JP2831786B2 - Thermoplastic resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent heat resistance, impact resistance, damage resistance, water resistance, and surface gloss.

[Prior art] Crystalline polypropylene is used in a wide range of fields having excellent mechanical properties and moldability, but it cannot be said that both heat resistance and impact resistance are sufficient for use in industrial parts. . As a method for improving heat resistance, mixing of an inorganic filler, and as a method for improving impact resistance, ethylene / α is used.
-Methods of mixing olefin copolymer rubber and polyethylene have been conventionally used, but the mixing of inorganic fillers significantly reduces the impact resistance of polypropylene, and also makes it possible to mix ethylene / α-olefin copolymer rubber and Mixing polyethylene has the disadvantage of lowering the rigidity, heat resistance, and oil resistance of polypropylene, and even if these are used in combination, the performance does not deviate from the additive range and is sufficient as an improved method. I can't say.

On the other hand, attempts have been made to improve the heat resistance, oil resistance, and the like of polypropylene by mixing polyamide with polypropylene without observing a drop in impact resistance. However, since polypropylene and polyamide are not compatible at all,
Even if these are melt-mixed as they are, delamination occurs, and a desired material cannot be obtained. Therefore, a modified polypropylene obtained by graft-modifying a polypropylene with an unsaturated carboxylic acid or a derivative thereof is generally used (JP-B-45-3094).
Five). By this method, the compatibility between the polypropylene and the polyamide is improved, and the heat resistance of the polypropylene is improved without any decrease in impact resistance.

[Problems to be Solved by the Invention] However, the improvement of polypropylene by mixing the above-mentioned conventional polyamides has no effect as far as polyamides such as nylon-6, ninelon-6,6 and nylon-12 are used. It was not satisfactory. Recently, a proposal has been made to obtain a high-strength, low-water-absorbing material by mixing an aromatic polyamide and glass fiber (Japanese Patent Application Laid-Open No. 60-203654). It is not sufficient from the viewpoint of both impact resistance improvement. In order to greatly improve the heat resistance and impact resistance of polypropylene by mixing polyamide with polypropylene, the dispersibility of polyamide particles and the strength of cohesion of the particles are particularly important. I needed to.

Accordingly, the present inventors have found that, in a mixture of polypropylene and polyamide, for polyamide having a large effect of improving heat resistance and impact resistance of polypropylene, the dispersibility of particles is particularly excellent with respect to polypropylene, and the cohesive force of the particles is also high. We worked diligently on very strong polyamides.
As a result, when a specific modified polyamide is mixed with polypropylene, heat resistance, impact resistance, damage resistance and deformation of a molded article, etc., are superior to those of the conventional polypropylene-polyamide mixture. It has been found that they can be obtained and led to the present invention.

When the modified polyamide of the present invention is mixed with polypropylene, the moldability is substantially the same as that of a normal polyamide, but the heat resistance and impact resistance are dramatically improved, and the mechanical strength and There is a great feature in that the deformation of the molded product is also improved.

[Means for Solving the Problems] That is, according to the present invention, component (a) a modified polypropylene graft-modified with an unsaturated carboxylic acid or / and a derivative thereof, or at least 5
95% to 5% by weight of crystalline polypropylene
And a thermoplastic resin composition comprising from 5 to 95% by weight of a modified polyamide partially or wholly modified with a clay mineral.

Further, 100 parts by weight of the thermoplastic resin composition comprising the component (a) and the component (b) is added to the component (c)
thermoplastic resin further containing 1 to 100 parts by weight of an α-olefin copolymer rubber or a modified ethylene / α-olefin copolymer rubber partially or wholly graft-modified with an unsaturated carboxylic acid and / or a derivative thereof A composition is provided.

