 0 to 37% by mole of a copolymerizable monomer group of (B) 40 to 80% by weight of a polyamide,
And (C) a composition comprising, as an active ingredient, 3 to 40% by weight of a modified polyolefin polymer modified with 0.1 to 10% by weight of an unsaturated dicarboxylic anhydride monomer group and / or an unsaturated carboxylic acid monomer group. In the product, the maleimide copolymer is
A thermoplastic resin composition formed with dispersed particles of 0.01 to 1.0 microns. 2. The modified polyolefin polymer is amorphous,
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is substantially uniformly dispersed. 3. The composition according to claim 1, which comprises an organic metal salt and / or an aliphatic amide.