JPH11335553A - Thermoplastic resin composition and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin compsn. excellent in mechanical properties such as strength and impact resistance and in moldability, compatibility, and chemical resistance by combining a polyamide resin with specific polyolefin resins and a molded article obtd. from the compsn. SOLUTION: This compsn. comprises (A) 100 pts.wt. polyamide resin, (B) 5-100 pts.wt. copolymer comprising an ethylene/α-olefin copolymer formed from ethylene and a 3-20C α-olefin and having a ratio (Mw/Mn) of the wt. average mol.wt. (Mw) to the number average mol.wt. (Mn) calculated by gel permeation chromatography(GPC) of 3.0 or lower and/or a modified ethylene/α-olefin copolymer obtd. by modifying the above-mentioned ethylene/α-olefin copolymer with a carboxylic acid deriv., and (C) 5-100 pts.wt. modified polyolefin resin other than ingredient B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having excellent mechanical properties such as strength and impact resistance, moldability and chemical resistance. The present invention relates to a thermopolyamide resin composition having excellent mechanical properties, moldability, and chemical resistance obtained by combining a polyolefin resin.

[0002]

2. Description of the Related Art Polyamide resins have excellent mechanical properties such as rigidity and toughness, and excellent chemical resistance such as oil resistance. For this reason, applications for various functional parts such as automobile parts and electric / electronic parts have been developed. However, the performance of the polyamide resin, such as impact resistance and flexibility, is not sufficient to satisfy the demands of the market, especially in a completely dry state, and various improvements have been studied.

Conventionally, as a method for improving the impact resistance of a polyamide resin, for example, an ethylene propylene copolymer or an ethylene 1-butene copolymer obtained by grafting an α, β-unsaturated carboxylic acid to a polyamide resin is used. A method of adding more than 2/3 has been attempted (Japanese Patent Publication No. 62-13379). By this method, a polyamide resin composition excellent in impact resistance and flexibility can be obtained,
There is a problem that the moldability is significantly reduced.

A modified olefin polymer in which a specific amount of an ethylenically unsaturated group-containing carboxylic acid or a derivative thereof is bonded to a polar thermoplastic polymer such as a polyamide resin and a basic olefin polymer having a specific structure. Attempts have been made to improve the impact resistance by using a combination with a coalescence (Japanese Patent Application Laid-Open No. 9-87476). However, even with these conventionally proposed thermoplastic resin compositions, the requirements for materials have become severe, and the problem is that they are not yet perfect in that they simultaneously satisfy all of extremely high impact resistance, moldability, and compatibility. There is a point.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to achieve a high balance between excellent impact resistance, molding workability, and compatibility, which is a problem in the above-mentioned conventional polyamide resin. Another object of the present invention is to obtain a polyamide resin composition which is excellent in balance with the intrinsic properties of polyamide resin such as mechanical properties other than the properties and chemical resistance such as oil resistance, and is also excellent in industrial productivity.

[0006]

The inventors of the present invention have studied to solve the above-mentioned problems, and have found that (a) a polyamide resin, (b) ethylene having a specific structure and a molecular weight distribution, and ethylene having 3 to 3 carbon atoms. The above object can be attained by selectively using an ethylene / α-olefin-based copolymer composed of α-olefin of No. 20 and (c) a modified polyolefin resin other than the copolymer used as the component (b). The present invention has been found to be solved.