Further, with respect to 100 parts by weight of the thermoplastic resin composition comprising the component (a) and the component (b), the component (d) has a general formula:
A- (BA) _n (where A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5). A thermoplastic further comprising a copolymer or a hydrogenated derivative of the block copolymer or a modified block copolymer obtained by graft-modifying the block copolymer with an unsaturated carboxylic acid and / or a derivative thereof; A resin composition is provided.

Further, there is provided a thermoplastic resin composition further containing 5 to 150 parts by weight of an inorganic filler for component (e) based on 100 parts by weight of the thermoplastic resin composition comprising component (a) and component (b). .

Furthermore, the thermoplastic resin composition comprising the component (a) and the component (b) further contains 1 to 100 parts by weight of the component (c) and the component (d) in total with respect to 0 part by weight of the 10-position. A thermoplastic resin composition is provided, and a thermoplastic resin composition comprising the component (a) and the component (b).
A thermoplastic resin composition further comprising 1 to 100 parts by weight of the components (c) and / or (d) in total and 0 to 150 parts by weight of the component (e) with respect to 0 parts by weight. Is done.

 Hereinafter, the present invention will be described in more detail.

The crystalline polypropylene used as the component (a) in the present invention has a melt index (ASTMD1238, 230 ° C).
2160 g) may be a crystalline polypropylene of 0.3 to 70 g / 10 min, a propylene crystalline homopolymer, a random or block copolymer with ethylene, or a mixture thereof. The ethylene-propylene copolymer preferably has an ethylene content of 5 parts by weight or less for a random copolymer and 3 to 15 parts by weight for a block copolymer.

Among the crystalline polypropylenes, particularly preferred is an ethylene-propylene block copolymer having a melt index of 0.3 to 50 g / 10 minutes and an ethylene content of 3 to 10 parts by weight.

The modified polypropylene of the component (a) used in the present invention comprises:
The crystalline polypropylene can be obtained by graft modification. Unsaturated carboxylic acids and derivatives thereof are used as monomers for the graft-modified raw materials.

Examples of unsaturated carboxylic acids and derivatives thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, crotonic acid, glycidyl methacrylate, 2-hydroxyethyl methacrylate, polyethylene glycol dimethacrylate, and N-methylol methacryl. Amide, calcium methacrylate, γ-methacryloxypropyltrimethoxysilane, acrylamide, methacrylamide, and the like, maleic anhydride, itaconic anhydride, citraconic anhydride, and the like are used. Preferred are acid anhydrides such as maleic anhydride and itaconic anhydride.

The reaction initiator is not particularly limited,
Has a half-life of 1 minute, and the decomposition temperature to obtain said half-life is
What is necessary is just the thing which is more than the melting point of raw material polypropylene and 250 degrees C or less. If the required decomposition temperature exceeds 250 ° C., the amount of radicals generated at the time of graft modification decreases, so that the graft reaction may not be performed efficiently. Examples of such a reaction initiator include organic peroxides such as hydroperoxide, dialkyl peroxide, and peroxyester. Examples of the organic peroxide used in the present invention include t-butylperoxybenzoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, methylethylketone peroxide, Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and the like. At the time of use, it can be appropriately selected according to reaction conditions and the like.

The acid-graft-modified crystalline polypropylene can be obtained by mixing the crystalline polypropylene with the modified raw material monomer and the reaction initiator, and melt-kneading the mixture in a nitrogen stream or air. Alternatively, it can also be obtained by dissolving under pressure and heat in xylene, and stirring and mixing while dropping the modified starting monomer and the reaction initiator. Melt kneading may be carried out using a kneader such as a twin-screw extruder, a kneader, or a Banbury mixer, but usually a single-screw extruder can be used. The mixing temperature is not lower than the melting point of the raw material polypropylene and is usually about 175 to 280 ° C. Melt mixing time is
Although it depends on the raw materials and the like, it can be generally carried out in about 1 to 20 minutes.

