Polyamide resin composition

Abstract

To provide a polyamide resin composition which enables production of a molding material that has an excellent balance between flowability and impact resistance during molding and contains aliphatic polyamide, a modified ethylene-α-olefin copolymer and an ethylene-α-olefin copolymer, contains aliphatic polyamide, a modified ethylene-α-olefin copolymer and a low-molecular-weight ethylene-α-olefin copolymer, and is excellent in handleability such as pelletization property, bleed-out resistance and blocking resistance, and a method for producing the same.SOLUTION: A polyamide resin composition contains 30 to 90 mass% of specific aliphatic polyamide (A), 1 to 50 mass% of a specific acid-modified ethylene-α-olefin copolymer (B), and 1 to 50 mass% of a specific ethylene-α-olefin copolymer (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamide resin composition containing a specific aliphatic polyamide, a modified ethylene-α-olefin copolymer, and an ethylene-α-olefin copolymer, a method for producing the resin composition, and a molded article obtained from the resin composition.

Background Art

[0002] Polyamide (nylon) is expected to have a large demand as an engineering plastic due to its excellent physical properties. However, in general, the balance between mechanical strengths such as impact resistance and rigidity and the fluidity during molding of polyamide is not yet sufficient, and various improvements have been studied.

[0003] As a method for improving the impact resistance of polyamide, for example, a method of blending an ethylene-α-olefin copolymer grafted with an α,β-unsaturated carboxylic acid into polyamide has been proposed in Patent Document 1. However, in the proposed polyamide composition, when attempting to improve the impact resistance, a tendency for a decrease in rigidity and fluidity has been recognized.

[0004] As methods for improving the fluidity of polyamide, for example, there are a method of adding a polyamide having a low molecular weight and a method of adding a fluidity modifier (plasticizer or waxes). However, simply adding these materials may cause problems such as a decrease in impact strength, gas generation during molding, silver streaks, and pinhole generation, and there are limitations in the application of these methods. For example, Patent Document 2 discloses a polyamide composition in which the fluidity is improved using a low molecular weight ethylene-α-olefin random copolymer, but a tendency for insufficient impact strength has been recognized.

[0005] As a method for providing a polyamide excellent in the balance between impact resistance and fluidity, for example, a method of adding both an ethylene-α-olefin copolymer grafted with an α,β-unsaturated carboxylic acid and a low molecular weight ethylene-α-olefin copolymer has been proposed in Patent Document 3.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, low-molecular-weight ethylene-α-olefin copolymers are high-viscosity liquids, making it difficult to add them to an extruder for kneading with polyamide, and there are problems with the handleability as a molding material. Considering the ease of addition to the extruder, it is required to be in pellet form, without bleed-out of the liquid component from the pellets, and without blocking between the pellets.

[0008] An object of the present invention is to provide a polyamide resin composition excellent in handleability such as pelletizability, bleed-out resistance, and blocking resistance, which can produce a molding material containing an aliphatic polyamide, a modified ethylene-α-olefin copolymer, and an ethylene-α-olefin copolymer, and is well-balanced and excellent in fluidity, impact resistance, etc. during molding, and a method for producing the same.

Means for Solving the Problems

[0009] The inventors of the present invention have conducted intensive studies to solve the above problems. As a result, it has been found that a polyamide resin composition containing a specific aliphatic polyamide (A), a specific modified ethylene-α-olefin copolymer (B), and a low molecular weight ethylene-α-olefin copolymer (C) has excellent handleability such as pelletizability, bleed-out resistance, and blocking resistance, and this polyamide resin composition can be used as a masterbatch.

[0010] That is, the present invention relates to the following [1] to

[14] . [1] 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66, 1 to 50% by mass of an acid-modified ethylene-α-olefin copolymer (B) that satisfies the following requirements (b-1) to (b-3), 1 to 50% by mass of an ethylene-α-olefin copolymer (C) that satisfies the following requirements (c-1) and (c-2), and a polyamide resin composition containing the same; (However, the total of the aliphatic polyamide (A), the acid-modified ethylene-α-olefin copolymer (B), and the ethylene-α-olefin copolymer (C) is 100% by mass.) (b-1) The melt flow rate (MFR) measured at 190°C and a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The content of the structural unit derived from maleic acid or maleic anhydride with respect to 100% by mass of the acid-modified ethylene-α-olefin copolymer (B) is in the range of 0.1 to 5% by mass; (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%).