That is, the present invention provides: "The ratio (Mw / Mn) of (a) 100 parts by weight of a polyamide resin and (b) the weight-average molecular weight (Mw) to number-average molecular weight (Mn) calculated by gel permeation chromatography (GPC) is 3. An ethylene / α-olefin-based copolymer comprising ethylene of 0 or less and an α-olefin having 3 to 20 carbon atoms, and / or an ethylene / α-olefin-based copolymer modified with a carboxylic acid derivative. 5 to 100 parts by weight of a modified ethylene / α-olefin copolymer to be obtained and (c) 5 to 100 parts by weight of a modified polyolefin resin other than the copolymer used as the component (b). 1. Thermoplastic resin composition. ""The content of the α-olefin having 3 to 20 carbon atoms contained in the ethylene / α-olefin-based copolymer or the modified ethylene / α-olefin-based copolymer of the component (b) is 6;
２５25 mol%. 2. "Either of the above-mentioned, wherein the ethylene / α-olefin-based copolymer or the modified ethylene / α-olefin-based copolymer as the component (b) is a copolymer obtained by polymerization using a metallocene-based catalyst. 3. Thermoplastic resin composition. " 4. The thermoplastic resin composition according to any one of the above, wherein the component (b) is an unmodified ethylene / α-olefin-based copolymer. "The component (b) is a modified ethylene / α-olefin-based copolymer modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof. 3. Any one of the thermoplastic resin compositions. " 6. The thermoplastic resin composition according to any one of the above, wherein the polyamide resin of the component (a) is a nylon 6 resin. 7. The thermoplastic resin composition according to any one of the above 1 to 5, wherein the polyamide resin of the component (a) is a nylon 66 resin. "(A) The polyamide resin of the component is a copolymerized nylon of nylon 66 / nylon 6 and the copolymerization ratio is 9
The thermoplastic resin composition according to any one of the above 1 to 5, wherein the thermoplastic resin composition is 9.5 / 0.5 to 95/5 mol%. 9. "A polyamide resin as the component (a) has a structural unit derived from an aliphatic diamine and terephthalic acid of 70 to 30 mol%.
The thermoplastic resin composition according to any one of the above 1 to 5, which is a copolymerized polyamide containing: 10. 10. The thermoplastic resin composition according to 9, wherein the polyamide resin as the component (a) is a copolymerized polyamide containing 70 to 30 mol% of hexamethylene terephthalamide units. "The modified polyolefin resin of the component (c) is α, β
The above-mentioned 1-10, which is a polyolefin modified by copolymerization of an unsaturated carboxylic acid and / or a derivative thereof;
Any thermoplastic resin composition. 12. "The modified polyolefin resin of the component (c) is α, β
-The thermoplastic resin composition according to any one of the above 1 to 11, which is an ethylene / α-olefin random copolymer modified by copolymerization of an unsaturated carboxylic acid and / or a derivative thereof. 13. "(A) 100 parts by weight of a polyamide resin, and (b)
Ethylene having a ratio (Mw / Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn) calculated by gel permeation chromatography (GPC) of 3.0 or less and α having 3 to 20 carbon atoms Ethylene / α-olefin-based copolymer comprising olefin and / or modified ethylene / α-olefin-based copolymer obtained by modifying the ethylene / α-olefin-based copolymer with a carboxylic acid derivative 5 to 100 A method for producing a thermoplastic resin composition, comprising melt-kneading 5 parts by weight and 100 parts by weight of (c) a modified polyolefin resin other than the copolymer used as the component (b). 14. 14. A molded article comprising the thermoplastic resin composition of any of the above 1 to 12. "The molded article according to the above item 14, wherein the molded article is a mechanical mechanism part, an electric / electronic part or an automobile part."

[0008]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The polyamide resin used as the component (a) in the present invention is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid;
lactams such as ε-caprolactam, ω-laurolactam, tetramethylenediamine, hexamerenediamine,
2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta-xylylenediamine, Paraxylylenediamine, 1,
3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-
Aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane,
2,2-bis (4-aminocyclohexyl) propane,
Aliphatic, alicyclic, and aromatic diamines such as bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, spearic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-
Aliphatic such as chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid;
Alicyclic and aromatic dicarboxylic acids are mentioned. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, particularly useful polyamide resins are polyamide resins having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecaneamide (nylon 1)
1), polydodecaneamide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexa Methylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 /
6T / 6I), polyxylylene adipamide (nylon X
D6), polyhexamethylene terephthalamide / poly-
Examples include 2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T) and mixtures thereof.