The mixing ratio of the raw materials is about 0.05 to 5 parts by weight of the raw material-modified monomer per 100 parts by weight of the raw material polypropylene, and preferably 0.1 to 5 parts by weight.
1 to 3.0 parts by weight, and about 0.002 to 1 part by weight of a reaction initiator.

When the amount of the monomer is less than about 0.05 part by weight, the effect of the modification cannot be obtained. On the other hand, when the amount exceeds 5 parts by weight, the grafting efficiency of the monomer is extremely lowered, and the unreacted monomer increases, which is not preferable.

The modified polypropylene obtained as described above has a graft ratio of the monomer of 0.03 parts by weight or more, preferably 0.1 to
5.0 parts by weight, melt index 0.5-200g / 1
0 minutes is good. If the melt index is less than 0.5 g / 10 min, the moldability may be reduced after melt mixing with polyamide, while if it exceeds 200 g / 10 min, the molecular weight is too low, so that the desired performance is obtained. No material available.

The modified polyamide resin used as the component (b) in the present invention is 0.05 to 10 parts by weight based on 100 parts by weight of the polyamide.
In particular, a specific clay mineral in an amount of 0.1 to 7 parts by weight, preferably 0.1 to 7 parts by weight, is uniformly dispersed and compounded to greatly improve heat resistance. If the proportion of the clay mineral is less than 0.05 parts by weight, no effect of improving heat resistance is observed, and if it exceeds 15 parts by weight, the fluidity at the time of melting is remarkably reduced and injection molding may not be possible.

Examples of the polyamide resin used in the modified polyamide of the present invention include polyamides and lactams obtained by polycondensation of aliphatic, alicyclic and aromatic diamines with aliphatic, alicyclic and aromatic dicarboxylic acids. And polyamides obtained by condensation of aminocarboxylic acids or copolymerized polyamides comprising these components. Specifically, nylon-6, nylon-6,
6, nylon-6,10, nylon-9, nylon-11, nylon-12, nylon-6 / 6,6, nylon-12,12 and the like.

The clay mineral for modifying the polyamide resin is mainly a layered silicate, the shape of which usually has a side length of 0.00.
As a raw material of such a layered silicate having a thickness of 2 to 1 μm and a thickness of 6 to 20 °, there is, for example, a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate. Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, and baroysite. These may be natural or synthetic.
Among these, montmorillonite is particularly preferred.

Preferably, each layered silicate is uniformly dispersed in the polyamide at an average distance of 20 ° or more. There is no particular limitation on the method of uniformly dispersing the layered silicate in the polyamide resin, but when the raw material of the layered silicate is a multilayer clay mineral, the layered silicate is brought into contact with a swelling agent to expand the layers in advance. After the monomer is easily taken in between the layers, it may be mixed with a polyamide monomer and polymerized (JP-A-62-64827, JP-A-62-72723, JP-A-62-74957). In addition, a polymer compound is used as a swelling agent, and 100
It is also possible to adopt a method in which the above is expanded and melt-mixed with a polyamide resin.

The modified polyamide resin of the present invention may be used alone, or may be used as a mixture with another modified polyamide resin or an ordinary polyamide resin.

Ethylene used as component (c) in the present invention
α-olefin copolymer rubber has an ethylene content of 30 to
95% by weight, preferably 60 to 90% by weight of an ethylene / α-olefin copolymer rubber. α-Olefin components include those having 3 to 20 carbon atoms, such as propylene,
-Butene, 1-hexene, 4-methyl-1-pentene,
1-decene and the like can be mentioned. The α-olefin component may be used alone or as a mixture of two or more.
In some cases, a trace amount of a diene component may be contained.

