JPH09137035A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition comprising a specific olefinic copolymer composition and talc, showing good processability on injection molding, excellent in appearance, flexural modulus, tensile elongation, heat resistance, surface hardness and shock resistance and useful as interior parts for motor vehicles. SOLUTION: This composition comprises (A) a propylene-ethylene block copolymer having the propylene homopolymerization part with a melt flow rate (M) of 20-100g/10min and an isotactic pentad fraction of >=0.98 and having M=10-100 and the ratio of the weight-average molecular weight to the number- average molecular weight of 5-7, (B) an ethylene-butene random copolymer (EB) resin with a melting point (Tm) of 60-100 deg.C, M of 0.5-10, (C) an EB rubber with no Tm at 30 deg.C and M of 0.5-10, (D) an elastomer having the PE-EB-(PE) structure containing 20-40% of polyethylene (PE) crystalline region with Tm of 80-110 deg.C, M of 0.5-20 and 60-80% of the random elastomer region and (E) a talc with an average particle size of <=5μm and a specific surface area of >=3.5m<2> /g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene / ethylene block copolymer, a low crystalline ethylene / butene random copolymer resin, an amorphous ethylene / butene random copolymer rubber, and a specific elastomer having a block structure. , And talc, which has good workability during injection molding, excellent appearance, and good bending elastic modulus, impact resistance, tensile elongation, heat resistance, and surface hardness, especially for automobile interior parts The present invention relates to a thermoplastic resin composition suitable for molded articles.

[0002]

2. Description of the Related Art There have been many attempts to improve impact resistance and rigidity by adding ethylene / propylene copolymers, various ethylene copolymers and talc to polypropylene. For example, the compositions described in JP-B-63-42929, JP-A-64-150, JP-A-64-66263, and JP-A-1-204946, which have excellent impact resistance, are known. There is. However, the composition described in Japanese Patent Publication No. 63-42929 does not have sufficient flexural modulus and heat resistance because polypropylene having a significantly high crystallinity is not used. Also, JP-A-64-150, JP-A-64-66263 and JP-A-1
The compositions described in the respective publications of -204946 are suitable for applications such as bumpers due to the low content of talc, but the flexural modulus is significantly insufficient for use as interior materials. is there. In addition, JP-B-4-1593 containing an ethylene / α-olefin copolymer and a large amount of an inorganic filler.
The composition described in Japanese Patent Publication No. 45 is known, but it is not preferable from the viewpoint of having a large specific gravity and reducing the weight of an automobile. On the other hand, a composition described in JP-A-7-53843 has been proposed as an attempt to improve the above-mentioned drawbacks, but in a use requiring low pressure and high cycle molding, the composition has higher fluidity. There is a need for certain materials, and the composition has insufficient flowability to meet these high requirements.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, and has an instrument panel including high fluidity, good physical properties and excellent moldability. The object is to provide a composition suitable for automobile interior parts.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that propylene / ethylene having a propylene homopolymer portion having high fluidity and extremely high crystallinity. Block copolymer, resin-like copolymer containing a crystalline segment in the molecule, a substantially elastomeric copolymer containing few crystalline segments in the molecule, a specific polyethylene structure and high butene content By blending a block elastomer composed of an ethylene / 1-butene copolymer structure and talc in a specific ratio, the composition exhibits the above-mentioned high fluidity and good physical properties and is excellent in molding processability. The inventors have found that a product can be obtained and completed the present invention.

That is, the thermoplastic resin composition of the present invention is a thermoplastic resin composition characterized by comprising the following components (A) to (E). Component (A): The propylene homopolymer portion has a melt flow rate (MFR) of 20 to 200 g / 10 minutes, an isotactic pentad fraction of 0.98 or more, and a block copolymer MFR of Propylene / ethylene block copolymer weight with a ratio (Mw / Mn) of the same weight average molecular weight (Mw) and number average molecular weight (Mn) of 5 to 7 at 10 to 100 g / 10 minutes (230 ° C., 2.16 kg load). Combined 50 to 75% by weight (B) component: Ethylene / butene random copolymer resin having a melting temperature of 60 to 100 ° C. and MFR of 0.5 to 10 g / 10 minutes 5 to 10% by weight (C) component : Ethylene / butene random copolymer rubber having a melting temperature of 30 ° C or higher and an MFR of 0.5 to 10 g / 10 minutes 5 to 10% by weight (D) component: Melting temperature at 80 to 110 ° C The following formula [I] and / or formula [II], which has a MFR of 0.5 to 20 g / 10 minutes, a polyethylene crystalline portion of 20 to 40% by weight, and a random elastomer portion of 60 to 80% by weight. An elastomer having a block structure represented by 0.3 to 5% by weight Polyethylene / (ethylene / butene random part) / polyethylene [I] Polyethylene / (ethylene / butene random part) [II] (E) component: average particle size Is 5 μm or less, and the specific surface area is 3.5 m ² / g or more, talc 15 to 25% by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