Particularly preferred polyamide resins include hexamethylerephthalamide, such as nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer, and nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, and nylon 6T / 6 copolymer. Copolymers having a unit can be mentioned, and it is also practically preferable to use these polyamide resins as a mixture depending on required properties such as impact resistance, moldability and compatibility.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, especially 2.0 to 4.0. Polyamide resins in the range of 0 are preferred.

The specific ethylene / α-olefin copolymer used as the component (b) of the present invention comprises ethylene and at least one or more α-olefins having 3 to 20 carbon atoms, It is a copolymer defined by the following requirements. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
-Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene , 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-
Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl- 1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because improvement in mechanical strength and further improvement in a reforming effect can be seen.

The ethylene / α-olefin-based copolymer used in the present invention has a weight average molecular weight (M) calculated by gel permeation chromatography (GPC).
The ratio (Mw / Mn) of w) to the number average molecular weight (Mn) needs to be 3.0 or less, and preferably 2.9.
The value is more preferably 2.8 or less. The copolymer whose molecular weight distribution is limited to an extremely narrow range of 3.0 or less has a small amount of low molecular weight components and is excellent in mechanical properties and moldability, so that the use of the copolymer results in excellent properties of the composition of the present invention. It becomes possible.

The ethylene / α-olefin copolymer preferably has an α-olefin content of 6 to 25 mol%,
More preferably 8 to 22 mol%, even more preferably 10 to 22 mol%.
~ 20 mol%. By using an ethylene / α-olefin copolymer having an α-olefin content in the above range, a polyamide resin composition capable of providing a molded article excellent in flexibility and impact resistance can be obtained.

Such an ethylene / α-olefin copolymer can be produced by polymerization using a metallocene catalyst. The metallocene-based catalyst is composed of a cyclopentadienyl derivative of a Group IV metal such as titanium or zirconium and a co-catalyst. Metallocene-based catalysts are highly active, and compared to conventional catalysts represented by Ziegler-based catalysts,
The resulting polymer has a narrow molecular weight distribution and a uniform distribution of the α-olefin, which is a comonomer component of the copolymer, so that it has excellent flexibility and impact resistance.

In the present invention, when the ethylene / α-olefin-based copolymer is used in an unmodified state, a material having both excellent impact resistance and excellent moldability can be obtained.

In the present invention, the ethylene · α
The olefin copolymer may be modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides and derivatives thereof. By using the modified ethylene / α-olefin-based copolymer modified in this way, the compatibility is further improved, and there is a feature that the impact resistance is extremely excellent while the moldability is maintained.
Examples of compounds selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof used as a modifier include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and methylmaleic acid. , Methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylic acid Hydroxyethyl, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2 1) -5-heptene-2,3-dicarboxylic acid, Endobishikuro - (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N
-Ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.

Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid, 5-norbornene-2,3-dicarboxylic acid or acid anhydrides thereof are particularly preferable.

As the modified polyolefin resin used as the component (c) of the present invention, a modified polyolefin modified with a carboxylic acid and / or a derivative thereof is preferably used. Such a component is a polyolefin containing in its molecule a functional group having an affinity for the polyamide resin, and particularly a carboxylic acid group, a carboxylic acid anhydride group, a carboxylic acid ester group, and a carboxylic acid metal base. An α-olefin homopolymer or copolymer containing at least one selected from them in the polymer molecular chain is preferred.

Specific examples of α-olefin homopolymers or copolymers include homopolymers such as polyethylene, polypropylene, polybutene-1, polypentene-1, and polymethylpentene, ethylene, propylene, butene-1, pentene-1,4, and the like. -Methylpentene-
1, hexene-1, octene-1, α-olefins such as isobutylene, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1 Examples include polyolefins obtained by radical polymerization of at least one non-conjugated diene such as' -probenyl) -2-norbornene using a usual metal catalyst.