The graft-modified starting monomer of the modified ethylene / α-olefin copolymer rubber obtained from the ethylene / α-olefin copolymer rubber is an unsaturated carboxylic acid or a derivative thereof similar to the graft-modified monomer of the modified propylene. . As the reaction initiator for graft modification, the above-mentioned radical-generating compounds such as organic peroxides can be used in the same manner. In some cases, graft modification may be caused by heat treatment without using a reaction initiator. The modified ethylene / α-olefin copolymer rubber is obtained by heating and mixing and stirring the raw material ethylene / α-olefin copolymer rubber and the graft-modified raw material monomer in a solution in the presence of an initiator, or It is manufactured by heat-melting and kneading an olefin copolymer rubber and a graft-modified raw material monomer. The modified ethylene / α-olefin copolymer rubber thus produced has a raw material monomer graft ratio of about 0.05 to 5.0% by weight, preferably about 0.1 to 3.0% by weight, and a melt index of about 0.01 to 20 g / The ratio of each raw material and the reaction conditions are appropriately selected so as to be 10 minutes, preferably 0.05 to 15 g / 10 minutes.

If the monomer graft ratio of the modified ethylene / α-olefin copolymer rubber is less than 0.05% by weight, the effect of modification cannot be obtained. If it exceeds 5.0% by weight, the degree of crosslinking of the rubber at the time of graft modification increases, and Melt mixing becomes difficult.
As mentioned above, polypropylene and ethylene α
-The method of graft modification of the olefin copolymer rubber may be performed independently, but after mixing the polypropylene and the ethylene / α-olefin copolymer rubber, the graft-modified starting monomer and the initiator are added, and the grafting is performed at the same time. A denaturation treatment can also be performed.

The block copolymer used as the component (d) in the present invention is a block copolymer represented by the general formula A- (BA) _n or hydrogen obtained by hydrogenating this block copolymer. It is an additive derivative. Here, in the above general formula, A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5.

The monovinyl-substituted aromatic hydrocarbon of the monomer constituting the polymer block A is preferably styrene,
Methylstyrene, vinyltoluene and other lower alkyl-substituted styrene and vinylnaphthalene groups are also used. The conjugated diene monomer in the polymer block B is preferably butadiene or isoprene, or may be a mixture of both. When butadiene is used as a single conjugated diene monomer to form polymer block B, the block copolymer retains elastomeric properties after hydrogenation and saturation of the double bonds. For this purpose, it is preferable to employ polymerization conditions in which the 1,2-microstructure in the microstructure of the polybutadiene block is 20 to 50%. More preferably, the 1,2-microstructure is 35-45%.

The weight average molecular weight of the polymer block A in the block copolymer is 5,000 to 125,000, and that of the polymer block B is 15,0
It is preferably in the range of 00 to 250,000.

Numerous methods have been proposed for producing these block copolymers. As a typical method, there is, for example, a method described in Japanese Patent Publication No. 40-23798, in which block copolymerization is carried out in an inert solvent using a lithium solvent or a Ziegler type catalyst.

The hydrogenation treatment of these block copolymers is described, for example, in JP-B-42-8704, JP-B-43-6636 or JP-B-46-20814.
The reaction is carried out by hydrogenation in an inert solvent in the presence of a hydrogenation catalyst according to the methods described in the specifications of each publication. In this hydrogenation, at least 50%, preferably 80%, of the olefin group double bonds in polymer block B
% Or more, and 25% or less of the aromatic unsaturated bonds in the polymer block A are hydrogenated.

Specific examples of the block copolymer of the above component (d) include styrene / butylene / styrene copolymer (SBS),
Styrene / isoprene / styrene copolymer (SIS), SBS
And hydrogenated SIS (SEBS) and SIS hydrogenated copolymer (SEPS).

Further, the graft-modified starting monomer, the graft-modifying reaction initiator, the production method and the graft-modified starting monomer graft ratio of the modified block copolymer obtained by graft-modifying the above block copolymer are the same as those of the modified ethylene / α.
-Same as the olefin copolymer rubber. These block copolymers and modified block copolymers may be used alone or as a mixture of two or more. Further, the component (c) and the component (d) can be used in combination.