[I] Component (A) Propylene / ethylene block copolymer ((A)
Component) Physical Properties of Propylene / Ethylene Block Copolymer The propylene / ethylene block copolymer ((A) component) constituting the thermoplastic resin composition of the present invention has a melt flow rate (MFR: 230 ° C., 2.16 kg load). ) Is 1
0 to 100 g / 10 minutes, preferably 20 to 80 g / 10
Min, particularly preferably 30 to 60 g / 10 min. MF of propylene / ethylene block copolymer
When R is less than the above range, the fluidity is insufficient, and a molding machine having a large mold clamping force is required when molding a thin-walled molded product, or it is necessary to raise the molding temperature. It adversely affects productivity. On the contrary, when the MFR of the propylene / ethylene block copolymer exceeds the above range,
Insufficient properties such as impact resistance. The MFR of the propylene / ethylene block copolymer may be adjusted at the time of polymerization, or may be adjusted after polymerization with an organic peroxide such as diacyl peroxide or dialkyl peroxide.

The ratio (Mw / M) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the block copolymer, which represents the molecular weight distribution of the propylene / ethylene block copolymer.
The n) used is within the range of 5 to 7, preferably 5.5 to 6.5. If the content is out of these ranges, the impact strength will be reduced. MFR of the propylene homopolymer portion in the propylene / ethylene block copolymer is 20 to 200 g.
/ 10 min, preferably 30 to 150 g / 10 min, particularly preferably 40 to 100 g / 10 min, and the isotactic pentad fraction thereof is 0.98 or more, preferably 0.985 or more. M of the propylene homopolymer portion in the propylene / ethylene block copolymer
When FR is less than the above range, the fluidity becomes insufficient, and when MFR exceeds the above range, the impact resistance is poor.

Further, if the isotactic pentad fraction (P) of the propylene homopolymer portion in the propylene / ethylene block copolymer is less than the above range, the flexural modulus is insufficient, which is not suitable. The isotactic pentad fraction (P) is the isotactic fraction in the pentad unit in the polypropylene molecular chain measured by ¹³ C-NMR. The ethylene content in the propylene / ethylene block copolymer is 2
The ethylene content of the elastomer portion in the block copolymer is preferably 30 to 50% by weight. When the ethylene content is less than the above range, heat resistance tends to be poor, and when the ethylene content exceeds the above range, bending elasticity and surface hardness tend to be insufficient.

Of propylene / ethylene block copolymer
Production A highly stereoregular catalyst is used in the production of the propylene / ethylene block copolymer. Examples of the production of the above catalyst include titanium trichloride compositions obtained by reducing titanium tetrachloride with an organoaluminum compound and further treating it with various electron donors and electron acceptors, an organoaluminum compound and an aromatic carboxylic acid. Method of combining with acid ester (JP-A-56-100806, JP-A-56-1207)
12, see JP-A-58-104907).
Also, a method of a supported catalyst in which titanium tetrachloride and various electron donors are brought into contact with magnesium halide (JP-A-57 / 1982)
-63310, JP-A-63-43915, JP-A-6-63
No. 3-83116). In the presence of the above catalyst, a gas phase fluidized bed, a solution method,
It can be obtained by applying a manufacturing process such as a slurry method to block-copolymerize propylene and ethylene.

Blending ratio The blending amount of the above propylene / ethylene block copolymer is 50 to 75% by weight, preferably 53 to 72% by weight, particularly preferably 55% by weight in the thermoplastic resin composition of the present invention.
It is important to contain ˜70% by weight. If the content is less than the above range, the flexural modulus will be poor, and conversely, if it exceeds the range, the impact resistance will be reduced.