[0011] [2] In the requirement (c-1), the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 2,000 to 10,000, In the requirement (c-2), the content ratio of the structural unit derived from ethylene is 35 to 65 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 35 to 65 mol%. The polyamide resin composition according to [1]. [3] 40 to 80% by mass of the aliphatic polyamide (A), 10 to 40% by mass of the acid-modified ethylene·α-olefin copolymer (B), 5 to 30% by mass of the ethylene·α-olefin copolymer (C), The polyamide resin composition according to [1] or [2], which contains (however, the total of the aliphatic polyamide (A), the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C) is taken as 100% by mass).

[0012] [4] A resin composition for masterbatch containing the polyamide resin composition according to any one of [1] to [3].

[0013] [5] A molded article containing the polyamide resin composition according to any one of [1] to [3]. [6] Interior and exterior automotive materials containing the polyamide resin composition according to any one of [1] to [3]. [7] An automotive cover member containing the polyamide resin composition according to any one of [1] to [3]. [8] A member for automotive doors containing the polyamide resin composition according to any one of [1] to [3]. [9] An electronic member containing the polyamide resin composition according to any one of [1] to [3].

[0014]

[10] A step of melt-kneading 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66 and 1 to 50% by mass of an acid-modified ethylene·α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3); A step of melt-kneading a polymer mixture (1) containing the aliphatic polyamide (A) and the acid-modified copolymer (B) obtained by the above melt-kneading and 1 to 50% by mass of an ethylene·α-olefin copolymer (C) satisfying the following requirements (c-1) and (c-2); A method for producing a polyamide resin composition comprising; (b-1) The melt flow rate (MFR) measured at 190 °C under a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The content of the structural unit derived from maleic acid or maleic anhydride in 100% by mass of the acid-modified ethylene·α-olefin copolymer (B) is in the range of 0.1 to 5% by mass; (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 100 mol).

[0015]

[11] A step of melt-kneading 1 to 50% by mass of an acid-modified ethylene·α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3) and 1 to 50% by mass of an ethylene·α-olefin copolymer (C) satisfying the following requirements (c-1) and (c-2); A step of melt-kneading a polymer mixture (2) containing the acid-modified copolymer (B) and the ethylene·α-olefin copolymer (C) obtained by the melt-kneading and 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66; A method for producing a polyamide resin composition; (b-1) The melt flow rate (MFR) measured at 190 °C under a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The content ratio of the structural unit derived from maleic acid or maleic anhydride is in the range of 0.1 to 5% by mass with respect to 100% by mass of the acid-modified ethylene·α-olefin copolymer (B); (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 100 mol%).

[0016]

[12] The production method according to

[10] or

[11] , wherein the ethylene·α-olefin copolymer (C) is an ethylene·α-olefin copolymer (C) produced by the following method (α); Method (α): A crosslinked metallocene compound (P-1) represented by the following formula (1), and A method comprising a step of polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst system containing at least one compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the crosslinked metallocene compound (P-1) to form an ion pair.

[0017]

Chemical formula

[0018]

[13] In the formula (1), R 13 and R 14 The production method according to

[12] , wherein one or both of them are aryl groups.

[14] In the formula (1), R 13 and R 14 are both aryl groups, and one of R 2 and R 3 is a saturated hydrocarbon group having 4 carbon atoms. The production method according to

[12] .

Advantages of the Invention

[0019] According to the present invention, it is possible to produce a molding material containing an aliphatic polyamide, a modified ethylene-α-olefin copolymer, and an ethylene-α-olefin copolymer, which is excellently balanced in fluidity, impact resistance, etc. during molding. Provided are a polyamide resin composition excellent in handleability such as pelletizability, bleed-out resistance, and blocking resistance, and a method for producing the same, which includes an aliphatic polyamide, a modified ethylene-α-olefin copolymer, and a low molecular weight ethylene-α-olefin copolymer.

Embodiments for Carrying Out the Invention

[0020] [Aliphatic Polyamide (A)] The aliphatic polyamide (A) used in the present invention is one or more selected from the group consisting of polyamide 6 and polyamide 66. Polyamide 6 is polycapramide, which is a ring-opening polymer of ε-caprolactam, and polyamide 66 is polyhexamethylene adipamide, which is a polycondensate of hexamethylenediamine and adipic acid. As the aliphatic polyamide (A), polyamide 6 or polyamide 66 may be used alone, or two or more of these polyamides may be used in combination. The aliphatic polyamide (A) used in the present invention may be an aliphatic polyamide derived from biomass, an aliphatic polyamide derived from fossil fuel, or both an aliphatic polyamide derived from biomass and an aliphatic polyamide derived from fossil fuel may be used.

[0021] [Acid-modified ethylene·α-olefin copolymer (B)] The acid-modified ethylene·α-olefin copolymer (B) used in the present invention is characterized by satisfying the following requirements (b-1) to (b-3).