The diene elastomer is an AB or ABA 'type block copolymer elastic body composed of a vinyl aromatic hydrocarbon and a conjugated diene, and has terminal blocks A and A'. May be the same or different, and include a thermoplastic homopolymer or copolymer derived from a vinyl aromatic hydrocarbon in which the aromatic portion may be monocyclic or polycyclic, and such a vinyl aromatic hydrocarbon Examples include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene, and mixtures thereof. The intermediate polymer block B is made of a conjugated diene-based hydrocarbon, and examples thereof include polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and a mixture thereof. . In the present invention, those obtained by subjecting the intermediate polymer block B of the block copolymer to a hydrogenation treatment are also included.

Specific examples of the polyolefin copolymer include ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / hexene-1 copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated polybutadiene, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, unhydrogenated or hydrogenated styrene / butadiene /
Styrene triblock copolymer and the like can be mentioned.

The functional groups that modify these polyolefins include carboxylic acid groups, carboxylic acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal base carboxylic acid imide groups, and carboxylic acid amide groups. Examples of compounds containing: acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methyl maleic acid, methyl fumaric acid, mesaconic acid,
Citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,
1) -5-heptene-2,3-dicarboxylic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide,
N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, 5-norbornene-2,3-dicarboxylic acid, and the like.

The method of introducing these functional group-containing components into the olefin compound is not particularly limited, and the olefin compound as the main component and the functional group-containing olefin compound may be previously copolymerized, or the functional group-containing olefin compound may be added to the unmodified polyolefin. A method such as graft introduction using a radical initiator can be used. The amount of the functional group-containing component to be introduced is suitably in the range of preferably 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on the entire olefin monomer in the modified polyolefin.

Specific examples of the modified polyolefin particularly useful as the component (c) in the present invention include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer and Some or all of the carboxylic acid moieties in these copolymers are converted into salts with sodium, lithium, potassium, zinc and calcium, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / Methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer, (“g” represents a graft, the same applies hereinafter), ethylene / methyl methacrylate -G-maleic anhydride copolymer, ethylene / ethyl acrylate Imide copolymer, ethylene / ethyl acrylate-g-N-phenylmaleimide copolymer and partially saponified products of these copolymers, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate / glycidyl methacrylate copolymer, ethylene /
Methyl methacrylate / glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / vinyl acetate / glycidyl acrylate copolymer, ethylene / glycidyl ether copolymer, ethylene / propylene-g-maleic anhydride copolymer, Ethylene / butene-1-g-maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer Ethylene / propylene / 2,5-norbornadiene-g-maleic anhydride copolymer, ethylene / propylene-g-N-phenylmaleimide copolymer, ethylene / butene-1-g-N
-Phenylmaleimide copolymer, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride copolymer, ethylene / propylene-g-glycidyl methacrylate Copolymer, ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / propylene / 1,
4-hexadiene-g-glycidyl methacrylate copolymer, ethylene / propylene / dicyclopentadiene-g
-Glycidyl methacrylate copolymer, hydrogenated styrene / butadiene / styrene-g-glycidyl methacrylate copolymer, and the like.

Further, the thermoplastic resin composition of the present invention includes:
A fibrous and / or non-fibrous filler may be blended according to the purpose and application. Specific examples of such a fibrous and / or non-fibrous filler include glass fiber, glass milled fiber, carbon fiber, potassium whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, and ceramic. Fibrous fillers such as fibers, asbestos fibers, masonry fibers, metal fibers, etc., silicates such as walasteinite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, alumina silicate, alumina,
Metal compounds such as silicon oxide, magnesium oxide, zirconium oxide, titanium oxide and iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; magnesium hydroxide; calcium hydroxide; water Hydroxides such as aluminum oxide, glass beads, ceramic beads, boron nitride,
Examples include non-fibrous fillers such as silicon carbide and silica, which may be hollow, or two or more of these fillers may be used in combination.

These fibrous and / or non-fibrous fillers are used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. This is preferable in that higher mechanical strength is obtained. When such a fibrous and / or non-fibrous filler is used, its amount is usually in the range of 5 to 80 parts by weight based on the total composition.