(B) Ethylene / Butene Random Copolymer Resin (Component (B)) The ethylene / butene random copolymer resin (component (B)) constituting the thermoplastic resin composition of the present invention is a thermoplastic resin. It is used for the purpose of maintaining good surface hardness while improving the impact resistance of the composition.

Of ethylene / butene random copolymer resin
Physical Properties The ethylene / butene random copolymer resin (component (B)) can exhibit a higher degree of physical property balance when used in combination with the components (C) and (D) described below. This ethylene-butene random copolymer resin (component (B)) is a differential scanning calorimeter (DSC: Diff).
erential scanning calorim
60 to 100 ° C., preferably 6
Those having a melting temperature of 5 to 90 ° C., particularly preferably 70 to 80 ° C. are used. When the melting temperature is less than the above range, the crystallinity is low and the surface hardness is insufficient. On the contrary, if it exceeds the above range, the impact resistance becomes insufficient. It is sufficient that the melting temperature is within the above range regardless of the butene content. The butene content is 15
From about 25 to 25% by weight, particularly from 17 to 23% by weight, is preferable from the viewpoint of impact resistance and surface hardness.

Further, the melt flow rate of ethylene / butene random copolymer resin (MFR: 230 ° C., 2.1
The load (6 kg) is 0.5 to 10 g / 10 min, preferably 1 to 8 g / 10 min, and particularly preferably 2 to 7 g / 10 min. If the MFR is less than the above range or more than the above range, the impact resistance is lowered. The density of the ethylene / butene random copolymer resin (component (B)) is 0.90 g /
It is preferably less than cm ³ , particularly 0.87 to 0.89 g / cm ^{3 because} it is more favorable from the viewpoint of impact resistance and surface hardness. The ethylene / butene random copolymer resin does not have to be one type, and may be a mixture of two or more types.

Ethylene-butene random copolymer resin
Production The ethylene / butene random copolymer resin is produced by applying a production process such as a gas phase fluidized bed, a solution method, or a slurry method in the presence of an ion polymerization catalyst such as a Ziegler type catalyst or a Phillips type catalyst to produce ethylene and butene. It can be obtained by copolymerizing.

Blending Ratio The blending amount of the above ethylene / butene random copolymer resin is 5 to 10% by weight in the thermoplastic resin composition of the present invention.
It is important to contain preferably 6 to 9% by weight.
If the compounded amount is less than the above range, the Rockwell hardness will decrease, and conversely, if it exceeds the above range, the bending elasticity will decrease.

(C) Ethylene / butene random copolymer rubber ((C) component) The ethylene / butene random copolymer rubber ((C) component) constituting the thermoplastic resin composition of the present invention has a high resistance to It is used for the purpose of developing impact resistance. This ethylene / butene random copolymer rubber ((C) component) is a differential scanning calorimeter (DSC: Differential Scan).
Ning Calorimeter)
It is suitable to use a substantially amorphous elastomer which does not have a melting temperature above 0 ° C. If it has a melting temperature of 30 ° C. or higher, the impact resistance becomes insufficient. The melt flow rate (MFR: 230 ° C., 2.16 kg load) of the ethylene / butene random copolymer rubber is 0.5 to
10 g / 10 min, preferably 1 to 8 g / 10 min, particularly preferably 2 to 7 g / 10 min are used.
If the MFR of the copolymer rubber is outside the above range, the impact resistance becomes insufficient. Also preferred density of the ethylene-butene random copolymer rubber is less than 0.90 g / cm ^3, especially since those of 0.87~0.89g / cm ^3, becomes excellent in terms of impact resistance . The ethylene / butene random copolymer rubber does not have to be one type, and may be a mixture of two or more types.

Of ethylene / butene random copolymer rubber
Production The ethylene / butene random copolymer rubber is produced by the gas phase fluidized bed, the solution method, the slurry method, etc. in the presence of an ion polymerization catalyst such as a Ziegler type catalyst or a Phillips type catalyst in the same manner as the component (B). It is obtained by applying a process to copolymerize ethylene and butene.
Any substantially amorphous elastomeric material may be used regardless of the butene content. The butene content is 25% by weight
It is preferable that the amount exceeds 30% by weight, especially 30% by weight or more, because it is good from the viewpoint of improving impact resistance.