[0022] (b-1) The melt flow rate (MFR) measured at 190 °C and a load of 2.16 kg is 0.01 to 100 g / 10 min. The melt flow rate (MFR) is preferably 0.05 to 50 g / 10 min, more preferably 0.07 to 20 g / 10 min, and still more preferably 0.1 to 5 g / 10 min. By controlling the MFR of the ethylene·α-olefin copolymer (B) within this range, when a molded article is produced from a molding material containing the polyamide resin composition of the present invention, not only is the fluidity during molding excellent, but also a molded article excellent in impact resistance can be obtained.

[0023] (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%). In the above, the content ratio of the structural unit derived from ethylene is preferably 60 to 92 mol%, more preferably 65 to 90 mol%, still more preferably 70 to 88 mol%, and particularly preferably 75 to 88 mol%. The content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is preferably 8 to 40 mol%, more preferably 10 to 35 mol%, still more preferably 12 to 30 mol%, and particularly preferably 12 to 25 mol%. When the content ratio of each structural unit is within such a range, the acid-modified ethylene-α-olefin copolymer (B) has appropriate hardness, which makes it easy to handle. In addition, the blocking resistance of the obtained polyamide resin composition is improved. Furthermore, the bleed-out resistance of the polyamide resin composition is improved because of its excellent compatibility with the ethylene-α-olefin copolymer (C) described later.

[0024] Examples of the α-olefin having 3 to 8 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-heptene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 1-octene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, and combinations thereof. Among them, propylene, 1-butene, and 1-octene are particularly preferred. Ethylene, α-olefin, maleic acid, and maleic anhydride constituting the acid-modified ethylene-α-olefin copolymer (B) used in the present invention may be derived from biomass, may be derived from fossil fuels, or may use both biomass-derived monomers and fossil fuel-derived monomers.

[0025] (b-3) The content (hereinafter simply referred to as the modification amount M B as well.) of the structural unit derived from maleic acid or maleic anhydride with respect to 100% by mass of the acid-modified ethylene-α-olefin copolymer (B) is 0.1 to 5% by mass. The modification amount M B is preferably 0.2 to 3% by mass, more preferably 0.3 to 2% by mass. The modification amount MB If it is too small, the impact resistance of the molded article obtained from the molding material containing the polyamide resin composition of the present invention may decrease. On the other hand, when the modification amount M B is too large, it is necessary to increase the charging amount of the polar monomer or the organic peroxide during modification by the ordinary modification method. However, in such a modification method, foreign matters such as gels may be mixed into the acid-modified ethylene-α-olefin copolymer (B). In addition, the fluidity of the molded article obtained from the molding material containing the polyamide resin composition of the present invention may decrease. The modification amount M B is determined from a calibration curve prepared separately based on the peak intensity of the wave number 1780 cm -1 attributed to the carbonyl group by FT-IR as described later.

[0026] The acid-modified ethylene-α-olefin copolymer (B) used in the present invention satisfies the above requirements (b-1) to (b-3), and preferably further satisfies the following requirement (b-4).

[0027] (b-4) The density D of the acid-modified ethylene-α-olefin copolymer (B) measured in accordance with ASTM D1505 B is 820 to 900 kg / m 3 . The density D of the acid-modified ethylene-α-olefin copolymer (B) B is preferably 830 to 890 kg / m 3 , more preferably 850 to 890 kg / m 3 , particularly preferably 850 to 880 kg / m 3 . When the density D B is in such a range, the flexibility of the acid-modified ethylene-α-olefin copolymer (B) is good, and the molded article obtained from the molding material containing the polyamide resin composition of the present invention tends to be excellent in low-temperature impact resistance.

[0028] [Production method of acid-modified ethylene-α-olefin copolymer (B)] The acid-modified ethylene-α-olefin copolymer (B) used in the present invention can be obtained by graft-modifying an unmodified ethylene-α-olefin copolymer (r) with maleic acid or its anhydride.

[0029] The unmodified ethylene-α-olefin copolymer (r) contains 60 to 95 mol% of structural units derived from ethylene and 5 to 40 mol% of structural units derived from an α-olefin having 3 to 8 carbon atoms (the total amount of the structural units derived from ethylene and the structural units derived from the α-olefin is 100 mol%).

[0030] The unmodified ethylene-α-olefin copolymer (r) has an MFR measured at 190°C under a load of 2.16 kg of 0.01 to 200 g / 10 min, preferably 0.1 to 100 g / 10 min, more preferably 0.1 to 10 g / 10 min. When the MFR is in such a range, the blendability of the resulting acid-modified ethylene-α-olefin copolymer (B) and the aliphatic polyamide (A), and the balance between the fluidity and impact resistance of the molding material containing the resulting polyamide resin composition are improved.

