JP3477227B2 - Polyamide resin composition and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamide resin composition having excellent ductility, toughness, rigidity at high temperature and moisture absorption, small molding shrinkage and high heat distortion temperature, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Various approaches have been taken to improve the toughness of polyamides (GB 9984).
39, U.S. Pat. Nos. 3,845,163 and 3,3831.
No. 86, No. 3465059, No. 3668274
No., JP-B-55-44108). Above all
The polyamide resin composition disclosed in No. 44108 comprises 60 to 99% by weight of one phase containing a polyamide matrix resin having a number average molecular weight of at least 5000.
And at least one kind of polymer particles selected from the group consisting of branched and straight chain polymers,
Consisting essentially of 1-40% by weight of at least one other phase having a particle size in the range of -1.0 micron (μm) and having sites for adhesion to the polyamide matrix resin,
The at least one polymer has a specific formula and is from about 1.0 to 20,000 psi (0.0705 to 1410).
a tensile modulus in the range of kg / cm ² ) and a ratio of the tensile modulus of the polyamide matrix resin to the tensile modulus of the at least one polymer is 10:
Greater than 1, the at least one polymer comprises at least 20% by weight of the at least one other phase, and is a composition having improved ductility or toughness.

[0003]

However, since the polyamide resin composition has come to be used in various fields such as the field of home electric appliances and the interior and exterior of automobiles, it has improved ductility or toughness and excellent rigidity. It is desired to develop a composition having a high heat distortion temperature and having a small warpage after molding.

Therefore, the polyamide resin composition having the above-described improved ductility or toughness may have insufficient rigidity. In such a field, glass fiber, minerals and the like are further added. Therefore, a polyamide resin composition having enhanced rigidity is used.

However, in applications such as automobile wheel covers, there is a problem that the specific gravity of the polyamide resin composition reinforced with glass fiber or mineral is too large. Moreover, when a resin composition reinforced with glass fibers is used, warpage occurs in a molded product, which causes a problem in terms of dimensional stability.

In view of such circumstances, the present invention has improved ductility or toughness of conventional polyamide resin compositions, improved rigidity at high temperature and moisture absorption, high heat distortion temperature, and molding shrinkage. An object of the present invention is to provide a polyamide resin composition having a small value.

[0007]

A first polyamide resin composition according to the present invention which achieves the above object comprises: A polyamide resin of 10 to 89% by weight; and B of the following groups (a) to (d): 1 to 30 wt% of one or more selected elastomers, (a) an elastomer composed of ethylene / propylene / diene (b) an elastomer composed of graft-modified ethylene / propylene / diene (c) an ethylene / unsaturated carboxylic acid / Elastomer (d) graft-modified ethylene / unsaturated carboxylic acid containing an unsaturated carboxylic acid ester and having an unsaturated monomer which is at least reactive and is graft-modifiable
Elastomer C composed of unsaturated carboxylic acid ester C A copolymer of ethylene and an olefin having a cyclic structure, which is amorphous, and has a glass transition temperature of 100 to 190.
It is essentially composed of 10 to 60% by weight of polyolefin which is at 0 ° C.

In addition to the components A to C, the polyamide resin composition according to the present invention further comprises D carboxylic acid or carboxylic anhydride compound 0.01 to
It is characterized by containing 10.0% by weight.

The present invention will be described in detail below.

The polyamide resin A of the present invention is well known in the art and includes a semi-crystalline resin and an amorphous resin, and is generally called nylon. Suitable polyamides include U.S. Pat. Nos. 2,071,250, 2,
071,251, 2,130,523, 2,1
30,948, 2,241,322, 2,31
2,966, 2,512,606 and 3,3
Those described in No. 93,210 are included. The polyamide resin is produced by condensing a saturated dicarboxylic acid having 4 to 12 carbon atoms and a diamine having 4 to 14 carbon atoms in equimolar amounts. It is also possible to use diamine in excess so that the polyamide end groups have amine groups in excess of carboxyl groups. Examples of polyamides are polyhexamethylene adipamide (66 nylon), polyhexamethylene azelamide (69 nylon), polyhexamethylene sebacamide (610 nylon), and polyhexamethylene dodecanoamide (612 nylon); Polyamides produced by ring opening of lactams, namely polycaprolactam, polylaurinlactam, poly-11-amino-
Includes undecanoic acid, bis (p-aminocyclohexyl) methanddecanoamide. In the present invention, it is also possible to use a polyamide produced by copolymerization of two kinds of the above polymers or a terpolymer of the above polymers or their components, for example, adipic acid and hexamethylenediamine isophthalate copolymer. it can. Preferably the polyamide is a linear polymer having a melting point above 200 ° C.