Blending ratio The blending amount of the above ethylene / butene random copolymer rubber is 5 to 10% by weight in the thermoplastic resin composition of the present invention.
It is important to contain preferably 6 to 9% by weight.
If the blending amount is less than the above range, the impact resistance decreases, and conversely,
If it exceeds the above range, the flexural elasticity decreases.

(D) Block-Structure Elastomer (Component (D)) The block-structure elastomer ((D) component) constituting the thermoplastic resin composition of the present invention is the above-mentioned component (B), (C). It is for more effectively expressing the effect of improving the impact resistance of the component, and even if added in a small amount, the effect can be exhibited.

Physical Properties of Elastomer Having Block Structure Elastomer having this block structure (component (D))
The melting temperature of is measured by a differential scanning calorimeter (DSC: Differ).
ENTIAL SCANNING CALORIMET
er) measured at 80-110 ° C, preferably 90-
105 ° C. If the melting temperature is out of the above range, the impact resistance becomes insufficient. Further, the melt flow rate (MFR: 230 ° C., 2.16 kg load) of the block-structured elastomer (component (D)) used in the present invention is 0.5 to 20 g / 10 minutes, preferably 0.5 to 15 g /
10 minutes. If the MFR is less than the above range, or
If it exceeds the above range, the IZOD impact strength decreases.

The block-structured elastomer (component (D)) contains a polyethylene structure and an elastomer structure as essential components, and even if either structure is lacking, the above performance is not sufficiently exhibited. Can not. The elastomer having the block structure may have a triblock structure or a diblock structure as shown in the following formula. Polyethylene / (ethylene / butene random part) / polyethylene [I] Polyethylene / (ethylene / butene random part) [II] The ratio of the crystalline part having the polyethylene structure is 2
It is 0 to 40% by weight, preferably 23 to 35% by weight.
Further, the ratio of the portion having the elastomer structure is 60 to
80% by weight, preferably 65 to 77% by weight, and its butene content (1,2 polymerization ratio) is preferably 60 to 90% by weight, particularly preferably 65 to 85% by weight.
belongs to. If the ratio is out of this range, the impact resistance tends to be poor.

Production of Elastomer Having Block Structure The production method of these elastomers is not particularly limited, but for example, a method similar to the method described in JP-A-5-34513 is used, and the following method is used. It can be manufactured in this manner. For example, by polymerizing 1,4 butadiene, the polarity of the solvent can be adjusted to
The production ratio of polymerization can be improved. If hydrogenation is performed at this stage, the diblock structure elastomer represented by the formula [II] can be obtained. Further, by subjecting these to a coupling treatment and then hydrogenating, an elastomer having a triblock structure represented by the formula [I] can be obtained. As the polymerization method, so-called living polymerization can be used, and polymerization can be performed by the same method as a method of polymerizing a styrene-based elastomer such as SEBS (styrene / ethylene / butylene / styrene copolymer). The component (D) used in the present invention preferably has a ratio of 1,2 polymerization of 60 to 90% by weight, particularly preferably 65 to 85% by weight. These 1, 2
If the polymerization ratio is outside the above range, the above performance tends to be insufficiently exhibited.

Blending ratio Elastomer having the above block structure (component (D))
The compounding amount of 0.3 to 5% by weight, preferably 0.5 to 3
%, Particularly preferably 0.75 to 3% by weight. If the amount is too large, the Rockwell hardness will decrease. On the contrary, if the amount is too small, the above effect is lost.

(E) Physical Properties of Talc (Component (E)) Talc Talc ((E) which constitutes the thermoplastic resin composition of the present invention
(Component), the average particle size is 5 μm or less, preferably 0.5 to 3 μm, and the specific surface area is 3.5 m ² / g.
As described above, it is preferably 3.5 to ⁶ m ² / g. If they are out of the above range, the flexural modulus decreases, which is unsuitable. The average particle size is determined from the particle size value at a cumulative amount of 50% by weight read from a particle size cumulative curve measured by a liquid layer sedimentation type light transmission method (for example, CP type manufactured by Shimadzu Corporation). To be The measurement of the specific surface area is obtained from the measurement value by an air permeation method (for example, SS-100 type constant pressure ventilation type specific surface area measuring device manufactured by Shimadzu Corporation).
Further, these talcs are generally produced by dry pulverization and then dry classification. Talc may be surface-treated with various organic titanate coupling agents, silane coupling agents, fatty acids, fatty acid metal salts, fatty acid esters, etc. for the purpose of improving the adhesiveness or dispersibility with the polymer. good.