[0031] The unmodified ethylene-α-olefin copolymer (r) having the above-described characteristics can be produced by a conventionally known method using a vanadium-based catalyst composed of a soluble vanadium compound and an alkylaluminum halide compound, or a metallocene-based catalyst composed of a zirconocene metallocene compound of zirconium and an organoaluminum oxy compound (for example, the metallocene-based catalyst described in International Publication No. 97 / 10295).

[0032] The acid-modified ethylene-α-olefin copolymer (B) is usually obtained by adding an additive described later, if necessary, to the unmodified ethylene-α-olefin copolymer (r) described above, and subjecting maleic acid or its anhydride to graft polymerization preferably in the presence of a radical initiator.

[0033] The charged amount of maleic acid or its anhydride is usually 0.010 to 15 parts by mass, preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of the unmodified ethylene-α-olefin copolymer (r). The amount of the radical initiator used is usually 0.0010 to 1.0 parts by mass, preferably 0.0050 to 0.30 parts by mass, based on 100 parts by mass of the unmodified ethylene-α-olefin copolymer (r).

[0034] As the radical initiator, for example, an organic peroxide, an azo compound, a metal hydride, or the like can be used. Examples of the organic peroxide include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexene, and the like. Examples of the azo compound include azobisisobutyronitrile, dimethylazoisobutyrate, and the like.

[0035] The radical initiator can be used by mixing it as it is with maleic acid or its anhydride, the unmodified ethylene-α-olefin copolymer (r), and other components added as necessary, or it can also be used after dissolving it in a small amount of an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the radical initiator.

[0036] The graft modification with maleic acid or its anhydride can be carried out by a conventionally known method. For example, a method in which the unmodified ethylene-α-olefin copolymer (r) is dissolved in an organic solvent, and then maleic acid or its anhydride, a radical initiator, etc. are added to the solution and reacted at a temperature of 70 to 200°C, preferably 80 to 190°C, for 0.5 to 15 hours, preferably 1 to 10 hours, can be mentioned.

[0037] Further, a modified product can also be produced by reacting maleic acid or its anhydride with an unmodified ethylene-α-olefin copolymer (r) in the absence of a solvent and in the presence of a radical initiator using an extruder or the like. This reaction is usually desirably carried out at a temperature equal to or higher than the melting point of the unmodified ethylene-α-olefin copolymer (r) for usually 0.5 to 10 minutes.

[0038] [Ethylene-α-olefin copolymer (C)] The ethylene-α-olefin copolymer (C) used in the present invention is characterized by satisfying the following requirements (c-1) and (c-2). The ethylene-α-olefin copolymer (C) may be used alone or in combination of two or more.

[0039] (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 500 to 50,000. The Mw is preferably 700 to 20,000, more preferably 1,000 to 15,000, still more preferably 2,000 to 10,000, and particularly preferably 3,000 to 7,000. When Mw is below the lower limit, the bleed-out resistance of the polyamide resin composition of the present invention and the molding material containing the resin composition tends to deteriorate, and the impact resistance of the molded body obtained from the molding material containing the polyamide resin composition of the present invention may deteriorate. When Mw is above the upper limit, the surface appearance and the fluidity during molding may deteriorate. That is, when Mw is within the above range, not only the bleed-out resistance of the obtained polyamide resin composition and the molding material containing the resin composition is excellent, but also the fluidity during molding of the molded body obtained from the molding material containing the polyamide resin composition and the impact resistance of the obtained molded body are excellently balanced.

[0040] The molecular weight distribution (Mw / Mn) of the above ethylene-α-olefin copolymer (C) is not particularly limited, but is usually 3 or less, preferably 2.7 or less, and more preferably 2.5 or less.

[0041] The Mw and Mw / Mn of the ethylene-α-olefin copolymer (C) are values in terms of polystyrene measured by GPC calibrated using a standard substance with a known molecular weight (monodisperse polystyrene), and the GPC measurement can specifically be carried out by the method described in the following examples.

[0042] (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%).

[0043] Typical examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, etc. These α-olefins may be used alone or in combination of two or more. Among these α-olefins, α-olefins having 3 to 10 carbon atoms are preferred from the viewpoint of easy availability, and propylene is particularly preferred. Ethylene and α-olefin constituting the ethylene-α-olefin copolymer (C) used in the present invention may be derived from biomass, may be derived from fossil fuels, or may use both a biomass-derived monomer and a fossil fuel-derived monomer.