 Inorganic filler used as component (e) in the present invention
As the powdery filler, for example, alumina, magnesium oxide
Nesium, calcium oxide, magnesium oxide, potassium oxide
Oxides such as lucium and zinc white, aluminum hydroxide, water
Magnesium oxide, calcium hydroxide, tin oxide hydrate
Hydrated metal oxides such as calcium carbonate, mug carbonate
Carbonate such as nesium, talc, clay, bentonate, etc.
Silicates such as, boric acid such as barium borate etc.
Salts, phosphates such as aluminum phosphate, barium sulfate, etc.
Sulfates and mixtures of two or more of these, fibrous filling
As an agent, for example, glass fiber, potassium titanate fiber,
Ceramic fiber, wollastonite, carbon fiber, SUS fiber
Weiss, Moss Heidi Etc., other glass beads, glass free
And mica. Also inorganic filling
The surface of the agent with a silane compound such as vinyl ethoxy sila
2-aminopropyltriethoxysilane, 2-glycol
Sidoxypropyltrimethoxysilane or titanate
It may be treated with a compound or the like. Especially in these
Talc as powdery filler, glass as fibrous filler
Fibers are preferred.

The thermoplastic resin composition of the present invention comprises a modified polypropylene graft-modified with the unsaturated carboxylic acid of component (a) and / or a derivative thereof, or a crystalline polypropylene containing at least 5% by weight of the modified polypropylene.
95 to 5% by weight, preferably 80 to 20% by weight, and 5 to 95% by weight, preferably 20 to 80% by weight of a modified polyamide in which part or all of the component (b) is modified with a clay mineral. Things. When the component (b) is less than 5% by weight, the modified polyamide does not have the effect of improving heat resistance and impact resistance. On the other hand, when the component (b) exceeds 95% by weight, the moisture resistance and chemical resistance of polypropylene are reduced. No improvement effect is obtained.

In addition, the present invention relates to 100 parts by weight of the thermoplastic resin composition comprising the above component (a) and component (b),
1 to 100 parts by weight, preferably 3 to 100 parts by weight of an ethylene / α-olefin copolymer rubber or a modified ethylene / α-olefin copolymer rubber partially or wholly graft-modified with an unsaturated carboxylic acid and / or a derivative thereof. To 30 parts by weight, and 100 parts by weight of the thermoplastic resin composition comprising the components (a) and (b) with respect to 100 parts by weight of the general formula of the component (d), A- (BA) ) _N (where A is a polymerized block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymerized block of a conjugated diene: n is 1 to
It is an integer of 5. ) Or a hydrogenated derivative of this block copolymer or a modified block copolymer obtained by graft-modifying this block copolymer with an unsaturated carboxylic acid and / or a derivative thereof in an amount of 1 to 100 parts by weight. , Preferably 3 to 40 parts by weight, or 100 parts by weight of the thermoplastic resin composition comprising the above components (a) and (b), and
5 to 150 parts by weight, preferably 10 to 100 parts by weight of an inorganic filler. If the amount of the component (c) or the component (d) is less than 1 part by weight, the effect of improving the impact resistance cannot be obtained, and if it exceeds 100 parts by weight, the rigidity, heat resistance, moldability and the like are significantly impaired. When component (e) is less than 10 parts by weight, there is almost no effect of improving rigidity and heat resistance, and when it exceeds 100 parts by weight, moldability is remarkably reduced. The above (c), (d) and component (e) may be used alone for the thermoplastic resin composition comprising component (a) and component (b), or may be used in combination as necessary. May be used. That is, a component obtained by blending the components (c) and (d) with a thermoplastic resin composition comprising the component (a) and the component (b),
A mixture of component (c) and component (e), component (d)
And component (e), and components (c), (d) and (e). In this case, component (c)
When component (d) is blended with component (c), component (c) and component (d) are combined with 100 parts by weight of the thermoplastic resin composition comprising component (a) and component (b). 1-100
It is preferable to mix by weight.