Blending ratio The blending amount of talc is 15 to 25% by weight, preferably 17 to 23% by weight. If the blending amount of talc is less than the above range, the flexural modulus is insufficient, and if it exceeds the above range, the tensile elongation decreases.

(F) Additional component (optional component) The thermoplastic resin composition of the present invention comprises the above (A) to (E).
In addition to the above essential components, other additional components (component (F)) can be added within a range that does not significantly impair the effects of the present invention. Examples of such additional components (component (F)) include phenol-based and phosphorus-based antioxidants, hindered amine-based, benzophenone-based, benztriazole-based weathering deterioration inhibitors, aluminum compounds, and nucleating agents such as phosphorus compounds. , Dispersants represented by metal salts of stearic acid, quinacridone, perylene, phthalocyanine, coloring substances such as carbon black, fibrous potassium titanate, fibrous magnesium oxysulfate, fibrous aluminum borate, whiskers such as calcium carbonate, carbon Materials such as fibers and glass fibers can be exemplified.

[II] Method for Producing Thermoplastic Resin Composition (1) Kneading The thermoplastic resin composition of the present invention contains the above-mentioned components in a conventional extruder, Banbury mixer, roll, Brabender Plastograph, kneader. It is produced by kneading at room temperature by using, for example, but it is preferable to use an extruder, especially a twin-screw extruder among these.

(2) Molding Processing The molding method of the thermoplastic resin composition of the present invention is not particularly limited, but the injection molding method is most preferable in view of the effect of the invention. Are suitable.

[III] Thermoplastic Resin Composition (1) Physical Properties The thermoplastic resin composition of the present invention produced by the above method has good workability during injection molding, flexural modulus, impact resistance, and The following physical properties excellent in tensile elongation, surface hardness and heat resistance can be exhibited. (A) MFR: 20 g / 10 minutes or more, preferably 25 g / 10 minutes or more (b) Flexural modulus: 20,000 kg / cm ² or more,
Preferably 23,000-28,000 kg / cm ² (c) Izod impact value (23 ° C.): 1
5 kg · cm / cm or more, preferably 18 kg · cm /
cm or more (d) Tensile elongation: 400% or more, preferably 500
% Or more (e) Rockwell hardness: 75 or more, preferably 80
Above (f) Heat distortion temperature: 120 ° C. or above, preferably 130
that's all

(2) Applications It is possible to process various molded products because it is a material that can exhibit the above-mentioned physical properties. Among them, injection molded products such as automobile interior material parts, especially instrument panels. It is preferable to mold into a console box or the like.

[0031]

The present invention will be described more specifically with reference to the following experimental examples. [I] Measuring Method (1) MFR: Based on ASTM-D1238, it was measured at a temperature of 230 ° C. under a load of 2.16 kg. (2) Isotactic pentad fraction (P): ¹³
Macromolecule, 8, using C-NMR
687 (1975). (3) Melting temperature: Differential scanning calorimeter (DSC: Di
differential Scanning Calori
and melt the sample by heating it up to a temperature of 180 ° C. at a rate of 10 ° C./min to −100 ° C.
It was cooled to the temperature of 10 ° C., then heated at a rate of 20 ° C./min, and read from the peak position of the obtained thermogram. (4) Flexural modulus: In accordance with ASTM-D790,
It was measured at a bending speed of 2 mm / min at 23 ° C. (5) Impact resistance: In accordance with ASTM-D785,
It was evaluated by the Izod impact value at 23 ° C. (6) Tensile elongation: In accordance with ASTM-D638,
A tensile test was performed at 23 ° C. at a speed of 10 mm / min to measure the elongation rate. (7) Surface hardness: According to ASTM-D785,
The Rockwell hardness at 23 ° C. was evaluated on the R scale. (8) Heat distortion temperature: According to ASTM-D523,
It was measured under a load of 4.6 kg.