[0044] The ethylene-α-olefin copolymer (C) used in the present invention preferably has a structural unit derived from ethylene in an amount of 30 to 75 mol%, more preferably 35 to 65 mol%, still more preferably 40 to 60 mol%, and a structural unit derived from an α-olefin having 3 to 20 carbon atoms in an amount of preferably 25 to 70 mol%, more preferably 35 to 65 mol%, still more preferably 40 to 60 mol%. If the content ratio (ethylene content) of the structural unit derived from ethylene is too high or too low, the compatibility with the acid-modified ethylene-α-olefin copolymer (B) deteriorates, and the bleed-out resistance and blocking resistance of the polyamide resin composition of the present invention deteriorate, or the mechanical properties such as the tensile properties and heat resistance of the molded article obtained from the polyamide resin composition of the present invention may decrease.

[0045] The ethylene content of the ethylene-α-olefin copolymer (C) 13 can be measured by the C-NMR method. For example, the peaks can be identified and quantified according to the methods described later and the methods described in "Polymer Analysis Handbook" (published by Asakura Shoten, P. 163-170).

[0046] The ethylene-α-olefin copolymer (C) used in the present invention satisfies the above requirements (c-1) and (c-2), but preferably further satisfies at least one of the following requirements (c-3), (c-4), and (c-5).

[0047] (c-3) The kinematic viscosity at 100 °C (100 °C kinematic viscosity) is 1 to 5000 mm 2 / s. The ethylene-α-olefin copolymer (C) preferably has a kinematic viscosity at 100 °C of 2 15 to 3000 mm 2 / s, more preferably 30 to 2500 mm 2 / s, still more preferably 50 to 1000 mm 2 / s. When the kinematic viscosity at 100 °C of the ethylene-α-olefin copolymer is lower than the above lower limit value, the bleed-out resistance of the polyamide resin composition of the present invention and the molding material containing the resin composition tends to deteriorate, and the impact strength of the molded body obtained from the molding material containing the polyamide resin composition of the present invention may decrease. On the other hand, when the kinematic viscosity at 100 °C of the ethylene-α-olefin copolymer (C) is higher than the above upper limit value, the fluidity during molding of the molding material containing the polyamide resin composition of the present invention may decrease, or the surface appearance of the molded product may deteriorate. In other words, when the kinematic viscosity at 100 °C of the ethylene-α-olefin copolymer (C) is within the above numerical range, not only is the bleed-out resistance of the obtained polyamide resin composition and the molding material containing the resin composition excellent, but also the fluidity during molding of the molded body obtained from the molding material containing the polyamide resin composition and the impact resistance of the obtained molded body are excellently balanced.

[0048] (c-4) In the temperature range of 100 °C to 150 °C, no melting point measured by differential scanning calorimetry (DSC) is observed. It is preferable that the ethylene-α-olefin copolymer (C) used in the present invention has no melting point observed by differential scanning calorimetry (DSC). Here, no observed melting point (Tm) means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. That the heat of fusion (ΔH) is not substantially measured means that no peak is observed in the differential scanning calorimeter (DSC) measurement, or the observed heat of fusion is 1 J / g or less. The melting point (Tm) and heat of fusion (ΔH) of the ethylene-α-olefin polymer were determined by performing differential scanning calorimetry (DSC) measurement, cooling to -100 °C, and then heating to 150 °C at a heating rate of 10 °C / min, and analyzing the DSC curve with reference to JIS K7121. No observed melting point is preferable in terms of facilitating addition to a kneader such as an extruder when mixing with the aliphatic polyamide (A) and the acid-modified ethylene-α-olefin copolymer (B).

[0049] (c-5) The density D measured in accordance with JIS K2249 of the ethylene-α-olefin copolymer (C)C 820~910kg / m 3 and the density D of the acid-modified ethylene-α-olefin copolymer (B) measured in accordance with ASTM D1505 B Difference from |D B -D C | is 50kg / m 3 The following is the result.

[0050] Density D C is 820~910kg / m 3 , preferably 830 to 900 kg / m 3 It is. Also, density D C and the density D of the acid-modified ethylene-α-olefin copolymer (B). B Difference from |D B -D C is preferably 50 kg / m 3 Less than or equal to 40 kg / m 3 In the polyamide composition of the present invention and the molded article obtained therefrom, it is considered desirable to form a dispersed phase containing the acid-modified ethylene-α-olefin copolymer (B) in the aliphatic polyamide (A). Density D C and density D B When the difference between the above ranges, the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) become more compatible with each other, and the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) are more likely to be contained in the dispersed phase, and the ethylene-α-olefin copolymer (C) exerts an effect of reducing the viscosity of the acid-modified ethylene-α-olefin copolymer (B) during melt kneading, improving the dispersibility of the acid-modified ethylene-α-olefin copolymer (B). As a result, it is thought that the flowability of a molding material containing the polyamide resin composition of the present invention during molding and the impact resistance of a molded body can be easily improved in a well-balanced manner.