In the present invention, among the polyamide resins,
By using a polyamide resin having a relative viscosity Rv of 16 to 45, it is possible to further improve the toughness and the rigidity at high temperature and when absorbing moisture. That is, for example, when only the elastomer used in the present invention is added to the polyamide, the toughness is improved, but in such a system, if the polyamide having Rv of less than 43 is used, the physical properties are deteriorated. However, in the system in which the specific elastomer and the amorphous cyclic polyolefin are added as in the present invention, the lower the Rv of the polyamide resin is 16 to 45, the more the physical properties are improved. It is considered that this is because the polyamide easily wraps other components. Here, the relative viscosity Rv is J
It is measured according to IS K6810 using formic acid as a solvent.

Further, in the present invention, a polyamide resin having a high concentration of amine end groups, specifically, a concentration of 6 amine end groups is used.
0 × 10 ⁻⁶ mol / g or more, preferably 60 × 10 ⁻⁶
By using a polyamide resin of mol / g or more and 200 × 10 ⁻⁶ or less, more excellent physical properties can be obtained. Here, the concentration of the amine terminal group refers to that measured by dissolving the polyamide resin in a phenol / methanol solution and titrating with hydrochloric acid.

Preferred compositions are those which contain 30 to 65% by weight of polyamide, although as much as 10 to 89% by weight of the composition of the invention may consist of polyamide.

The composition of the present invention contains at least one elastomer B as described above. Here, the elastomer B is, as described above, an elastomer composed of ethylene / propylene / diene or an unsaturated monomer which is composed of ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester and has at least reactivity and is graft-modifiable. And an elastomer obtained by graft-modifying any of these. It is preferable to use an elastomer consisting essentially of ethylene / propylene / diene modified with carboxylic acid / carboxylic anhydride or an elastomer consisting essentially of ethylene / acrylate / methacrylate / unsaturated epoxide.

Elastomers consisting essentially of ethylene / propylene / diene modified with carboxylic acid / carboxylic anhydride include, for example, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride; ethylene / propylene / 1,4-hexadiene and ethylene /
Mixture with maleic anhydride; ethylene / propylene /
1,4-hexadiene and ethylene / propylene / 1,4
A mixture with hexadiene-g-maleic anhydride; ethylene / propylene / 1,4-hexadiene-g-fumaric acid; ethylene / propylene / 1,4-hexadiene / norbornadiene-g-maleic anhydride; ethylene / propylene / 1 , 4-hexadiene / norbornadiene-g
Maleic anhydride monoethyl ester; ethylene / propylene / 1,4-hexadiene / norbornadiene-g
Fumaric acid; a mixture of ethylene / propylene / 1,4-hexadiene and ethylene / monoethyl ester of maleic anhydride; a mixture of ethylene / propylene / 1,4-hexadiene and ethylene / monobutyl maleate; ethylene / propylene / Examples thereof include a mixture of 1,4-hexadiene and ethylene / maleic anhydride.

As the elastomer consisting essentially of ethylene acrylate methacrylate and unsaturated epoxide, for example, ethylene / methyl acrylate / glycidyl methacrylate; ethylene / butyl acrylate / glycidyl methacrylate; ethylene / methyl methacrylate /
Examples thereof include glycidyl acrylate.

The composition of the present invention contains C, which is a copolymer of ethylene and an olefin having a cyclic structure, is amorphous, and has a glass transition temperature of 100 to 190 ° C. Such an amorphous cyclic polyolefin C is, for example, Ziegler
It can be produced using a Natta catalyst, and examples of commercially available products include cyclic olefin copolymer "Apel" (registered trademark: Mitsui Petrochemical Industry Co., Ltd.). The composition of the present invention contains 10 to 60% by weight of such an amorphous cyclic polyolefin.