[II] Experimental Examples Examples 1 to 15 and Comparative Examples 1 to 25 The raw materials shown in Tables 1 to 5 were blended at the composition ratios shown in Tables 6 and 7 to 8, and further tetrakis [methylene- 3-
(3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] 0.1 part by weight of methane and 0.4 part by weight of magnesium stearate are blended and mixed for 5 minutes with a Kawada super mixer. After that, a thermoplastic resin composition was obtained by kneading and granulating at a set temperature of 210 ° C. with an FCM twin-screw kneader manufactured by Kobe Steel. Then, various test pieces were prepared at an injection molding machine having a mold clamping force of 100 tons at a molding temperature of 210 ° C. and measured according to the above-mentioned various measuring methods, and the evaluation results are shown in Tables 9 to 11.

[0033]

[Table 1]

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037]

[Table 5]

[0038]

[Table 6]

[0039]

[Table 7]

[0040]

[Table 8]

[0041]

[Table 9]

[0042]

[Table 10]

[0043]

[Table 11]

[0044]

The thermoplastic resin composition of the present invention has a propylene / ethylene block copolymer, a low crystalline ethylene / butene random copolymer resin, an ethylene / butene random copolymer rubber, and a block structure. Since it is composed of the elastomer and talc,
It has good workability during injection molding and has good appearance, flexural modulus, tensile elongation, heat resistance, surface hardness, and impact resistance, and can be suitably used for injection molded products such as automobile interior parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location C08L 53:00) (72) Inventor Yukika Hana Higashi Toho-cho, Yokkaichi-shi, Mie 1 Incorporated company Yokkaichi Research Institute (72) Inventor Ikuo Tsutsumi 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Corporation Incorporated Yokkaichi Research Institute (72) Inventor Hironari Sano 1 Toho-cho, Mie Prefecture Mitsubishi Chemical Incorporated company Yokkaichi Research Institute (72) Inventor Hiroki Sato 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Inc. Yokkaichi Research Institute

Claims (3)

[Claims] 1. A thermoplastic resin composition comprising the following components (A) to (E). Component (A): The propylene homopolymer portion has a melt flow rate (MFR) of 20 to 200 g / 10 minutes, an isotactic pentad fraction of 0.98 or more, and a block copolymer MFR of 50 to 75% by weight of a propylene / ethylene block copolymer having a ratio (Mw / Mn) of the same weight average molecular weight (Mw) to the number average molecular weight (Mn) of 5 to 7 at 10 to 100 g / 10 minutes ( Component B): ethylene / butene random copolymer resin having a melting temperature of 60 to 100 ° C and MFR of 0.5 to 10 g / 10 minutes 5 to 10% by weight (C) component: melting temperature of 30 ° C or higher And an ethylene / butene random copolymer rubber having an MFR of 0.5 to 10 g / 10 minutes 5 to 10% by weight (D) component: having a melting temperature of 80 to 110 ° C. and an MFR of 0.5. ~ 20 Elastomer having a block structure represented by the following formula [I] and / or formula [II], having a polyethylene content of 20 to 40% by weight and a random elastomer part of 60 to 80% by weight: 0.3 to 5 wt% Polyethylene / (ethylene / butene random part) / polyethylene [I] Polyethylene / (ethylene / butene random part) [II] (E) component: Average particle size is 5 μm or less and specific surface area is 3 Talc having a content of 0.5 m ² / g or more 15 to 25% by weight 2. The elastomer of component (D) is a hydrogenated product of a butadiene polymer, and the ratio of 1,2 polymerization of butadiene in the ethylene / butene random elastomer portion is 60 to 90% by weight. Item 2. The thermoplastic resin composition according to item 1. 3. The composition has a physical property of MFR of 20 g / 10 minutes or more, a flexural modulus of 20,000 kg / cm ² or more, an Izod impact value of 15 kg · cm / cm or more, and a tensile elongation of 400.
% Or more, heat distortion temperature 120 ° C or more, Rockwell hardness 7
The thermoplastic resin composition according to claim 1, which is 5 or more.