[0051] [Production method of ethylene-α-olefin copolymer (C)] The method for producing the ethylene-α-olefin copolymer (C) is not particularly limited and can be produced using known methods. For example, a method of copolymerizing ethylene and an α-olefin in the presence of a catalyst composed of a compound containing a transition metal such as vanadium, zirconium, titanium, hafnium, etc., an organoaluminum compound (including an organoaluminum oxy compound) and / or an ionizing ionic compound can be mentioned. Such methods include, for example, the methods described in International Publication No. 2000 / 34420, JP-A-62-121710, International Publication No. 2004 / 29062, JP-A-2004-175707, International Publication No. 2001 / 27124, etc. Among these, a method using a catalyst system containing a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) can produce a copolymer with high polymerization activity, and in addition, the chlorine content of the resulting copolymer and the amount of 1,1’ or 2,2’-bonding (inversion) of the α-olefin monomer can be reduced, so it is preferable.

[0052] The ethylene-α-olefin copolymer (C) can be produced by copolymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing at least one compound (Q) selected from the group consisting of a crosslinked metallocene compound (P) represented by the following general formula [I], an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the crosslinked metallocene compound (P) to form an ion pair.

[0053]

Chemical formula

[0054] 〔Crosslinked metallocene compound (P)〕 The crosslinked metallocene compound (P) is represented by the above formula [I]. Y, M, R 1 ~R 14 、Q, n and j will be described below.

[0055] (Y, M, R 1 ~R14 , Q, n, and j) Y is a Group 14 atom, and examples thereof include a carbon atom, a silicon atom, a germanium atom, and a tin atom. Preferably, Y is a carbon atom or a silicon atom, and more preferably, Y is a carbon atom.

[0056] M is a titanium atom, a zirconium atom, or a hafnium atom, and preferably, M is a zirconium atom. R 1 ~R 12 are atoms or substituents selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and they may be the same or different from each other. Further, adjacent substituents from R 1 to R 12 may be bonded to each other to form a ring, or may not be bonded to each other.

[0057] Here, the hydrocarbon group is typically a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, a chain unsaturated hydrocarbon group having 2 to 20 carbon atoms, a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, and the like.

[0058] Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an allyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decanyl group, etc., which are linear saturated hydrocarbon groups; an isopropyl group, an isobutyl group, an s-butyl group, a t-butyl group, a t-amyl group, a neopentyl group, a 3-methylpentyl group, a 1,1-diethylpropyl group, a 1,1-dimethylbutyl group, a 1-methyl-1-propylbutyl group, a 1,1-propylbutyl group, a 1,1-dimethyl-2-methylpropyl group, a 1-methyl-1-isopropyl-2-methylpropyl group, a cyclopropylmethyl group, etc., which are branched saturated hydrocarbon groups. The number of carbon atoms of the alkyl group is preferably 1 to 6.

[0059] Examples of the cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornenyl group, a 1-adamantyl group, a 2-adamantyl group, etc., which are cyclic saturated hydrocarbon groups, and groups in which a hydrogen atom of the cyclic saturated hydrocarbon group is replaced by a hydrocarbon group having 1 to 17 carbon atoms, such as a 3-methylcyclopentyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 4-cyclohexylcyclohexyl group, a 4-phenylcyclohexyl group, etc. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0060] Examples of the chain unsaturated hydrocarbon group having 2 to 20 carbon atoms include an alkenyl group such as an ethenyl group (vinyl group), a 1-propenyl group, a 2-propenyl group (allyl group), a 1-methylethenyl group (isopropenyl group), etc., and an alkynyl group such as an ethynyl group, a 1-propynyl group, a 2-propynyl group (propargyl group), etc. The number of carbon atoms of the chain unsaturated hydrocarbon group is preferably 2 to 4.

[0061] Examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms include a cyclopentadienyl group, a norbornyl group, a phenyl group, a naphthyl group, an indenyl group, an azulene group, a phenanthryl group, an anthracenyl group, etc., which are cyclic unsaturated hydrocarbon groups, and groups in which a hydrogen atom of the cyclic unsaturated hydrocarbon group is replaced by a hydrocarbon group having 1 to 15 carbon atoms, such as a 3-methylphenyl group (m-tolyl group), a 4-methylphenyl group (p-tolyl group), a 4-ethylphenyl group, a 4-tert-butylphenyl group, a 4-cyclohexylphenyl group, a biphenylyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group (mesityl group), etc., and groups in which a hydrogen atom of a linear hydrocarbon group or a branched saturated hydrocarbon group is replaced by a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group having 3 to 19 carbon atoms, such as a benzyl group, a cumyl group, etc. The number of carbon atoms of the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

[0062] Examples of the alkylene group having 1 to 20 carbon atoms include a methylene group, an ethylene group, a dimethylmethylene group (isopropylidene group), an ethylmethylene group, a methylethylene group, an n-propylene group, etc. The number of carbon atoms of the alkylene group is preferably 1 to 6.