In order to obtain the thermoplastic resin composition of the present invention, (a) a modified polypropylene and (b) a modified polyamide, and further (c) an ethylene / α-olefin copolymer or a modified ethylene / α-olefin copolymer Rubber, (d) block copolymer, modified block copolymer, (e) inorganic filler,
Or dry blending of (c), (d) and the component (e) in combination with various known methods within the above range, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, and the like; A twin-screw extruder, a twin-screw extruder provided with a raw material supply port in a cylinder in addition to a usual raw material supply port, a method of melting and mixing with a kneader, a Banbury mixer, or the like, and then pelletizing can be adopted.

The thermoplastic resin composition of the present invention includes an antioxidant, an ultraviolet absorber, a lubricant, a pigment, an antistatic agent, a copper damage inhibitor, a flame retardant, a neutralizing agent, a plasticizer, a nucleating agent, a dye, and a foaming agent. , A slip agent or the like may be blended within a range that does not impair the object of the present invention.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but it will be apparent that the present invention is not limited to these Examples.

The measuring method used in the examples of the present invention is as follows.

Tensile properties Tensile strength (TYS) (kg / cm ² ): ASTM D638 Bending properties Bending strength (FS) (kg / cm ² ): ASTM D2584 Flexural modulus (FM) (kg / cm ² ): ASTM D2584 Izod impact strength (IZOD) (kg · cm / cm): ASTM D256
Notched Heat deformation temperature (HDT) (° C): ASTM D648 Surface hardness (RH) (-): ASTM D785 High-speed impact strength (HSI) (-): 1.6 mm thick, 100 mm diameter
-30 ° C as a test piece
Then, the round missile was dropped on this disk at a speed of 2.5 m / sec, and the surface was measured by a surface impact measurement method (UBE method) calculated from the area of a stress-strain curve at the time of breaking.

Example 1 A crystalline ethylene-propylene block copolymer 100 having a melt index of 1.0 g / 10 minutes and an ethylene content of 10% by weight.
Modified polypropylene (hereinafter referred to as MPP) obtained by adding and melting and mixing 0.2 parts by weight of maleic anhydride and 0.2 parts by weight of t-butyl peroxybenzoate with respect to parts by weight.
-1. ) 30% by weight and melt index 5.0g / 10
30% by weight of a crystalline ethylene-propylene block copolymer (hereinafter referred to as PP-1) having an ethylene content of 10% by weight and a modified polyamide (hereinafter referred to as MPA-1). 40% by weight
Is dry blended with a V blender, and the screw diameter is 65mm
And then pelletized after melt mixing with a single screw extruder. The pellets were dried with a vacuum dryer, and then injection molded at 270 ° C. to produce test pieces for measuring physical properties. The modified polyamide used in the examples was produced by the following method.

Disperse 100 g of montmorillonite having an average thickness of one unit of the layered silicate of 9.5 mm and an average length of one side of about 0.1 μm in 10 water, and adding 51.2 g of 12-aminododecanoic acid and 24 m
l of concentrated hydrochloric acid was added, and the mixture was stirred for 5 minutes and filtered. After sufficiently washing this, it was vacuum-dried. Through this operation, a complex of ammonium 12-aminododecanoate ion and montmorillonite was prepared.

Next, 10 kg of ε-caprolactam, 1 kg of water and 200 g of the dried composite were placed in a reaction vessel equipped with a stirrer,
The mixture was stirred at ℃ so that the inside of the reaction system became uniform. The temperature was further raised to 260 ° C., and the mixture was stirred under a pressure of 15 kg / cm ² for 1 hour. Thereafter, the reaction was carried out at normal pressure for 3 hours while releasing the pressure to evaporate the water from the reaction vessel. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was water-cooled and cut to obtain a modified polyamide pellet comprising a polyamide having an average molecular weight of 15,000 and montmorillonite. The pellets were immersed in hot water to extract and remove unreacted monomers, and then dried with a vacuum dryer.