Further, the thermoplastic resin composition of the present invention comprises:
In a range that does not impair the properties of the obtained resin composition,
Crystal nucleating agents such as talc, kaolin, organic phosphorus compounds, polyetheretherketone, coloring inhibitors such as hypophosphite, antioxidants such as hindered phenols and hindered amines, heat stabilizers, lubricants, UV inhibitors, Colorant,
And other additives.

The method for preparing the thermoplastic resin composition of the present invention is not limited to a specific method, but specific and efficient examples include a raw material polyamide resin, an ethylene / α-olefin copolymer and / or a modified resin. The mixture of the ethylene / α-olefin-based copolymer and the modified polyolefin is supplied to a known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, depending on the melting point of the polyamide resin used. 180
A method of melting and kneading at a temperature of about 330 ° C. can be used.

The thermoplastic resin composition thus obtained is
Usually, it can be molded by a known method, and can be molded articles such as injection molding, extrusion molding and compression molding, and molded articles such as sheets and films. The thermoplastic resin composition of the present invention is particularly suitable for use in injection molding, and can be usefully used as a mechanical mechanism part, an electric / electronic part, and an automobile part by utilizing its features.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Further, in the following examples, the material strength,
The fluidity and compatibility were evaluated by the following methods.

[Material strength] Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod impact strength: ASTM D256 [Fluidity] Using a spiral flow measurement mold having a spiral shape with a width of 10 mm, a thickness of 2 mm and a total length of 600 mm,
Injection molding temperature The melting point of polyamide resin + 20 ° C, injection molding pressure of 450 kgf / cm 2, and mold temperature of 80 ° C When the material was injection-molded under the conditions, the flow distance in the mold was measured to measure the fluidity index. did. The longer the flow length, the better the fluidity.

[Compatibility] Each material is molded using a pin gate type mold for a box-shaped molded product, and the degree of peeling of the pin gate portion of the obtained molded product is observed with an optical microscope. Evaluation was performed in three stages of ○, Δ, and × from the better one.

Example 1 As an ethylene / α-olefin copolymer, an ethylene / 1-hexene copolymer 10 having Mw / Mn = 2.8 and α-olefin content = 6 mol% was used.
Parts by weight, 100 parts by weight of nylon 66 having a relative viscosity of 2.70 and 10 parts by weight of an ethylene / 1-butene copolymer modified with 0.8% by weight of maleic anhydride, and then biaxially φ30 mm The mixture was melt-kneaded and pelletized by an extruder, and vacuum dried at 80 ° C. overnight. The thermoplastic resin composition obtained here was injection-molded into various test pieces and the strength of the material was measured. The results are shown in Table 1. The results are excellent in compatibility, especially impact resistance, and moldability. Was found to be a composition.

Example 2 Nylon 6 was used as a polyamide resin, and M was used as an ethylene / α-olefin copolymer.
w / Mn = 2.6, α-olefin content = 8 mol% ethylene / 1-hexene copolymer and ethylene / 1-hexene modified as 0.8% by weight with maleic anhydride as a modified polyolefin resin Kneading, pelletizing, and kneading in exactly the same manner as described in Example 1 except that the polymer was used.
Injection molding and measurement of physical properties were performed. Table 1 shows the results.
As can be seen from the figure, the composition was excellent in impact resistance, molding processability, and compatibility.

Example 3 As a polyamide resin, ε-
Copolymer of 3 mol% of caprolactam and 97 mol% of equimolar salt of hexamethylenediamine and adipic acid (melting point 2
Kneading, pelletizing, and injection in exactly the same manner as described in Example 1 except that an ethylene / 1-hexene copolymer modified with maleic anhydride at 0.8% by weight was used as the modified polyolefin resin. Molding and physical properties were measured. The results are as shown in Table 1, and it can be seen that the composition was excellent in impact resistance, molding workability, and compatibility.