As described above, the composition of the present invention comprises 10 to 89% by weight of polyamide resin A, 1 to 30% by weight of specific elastomer B and 10 to 60% by weight of specific amorphous cyclic polyolefin C. Since the polyamide resin is combined, the toughness of the polyamide resin is enhanced, the rigidity at high temperature and when absorbing moisture is improved, the heat deformation temperature is high, and the molding shrinkage ratio is small.

Here, when the elastomer B is less than the above range, sufficient toughness cannot be strengthened. On the other hand, when the elastomer B is more than the above range, the flexural modulus becomes small. , Too soft, both are not preferable.

When the amount of the amorphous cyclic polyolefin C is less than the above range, the rigidity is not sufficiently enhanced at high temperature and when absorbing moisture, while the amount of the amorphous cyclic polyolefin C exceeds the above range. If the amount is large, there are many inconveniences in the process of producing a good composition, and the heat resistance decreases, which is not preferable.

The composition of the present invention comprises one or more conventional additives, such as stabilizers and inhibitors against deterioration by oxidation, heat and ultraviolet rays, lubricants and mold release agents, within the range not impairing the achievement of the object. , Colorants, including dyes and pigments, fibrous and granular fillers and reinforcing agents, nucleating agents,
It may be modified with a plasticizer or the like.

The stabilizer may be incorporated into the composition at any stage in the preparation of the composition of the present invention. Preferably, stabilizers are included to pre-empt the onset of degradation that occurs prior to protecting the composition. Such stabilizers must be compatible with the composition.

Oxidation stabilizers and heat stabilizers useful in the compositions of the present invention include those commonly used in addition polymers.
These are, for example, 1% by weight, based on the weight of the polyamide.
Group 1 metal halides such as sodium, potassium, lithium halides and cuprous halides such as chlorides, bromides, iodides, sterically hindered phenols, hydroquinones, and substituted member derivatives of these groups and their Including the combination of.

Based on the weight of polyamide, for example 2.0
The UV stabilizer added up to 100% may be one generally used in addition polymers. Examples of UV stabilizers include various substituted resorcinols, salicylates, benzotriazoles, benzophenones, and the like.

Suitable lubricants and mold release agents, such as up to 1.0% by weight of the composition of the lubricant and mold release agent, are:
Examples include stearic acid, stearyl alcohol, and stearamide; organic dyes such as nitrocin; pigments such as titanium dioxide, phthalocyanine, ultramarine blue, and carbon black.

The fibrous and granular fillers and reinforcing agents are, for example, carbon fiber, glass fiber, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica and feldspar. However, they can be added in an amount of up to 50% based on the weight of the composition, but they must be used to such an extent that the achievement of the purpose is not impaired.

Nucleating agents include, for example, talc, calcium fluoride,
Plasticizers such as sodium phenylphosphinate, alumina and ground polytetrafluoroethylene which may be compounded in amounts up to about 20% based on the weight of the composition are eg dioctyl phthalate, dibenzyl phthalate, butyl phthalate. Benzyl, hydrocarbon oil, Nn-butylbenzenesulfonamide, o- and p-tolueneethylsulfonamide and the like. Colorants (dyes and pigments) may be present in amounts up to about 5.0% by weight based on the weight of the composition.

The second polyamide resin composition of the present invention is
To obtain more excellent toughness and rigidity, a carboxylic acid or carboxylic acid anhydride compound is added.

The carboxylic acid or carboxylic acid anhydride compound reacts with the elastomer or the amorphous cyclic polyolefin contained in the composition of the present invention to form an acid anhydride bonded to these terminals, which is further added to the terminal of the polyamide. Therefore, a good composition can be formed.

As a method for producing the polyamide resin composition according to the present invention, known methods can be applied. The first polyamide resin composition is produced by mechanically blending all components (A to C) with an extruder, a kneader, or the like, or by dissolving all components in a suitable good solvent at the same time, or separately Examples of the method include a method of removing the solvent after dissolving and mixing in, and a method of performing a combination of these two methods.