[0063] Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4,4'-biphenylylene group, etc. The number of carbon atoms of the arylene group is preferably 6 to 12.

[0064] The silicon-containing group is typically a silicon-containing hydrocarbon group. Examples of the silicon-containing group include alkylsilyl groups such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a triisopropylsilyl group, etc., which are groups in which a carbon atom in a hydrocarbon group having 1 to 20 carbon atoms is replaced by a silicon atom; arylsilyl groups such as a dimethylphenylsilyl group, a methyldiphenylsilyl group, a t-butyldiphenylsilyl group, etc.; a pentamethyldisilanyl group, a trimethylsilylmethyl group, etc. The number of carbon atoms of the alkylsilyl group is preferably 1 to 10, and the number of carbon atoms of the arylsilyl group is preferably 6 to 18.

[0065] Examples of the nitrogen-containing group include an amino group; groups in which a =CH- structural unit in the above-described hydrocarbon group or silicon-containing group having 1 to 20 carbon atoms is replaced by a nitrogen atom; groups in which a -CH2- structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded; or groups in which a -CH3 structural unit is replaced by a nitrogen atom to which a hydrocarbon group having 1 to 20 carbon atoms is bonded or a nitrile group, such as a dimethylamino group, a diethylamino group, an N-morpholinyl group, a dimethylaminomethyl group, a cyano group, a pyrrolidinyl group, a piperidinyl group, a pyridinyl group, etc., an N-morpholinyl group and a nitro group, etc. As the nitrogen-containing group, a dimethylamino group and an N-morpholinyl group are preferable.

[0066] Examples of the oxygen-containing group include a hydroxyl group, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a nitrogen-containing group described above, a group in which a -CH2- structural unit is replaced by an oxygen atom or a carbonyl group, or a methoxy group, an ethoxy group, a t-butoxy group, a phenoxy group, a trimethylsiloxy group, a methoxyethoxy group, a hydroxymethyl group, a methoxymethyl group, an ethoxymethyl group, a t-butoxymethyl group, a 1-hydroxyethyl group, a 1-methoxyethyl group, a 1-ethoxyethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, an n-2-oxabutylene group, an n-2-oxapentylene group, an n-3-oxapentylene group, an aldehyde group, an acetyl group, a propionyl group, a benzoyl group, a trimethylsilylcarbonyl group, a carbamoyl group, a methylaminocarbonyl group, a carboxy group, a methoxycarbonyl group, a carboxymethyl group, an ethoxycarboxymethyl group, a carbamoylmethyl group, a furanyl group, a pyranyl group, etc. Among them, the methoxy group is preferable as the oxygen-containing group.

[0067] Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., which are Group 17 elements. Examples of the halogen-containing group include a trifluoromethyl group, a tribromomethyl group, a pentafluoroethyl group, a pentafluorophenyl group, etc., which are groups in which a hydrogen atom is replaced by a halogen atom in a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group or an oxygen-containing group described above.

[0068] Q is selected from a halogen atom, a hydrocarbon group (typically a hydrocarbon group having 1 to 20 carbon atoms), an anionic ligand and a neutral ligand capable of coordinating with a lone pair of electrons, in the same or different combinations. That is, Q is independently a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating with a lone pair of electrons. The details of the halogen atom and the hydrocarbon group having 1 to 20 carbon atoms are as described above. When Q is a halogen atom, a chlorine atom is preferred. When Q is a hydrocarbon group having 1 to 20 carbon atoms, the number of carbon atoms of the hydrocarbon group is preferably 1 to 7.

[0069] Examples of the anionic ligand include alkoxy groups such as methoxy group, t-butoxy group, and phenoxy group, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate.

[0070] Examples of the neutral ligand capable of coordinating with an unshared electron pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ether compounds such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane. j is an integer of 1 to 4, preferably 2. n is an integer of 1 to 4, preferably 1 or 2, more preferably 1.

[0071] R 13 and R 14 are an atom or a substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a substituted aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and may be the same or different from each other. Also, R 13 and R 14 may be bonded to each other to form a ring, or may not be bonded to each other.