Examples 2 and 3 The same procedures as in Example 1 were carried out except that the mixing ratio of PP-1 and MPA-1 was changed as shown in Table 1.

Example 4 MPP-1; 30% by weight, PP-1; 25% by weight, MPA-1; 40% by weight
And Mooney viscosity ▲ ML ^{100 ℃} _{1 + 4} ▼ 50, ethylene content 73
0.8% by weight of maleic anhydride and 0.4 part by weight of dicumyl peroxide were added to 100 parts by weight of an ethylene-propylene copolymer rubber of 100% by mass, and a melt index modified at 100 ° C. in paraxylene solution was 0.7 g / 10 minutes (230 minutes). ° C) modified ethylene-propylene copolymer rubber (hereinafter referred to as MEPR-1).
5% by weight was pelletized in the same manner as in Example 1 and injection molded to obtain a test piece.

Example 5 Instead of MEPR-1, SEBS-based block copolymer "Clayton G1657" (hereinafter referred to as SEBS) manufactured by Shell Chemical Company.
Example 4 was carried out except that was used.

Example 6 0.2 parts by weight of maleic anhydride and 100 parts by weight of a crystalline propylene homopolymer having a melt index of 1.0 g / 10 minutes and t
-32% by weight of modified polypropylene obtained by adding and mixing 0.2 part by weight of butyl peroxybenzoate, 48% by weight of MPA-1 and 20% by weight of glass fiber (hereinafter referred to as GF) having a length of 3 mm and a diameter of 11 µm. A test piece was obtained by pelletizing in the same manner as in Example 1.

Comparative Example 1 Instead of MPA-1, ordinary nylon having an average molecular weight of 15,000
Example 1 except that No. 6 (hereinafter referred to as PA-1) was used.
Was performed in the same manner as described above.

Comparative Example 2 Example 4 except that PA-1 was used instead of MPA-1.
Was performed in the same manner as described above.

Comparative Example 3 Example 5 except that PA-1 was used instead of MPA-1.
Was performed in the same manner as described above.

Comparative Example 4 Instead of MPA-1, ordinary nylon having an average molecular weight of 20,000
Example 6 was repeated except that 6,6 (hereinafter referred to as PA-2) was used.

Comparative Example 5 Instead of MPA-1, ordinary nylon having an average molecular weight of 11,000
Example 6 except that PA-6 (hereinafter referred to as PA-3) was used.
Was performed in the same manner as described above.

Comparative Example 6 In the same manner as in Example 1, except that 98% by weight of PA-1 and 2% by weight of montmorillonite were melt-mixed (hereinafter referred to as PA-4) instead of MPA-1. went.

Table 1 shows the results of Examples 1 to 6 and Comparative Examples 1 to 6.

Examples 7 to 11 and Comparative Examples 7 to 11 In the same manner as in Example 1, the respective components were blended at the composition ratios shown in Table 2, and respective resin compositions were obtained to produce test pieces.

Each physical property of the test piece of the obtained resin composition was measured. The results are shown in Table-2.

In Examples 9 to 10 and Comparative Examples 9 to 10, GF
Was replaced by powdered talc.

As is apparent from these results, the thermoplastic resin composition of the present invention significantly improves heat resistance and impact resistance by using the modified polyamide of the present invention as compared with the case of using a conventional polyamide. You can see that.

〔The invention's effect〕

The present invention uses a modified polyamide having a significantly improved heat resistance, rigidity and molecular cohesion in a thermoplastic resin in which a polyamide is blended with a polypropylene. By using the resin composition, the heat resistance and impact resistance of the resin composition are remarkably improved.