Example 4 As a polyamide resin, a copolymer (melting point: 280 ° C.) of 50 mol% of hexamethylene diammonium terephthalate and 50 mol% of hexamethylene diammonium sebacate, an ethylene / α-olefin copolymer , Mw / Mn = 2.8, α-olefin content = 6 mol% Kneading, pelletizing, and injection molding in exactly the same manner as described in Example 1 except that an ethylene / 1-hexene copolymer was used. And physical properties were measured.
The results are as shown in Table 1, and it can be seen that the composition was excellent in impact resistance, molding workability, and compatibility.

Example 5 As a modified ethylene / α-olefin-based copolymer, Mw / Mn modified with maleic anhydride at 0.8% by weight = 2.8, α-olefin content =
Kneading, pelletizing, injection molding, and measurement of physical properties were performed in exactly the same manner as described in Example 1 except that 6 mol% of the modified ethylene / 1-hexene copolymer was used. The results are as shown in Table 1, and it can be seen that the composition was excellent in impact resistance due to the use of the modified ethylene / α-olefin-based copolymer, particularly the moldability and compatibility.

Example 6 Kneading, pelletizing, injection molding and measurement of physical properties were performed in exactly the same manner as described in Example 1 except that polypropylene was used as the modified polyolefin resin. As shown in Table 1, the composition obtained here was excellent in impact resistance, molding workability, compatibility, and particularly excellent in molding workability and of high practical value.

Example 7 As an ethylene / α-olefin copolymer, 10 parts by weight of an ethylene / 1-butene copolymer having Mw / Mn = 2.9 and α-olefin content = 6 mol% Exactly the same as the method described in Example 1, except that 100 parts by weight of nylon 66 having a viscosity of 2.70 and 10 parts by weight of an ethylene / 1-butene copolymer modified with 0.8% by weight of maleic anhydride were used. The mixture was kneaded, pelletized, injection molded, and measured for physical properties. As shown in Table 2, the composition obtained here was found to be a composition excellent in compatibility, particularly impact resistance, and moldability.

Example 8 As an ethylene / α-olefin copolymer, an ethylene / 1-octene copolymer having Mw / Mn = 2.8 and α-olefin content = 6 mol% was used.
Example 1 was described except that 100 parts by weight of nylon 66 having a relative viscosity of 2.70 and 10 parts by weight of an ethylene / 1-butene copolymer modified with 0.8% by weight of maleic anhydride were used. Kneading, pelletizing, exactly the same way
Injection molding and physical properties were measured. As shown in Table 2, the composition obtained here was found to be a composition excellent in compatibility, particularly impact resistance, and moldability.

Comparative Example 1 A specific ethylene / α-olefin-based copolymer was used without using maleic anhydride.
Kneading, pelletizing, injection molding, and measurement of physical properties were performed in exactly the same manner as described in Example 1 except that 20 parts by weight of the ethylene / 1-butene copolymer modified by weight% was used.
The results are as shown in Table 2, and it can be seen that the obtained composition had a high level of impact resistance, but was extremely poor in moldability.

Comparative Example 2 Mw / M modified with maleic anhydride at 0.8% by weight as a modified ethylene / α-olefin copolymer without using a modified polyolefin resin
Kneading, pelletizing, and injection were performed in exactly the same manner as described in Example 1 except that 20 parts by weight of the modified ethylene / 1-hexene copolymer having n = 2.8 and an α-olefin content of 6 mol% was used. Molding and physical properties were measured. The results are as shown in Table 2, and it can be seen that the obtained composition had good moldability, but the impact resistance, particularly the compatibility, was extremely poor.