On the other hand, as the second method for producing the polyamide resin composition, in the first step, the elastomer B, the non-crystalline cyclic polyolefin C and the carboxylic acid or carboxylic acid anhydride compound D are machined by an extruder, a kneader or the like. Blending, or dissolving components B to D in a suitable good solvent at the same time, or dissolving each separately and then mixing and removing the solvent to obtain in the second stage, the first stage The pellets and the polyamide resin A are mechanically blended with an extruder, a kneader, or the like, or each component is dissolved in an appropriate good solvent at the same time, or each component is separately dissolved and mixed, and then the solvent is removed. There is a way to do it.

However, in such a method, since the kneading work is required twice, the thermal history of the resin increases, and the desired physical properties may not be obtained in some cases. Further, the work becomes complicated, and it takes time and cost.

Therefore, in the production of the second polyamide resin composition of the present invention, the first kneading zone on the upstream side and the second kneading zone on the downstream side are used.
Of the elastomer B, polyolefin C and carboxylic acid or carboxylic acid anhydride compound D into the first kneading zone under the condition that the average shear rate in the kneading operation is 50 sec ^-1 or more. Is supplied to graft-modify the elastomer and the polyolefin, and then the polyamide resin A is added to the second kneading zone.
Is preferably supplied to knead the polyamide resin A with the graft-modified elastomer and polyolefin to use the method for producing a polyamide resin composition. In such a production method, the target polyamide resin composition can be produced only by a series of kneading operations, so that the heat history is reduced, and it is possible to produce a polyamide resin composition having excellent ductility, toughness, and rigidity at high temperature / absorption time. it can.

In this manufacturing method, the elastomer B supplied to the first kneading zone, the amorphous cyclic polyolefin C, and the carboxylic acid or carboxylic anhydride compound D are used.
May be pre-mixed all or in any combination prior to feeding, or each may be melt-injected alone. Further, an organic peroxide may be added to the first region as a reaction initiator. Since the organic peroxide may cause deterioration of the resin, it is preferably 3% or less with respect to the total weight of the elastomer B and the amorphous cyclic polyolefin C.

Further, in this production method, the elastomer B and the amorphous cyclic polyolefin C are efficiently graft-modified with a carboxylic acid or a carboxylic acid anhydride compound D,
In order to obtain excellent physical properties by appropriately dispersing the modified elastomer B and the amorphous cyclic polyolefin C in the polyamide resin, the average shear rate in the kneading operation is 50 sec ^-1 or more, preferably 50 sec ^-1.
It is necessary to control the screw rotation speed of the extruder so as to be 150 sec ^-1 or less. Average shear rate is 5
If it is slower than 0 sec ^-1 , excellent physical properties cannot be realized because the dispersion of elastomer or the like in polyamide is not sufficient.
On the other hand, if the average shear rate is higher than 150 sec ^-1 , the resin to be kneaded is deteriorated and the expected physical properties cannot be obtained.

In this method, extruders having first and second regions each having a supply port and a vent for the first and second kneading regions (including a multi-screw extruder having two or more screws) are also included. ) Is preferably used. In particular, a vent is provided in the first region for the purpose of removing excess reaction raw material. The temperature of the first region is 50 below the supply port.
℃ below, 40 ~ 50 ℃ while reaching the kneading zone from the supply port,
In the first kneading zone, the glass transition temperature of the amorphous cyclic polyolefin is 100 to 190 ° C. to 30 to 150 ° C.
High temperature, preferably 50-10 than 100-190 ° C
The temperature is 0 ° C. higher. The temperature of the second region is 10 to 60 ° C. higher than the melting point of the polyamide resin, preferably 25 to 50 ° C. higher than the melting point. In the final part of the extruder, the temperature is set so that an appropriate extrusion pressure can be obtained. Also, the number of vents provided in the first region is 4
The pressure is set to 00 Torr or less, preferably 200 Torr or less, more preferably 100 Torr or less, and the vent provided in the second region is drawn to 100 Torr or less, preferably 60 Torr or less.

The polyamide resin composition of the present invention described above, particularly the polyamide resin composition produced by a series of kneading operations by the above-mentioned production method, is excellent in ductility, toughness and rigidity at high temperature and moisture absorption, and is thermally deformed. The temperature is high, and a highly accurate molded product can be obtained. For example, when an automobile outer panel component such as a wheel cover and a fender is molded using the composition of the present invention, it is excellent in ductility, toughness and rigidity, and at the same time, there is a problem of dimensional stability such as a warp and a problem that specific gravity is too heavy. You can get one without. The method for obtaining a molded product from the composition of the present invention may be carried out according to a conventional polyamide resin composition.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples.