Accordingly, the thermoplastic resin composition of the present invention has a very excellent balance between rigidity, heat resistance and impact resistance, and has significantly improved flaw resistance, flaw resistance, moldability and appearance of warpage of a molded product. , Bumpers, wheel caps,
It is suitable for a variety of industrial parts such as automotive interior and exterior parts such as spoilers, instrument panels and trims, home electric parts and machine parts, and other applications requiring both heat resistance and impact resistance.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomohiko Akakawa 3-1 Chikko Shinmachi, Sakai City, Osaka Ube Industries, Ltd. Inside the Sakai Plant (72) Inventor Ikunori Sakai 3-1 Chikko Shinmachi, Sakai City, Osaka Ube Industries, Ltd. (72) Inventor Takao Nomura 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Takezumi Nishio 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Corporation (72) Inventor Toshio Yokoi 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (72) Inventor Shinya Kawamura 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd.

Claims (7)

(57) [Claims] 1. Component (a) 95 to 5% by weight of a modified polypropylene graft-modified with an unsaturated carboxylic acid or / and a derivative thereof or 95 to 5% by weight of a crystalline polypropylene containing at least 5% by weight of the modified polypropylene; b) A thermoplastic resin composition comprising 5 to 95% by weight of a modified polyamide partially or entirely modified with a clay mineral. 2. The thermoplastic resin composition according to claim 1, wherein said component (a) is 80 to 20% by weight and said component (b) is 20 to 80% by weight. 3. An ethylene / α-olefin copolymer rubber or part or all of component (c) is further added to 100 parts by weight of the thermoplastic resin composition comprising component (a) and component (b). The thermoplastic resin composition according to claim 1, comprising 1 to 100 parts by weight of a modified ethylene / α-olefin copolymer rubber graft-modified with an unsaturated carboxylic acid and / or a derivative thereof. 4. A thermoplastic resin composition comprising the component (a) and the component (b), 100 parts by weight of the component (d), a general formula: A- (BA) _n (where A is A block copolymer represented by a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5) or
The heat according to claim 1 or 2, comprising 1 to 100 parts by weight of a hydrogenated derivative of the block copolymer or a modified block copolymer obtained by graft-modifying the block copolymer with an unsaturated carboxylic acid and / or a derivative thereof. Plastic resin composition. 5. The composition according to claim 1, further comprising 5 to 150 parts by weight of an inorganic filler of component (e) based on 100 parts by weight of the thermoplastic resin composition comprising component (a) and component (b). Thermoplastic resin composition. 6. An ethylene / α-olefin copolymer rubber or a part or all of the component (c) is further added to 100 parts by weight of the thermoplastic resin composition comprising the component (a) and the component (b). A modified ethylene / α-olefin copolymer rubber graft-modified with an unsaturated carboxylic acid and / or a derivative thereof, and a component (d) represented by the general formula: A- (B-
A) _n (where A is a polymer block of a monovinyl-substituted aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5), or The hydrogenated derivative of the block copolymer or a modified block copolymer obtained by graft-modifying the block copolymer with an unsaturated carboxylic acid and / or a derivative thereof, in an amount of 1 to 100 parts by weight. Thermoplastic resin composition. 7. An ethylene / α-olefin copolymer rubber or a part or all of the component (c) is further added to 100 parts by weight of the thermoplastic resin composition comprising the component (a) and the component (b). A modified ethylene / α-olefin copolymer rubber graft-modified with an unsaturated carboxylic acid and / or a derivative thereof and / or component (d), a general formula, A- (BA) _n (where A is monovinyl-substituted) A polymer block of an aromatic hydrocarbon, B is an elastomeric polymer block of a conjugated diene, and n is an integer of 1 to 5.) or a hydrogenated derivative of the block copolymer or A modified block copolymer obtained by graft-modifying the block copolymer with an unsaturated carboxylic acid and / or a derivative thereof in an amount of 1 to 100 parts by weight, and a component (e) an inorganic filler in an amount of 5 to 1 part by weight. The thermoplastic resin composition according to claim 1 or 2, which comprises 50 parts by weight.