Comparative Example 3 10 parts by weight of linear low-density polyethylene (LLDPE) having a Mw / Mn of 3.8 without using a metallocene catalyst in place of a specific ethylene / α-olefin copolymer Kneading, pelletizing, injection molding, and the like in exactly the same manner as described in Example 1 except that
Physical properties were measured. The results are as shown in Table 2, and it can be seen that the obtained composition had a high level of moldability, but had insufficient compatibility, particularly insufficient impact resistance.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

As described above, according to the thermoplastic resin composition of the present invention, a molded article having excellent impact resistance, moldability, and compatibility can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazuki Miyamoto 9-1, Oe-cho, Minato-ku, Nagoya-shi, Aichi Pref. Of the Toray Industries, Inc. Nagoya Office

Claims (15)

[Claims] (A) 100 parts by weight of a polyamide resin,
(B) Gel permeation chromatography (GP
Ethylene comprising a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) of 3.0 or less and an α-olefin having 3 to 20 carbon atoms. 5 to 100 parts by weight of an α-olefin copolymer and / or a modified ethylene / α-olefin copolymer obtained by modifying the ethylene / α-olefin copolymer with a carboxylic acid derivative, and (c) A thermoplastic resin composition comprising 5 to 100 parts by weight of a modified polyolefin resin other than the copolymer used as the component (b). 2. The content of the α-olefin having 3 to 20 carbon atoms in the ethylene / α-olefin-based copolymer or the modified ethylene / α-olefin-based copolymer of the component (b) is 6 to 25. The thermoplastic resin composition according to claim 1, wherein the amount is mol%. 3. The ethylene / α-olefin copolymer or the modified ethylene / α-olefin copolymer of the component (b) is a copolymer obtained by polymerization using a metallocene catalyst. The thermoplastic resin composition according to claim 1 or 2, wherein 4. The method according to claim 1, wherein said component (b) is unmodified ethylene.α.
The thermoplastic resin composition according to any one of claims 1 to 3, wherein the thermoplastic resin composition is an olefin-based copolymer. 5. The method according to claim 1, wherein the component (b) is a modified ethylene / α-olefin copolymer modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides and derivatives thereof. The thermoplastic resin composition according to any one of claims 1 to 3. 6. The thermoplastic resin composition according to claim 1, wherein the polyamide resin (a) is a nylon 6 resin. 7. The thermoplastic resin composition according to claim 1, wherein the polyamide resin (a) is a nylon 66 resin. 8. The polyamide resin as the component (a) is a nylon 66 / nylon 6 copolymerized nylon having a copolymerization ratio of 99.5 / 0.5 to 95/5 mol%. 5. The thermoplastic resin composition according to any one of 5. 9. The structural unit 70 wherein the polyamide resin (a) is derived from an aliphatic diamine and terephthalic acid.
The thermoplastic resin composition according to any one of claims 1 to 5, which is a copolymerized polyamide containing from 30 to 30 mol%. 10. The thermoplastic resin composition according to claim 9, wherein the polyamide resin (a) is a copolymer polyamide containing 70 to 30 mol% of hexamethylene terephthalamide units. 11. The heat according to claim 1, wherein the modified polyolefin resin as the component (c) is a polyolefin modified by copolymerization of an α, β-unsaturated carboxylic acid and / or a derivative thereof. Plastic resin composition. 12. The modified polyolefin resin of component (c) is an ethylene / α-olefin random copolymer modified by copolymerization of α, β-unsaturated carboxylic acid and / or a derivative thereof. 12. The thermoplastic resin composition according to any one of 11. 13. A ratio (Mw / Mn) of (a) 100 parts by weight of a polyamide resin and (b) a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) calculated by gel permeation chromatography (GPC). ) is 3.0 or less
An ethylene / α-olefin-based copolymer consisting of lower ethylene and an α-olefin having 3 to 20 carbon atoms and / or obtained by modifying the ethylene / α-olefin-based copolymer with a carboxylic acid derivative. Modified ethylene α-
5 to 100 parts by weight of the olefin copolymer and (c)
A method for producing a thermoplastic resin composition, comprising melting and kneading 5 to 100 parts by weight of a modified polyolefin resin other than the copolymer used as the component (b). 14. A molded article comprising the thermoplastic resin composition according to claim 1. 15. The molded article according to claim 14, wherein said molded article is a mechanical mechanism part, an electric / electronic part, or an automobile part.