( Reference Examples 1 to 3, Examples 4 to 6 and Comparative Examples 1 to 4) Components other than the polyamide resins shown in Tables 1 and 2 were melt-kneaded in a twin-screw extruder (Toshiba TEM35) and water-cooled. Later, pellets were produced. The obtained pellets and the polyamide resins shown in Tables 1 and 2 were melt-kneaded by a twin-screw extruder (Toshiba TEM35), cooled with water, and pellets were produced.

In order to measure the physical properties of the molded product, each resin pellet was subjected to ASTM D with an injection molding machine (Toshiba TEM35).
13 mm × 130 mm × 3.2 mm test pieces based on 638 were molded. Hold time is 5-6 minutes, barrel temperature is 270-280 ° C, nozzle temperature is 280-290 ° C.
And Also, the mold temperature is about 90 ° C., and the molding cycle 1
Performed at 0/20 or 20/20 molding cycles (ram advance seconds / hold seconds). The following various physical property values of the obtained molded article for physical property test were measured immediately after molding and in an equilibrium water absorption state at 50% relative humidity. The measurement of each physical property value was performed according to the following test methods.

Tensile Strength: ASTM D638-58T Elongation: ASTM D638-58T Bending Elastic Modulus: ASTM D790-58T Notched Izod: ASTM D256-56 Heat Deformation Temperature: ASTM D648 Also obtained for Mold Shrinkage. 3 inches x 5 inches x 1/8 inch (7.
A 62 cm × 12.7 cm × 0.32 cm) plate was molded and the molding shrinkage was measured.

The results are shown in Tables 3 and 4.

( Reference Examples 7 and 8 and Comparative Examples 5 and 6) A twin-screw extruder having first and second regions provided with a feed region and a vent for the first and second kneading regions, respectively (Japan TEX44 manufactured by Steel Works; L / D = 45.5) was used. The temperature of the first region is 50 ° C immediately below the supply port,
Was set to 250 ° C. in the kneading zone, the temperature of the second zone was set to 290 ° C. both immediately below the supply port, and the temperature of the final part of the extruder was set to 285 ° C.

Here, the screw rotation speeds shown in Table 5 were set, and the amorphous cyclic polyolefins E and E shown in Tables 1 and 2 were used.
PDM rubber, maleic anhydride and diluent of organic peroxide were premixed and fed from the feed port of the first region, and then polyamide resin A shown in Tables 1 and 2 was fed from the second region and kneaded. Extruded. Subsequently, the discharged resin was cooled with water and passed through a cutter to manufacture resin pellets.

The above-mentioned reference using this resin pellet
Molded into test pieces as in Examples 1-3 and Examples 4-6 ,
The physical property values were measured. The results are shown in Table 5.

(Comparative Example 7) Amorphous cyclic polyolefin, EPDM rubber, maleic anhydride and diluted organic peroxide shown in Tables 1 and 2 were twin-screw extruded at a temperature of 250 ° C and a screw rotation speed of 150 rpm. Machine (Toshiba TEM3
After melt-kneading in 5) and cooling with water, pellets were produced. 55% by weight of the obtained pellets and polyamide resin A shown in Table 2
(45% by weight) and a temperature of 280 ° C. and a screw rotation speed of 250 rpm are set in the twin-screw extruder (Toshiba TEM35).
After melt-kneading with and cooling with water, resin pellets were produced.

The above-mentioned reference using this resin pellet
Molded into test pieces as in Examples 1-3 and Examples 4-6 ,
The physical property values were measured. The results are shown in Table 5.

The resins used in Reference Examples, Examples and Comparative Examples are as follows.

Polyamide resin A: Nylon 66 Rv = 43 manufactured by DuPont Amine end group concentration = 47.6 × 10 ⁻⁶ mol / g Polyamide resin B: Nylon 66 Rv = manufactured by DuPont
25 Amine end group concentration = 161.0 × 10 ⁻⁶ mol / g Polyamide resin C: Nylon 66 Rv = manufactured by DuPont
52 Amorphous Cyclic Polyolefin: Mitsui Petrochemical Industry Co., Ltd.
APEL 150R modified EPDM (ethylene propylene diene monomer) rubber: DuPont modified ethylene acrylate rubber: DuPont maleic anhydride: Kanto Chemical Co., Ltd. special grade reagent or NOF Corporation Crystal MAN Table 3 , As shown in Table 4, Reference Examples 1 to 3 and Example 4
The compositions of Nos. 6 to 6 have toughness (especially,
Elongation, notched Izod) and stiffness (especially
The value of molding shrinkage and anisotropy are small, and warpage is small while maintaining the balance of flexural modulus. Further, the heat distortion temperature shows a high value under a load of 18.5 kg / cm ² , and the high temperature rigidity is improved. Further, as compared with the examples of Comparative Examples 1 and 2 not containing the rubber component, elongation and notched Izod are improved. In addition, Reference Examples 1 to 3 and Examples
4 in 6, in particular relative viscosity is low, Examples 4-6 the amine end group concentration with high polyamide B further physical properties as compared with Examples 1 and 2, particularly Izod elongation and notched Has been improved. Further, in Example 6 in which maleic anhydride was added, physical properties, particularly elongation and notched Izod, were further improved as compared with Examples 4 and 5.

As shown in Table 5, the compositions of Reference Examples 7 and 8 produced by one kneading operation were comparative kneading operations of one time, but Comparative Examples 5, 6 or 2 having a slow average shear speed. Compared with Comparative Example 7 produced by one-time kneading operation, the Izod with stretch notch is particularly improved.

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Table 5]

[0056]

As described above, since the polyamide resin composition of the present invention contains a specific elastomer and an amorphous cyclic polyolefin in the polyamide, it is excellent in ductility, toughness and rigidity and has a heat distortion temperature. Therefore, it is possible to provide a highly accurate molded product. Further, the method for producing a polyamide resin composition obtained by adding the carboxylic acid or carboxylic acid anhydride compound of the present invention is capable of producing a polyamide resin excellent in ductility, toughness and rigidity,
Moreover, the working time can be reduced to about half.

Front page continuation (72) Inventor Reiko Koshida 4997 Shinyoshida-cho, Kohoku-ku, Yokohama-shi, Kanagawa Dupont Japan Limited Central Technical Research Institute (56) Reference JP 4-226147 (JP, A) (58) Survey Areas (Int.Cl. ⁷ , DB name) C08L 23/00-23/36 C08L 77/00-77/12 WPI / L (QUESTEL)

Claims (4)

(57) [Claims] 1. The concentration of A amine end groups is 60 × 10.
^{-6 mol / g~200 × 10 -6 mol} / g <br/> and 10 to 80 wt% polyamide resin in the range of B the following (a) ~ 1 or more elastomers 1 selected from the group of (d) Up to 30% by weight, (a) an elastomer composed of ethylene / propylene / diene, (b) modified with a carboxylic acid / carboxylic anhydride
Elastomer formed of a ethylene-propylene-diene, an elastomer having a graft-modified unsaturated monomer having at least reactive with (c) consisting of ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid ester, (d ) An elastomer composed of graft-modified ethylene / unsaturated carboxylic acid / unsaturated carboxylic acid ester, C is a copolymer of ethylene and an olefin having a cyclic structure, and is amorphous and has a glass transition temperature of 100 to 190 ° C. A polyamide resin composition consisting essentially of 10 to 60% by weight. 2. The polyamide resin composition according to claim 1, containing 0.01 to 10.0% by weight of a D carboxylic acid or a carboxylic acid anhydride compound. 3. A method for producing the polyamide resin composition according to claim 2 by extrusion molding, wherein an extruder having a first kneading zone on the upstream side and a second kneading zone on the downstream side is used in kneading work. Under the condition that the average shear rate is 50 sec ^-1 or more, the elastomer B, the polyolefin C and the carboxylic acid or the carboxylic acid anhydride compound D are supplied to the first kneading zone to graft-modify the elastomer and the polyolefin. By supplying the polyamide resin A to the second kneading zone, the polyamide resin A
A method for producing a polyamide resin composition, comprising: kneading the graft-modified elastomer and a polyolefin. 4. An automobile outer panel component formed by using the polyamide resin composition according to claim 1.