[0072] The details of the hydrocarbon group having 1 to 20 carbon atoms, the silicon-containing group, the nitrogen-containing group, the oxygen-containing group, the halogen atom, and the halogen-containing group are as described above. Examples of the aryl group partially overlap with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, and include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an anthracenyl group, a phenanthrenyl group, a tetracenyl group, a chrysenyl group, a pyrenyl group, an indenyl group, an azulenyl group, a pyrrolyl group, a pyridyl group, a furanyl group, a thiophenyl group, etc., which are substituents derived from aromatic compounds. As the aryl group, a phenyl group or a 2-naphthyl group is preferable.

[0073] Examples of the aromatic compound include benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, thiophene, etc., which are aromatic hydrocarbons and heteroaromatic compounds.

[0074] Examples of the substituted aryl group partially overlap with the examples of the cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms described above, and include a group in which one or more hydrogen atoms of the aryl group are substituted by at least one substituent selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an aryl group, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group. Specifically, 3-methylphenyl group (m-tolyl group), 4-methylphenyl group (p-tolyl group), 3-ethylphenyl group, 4-ethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, biphenylyl group, 4-(trimethylsilyl)phenyl group, 4-aminophenyl group, 4-(dimethylamino)phenyl group, 4-(diethylamino)phenyl group, 4-morpholinylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 4-phenoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3-methyl-4-methoxyphenyl group, 3,5-dimethyl-4-methoxyphenyl group, 3-(trifluoromethyl)phenyl group, 4-(trifluoromethyl)phenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 5-methylnaphthyl group, 2-(6-methyl)pyridyl group, etc.

[0075] Among them, R 13 and R 14 A crosslinked metallocene compound (P) in which one or both of them are each independently an aryl group is preferred, and a crosslinked metallocene compound (P) in which both are independently aryl groups is more preferred.

[0076] In particular, for the crosslinked metallocene compound (P) in which both R 13 and R 14 are independently aryl groups, the polymerization activity for the copolymerization of ethylene and α-olefin is high. By using this crosslinked metallocene compound (P), the polymerization is selectively terminated by introducing hydrogen to the molecular end, so the unsaturated bonds in the obtained ethylene·α-olefin copolymer (C) are reduced. Therefore, an ethylene·α-olefin copolymer (C) with high saturation and excellent heat resistance can be obtained by simply performing a hydrogenation operation or without performing a hydrogenation operation, which is also excellent in terms of cost. In addition, the ethylene·α-olefin copolymer (C) obtained from the compound (P) has a high random copolymerizability and thus has a controlled molecular weight distribution.

[0077] In the crosslinked metallocene compound (P) represented by the above formula [I], n is preferably 1. Such a crosslinked metallocene compound (hereinafter also referred to as "crosslinked metallocene compound (P-1)") is represented by the following general formula (1).

[0078]

Chemical formula

[0079] Compared with the compound in which n in the above formula [I] is an integer of 2 to 4, the production process of the crosslinked metallocene compound (P-1) is simplified, the production cost is reduced, and ultimately, the production cost of the ethylene·α-olefin copolymer (C) can be reduced by using this crosslinked metallocene compound (P-1).

[0080] In the bridged metallocene compound (P) represented by the above general formula [I] and the bridged metallocene compound (P-1) represented by the above general formula (1), it is more preferable that M is a zirconium atom. When ethylene and one or more monomers selected from α-olefins having 3 to 20 carbon atoms are copolymerized in the presence of an olefin polymerization catalyst containing the bridged metallocene compound in which M is a zirconium atom, the polymerization activity is higher than when M is a titanium atom or a hafnium atom, and the advantage of reducing the production cost of the ethylene·α-olefin copolymer (C) is obtained.

[0081] In the bridged metallocene compound (P-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 and R 12 are each independently preferably a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and a plurality of adjacent groups may be linked to each other to form a ring structure. In the bridged metallocene compound (P-1), R 6 and R 11 are the same group as each other and are preferably a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R 7 and R 10 are the same group as each other and are preferably a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, R 6 and R 7 may be bonded to a hydrocarbon having 2 to 3 carbon atoms to form a ring structure. Further, in the bridged metallocene compound (P-1), R 6 , R 7 , R 10 and R 11 are preferably not hydrogen atoms at the same time.

[0082] Also in the bridged metallocene compound (P-1), R 13 and R 14The crosslinked metallocene compound (P-1) in which either one or both of them are aryl groups is preferable, and the crosslinked metallocene compound (P-1) in which both are independently aryl groups is more preferable. In the crosslinked metallocene compound (P-1), R 13 and R 14 are both aryl groups, and the crosslinked metallocene compound (P-1) in which either one of R 2 and R 3 is a saturated hydrocarbon group having 4 carbon atoms is even more preferable.

[0083] In particular, by the following method (α) using the crosslinked metallocene compound (P-1), an ethylene / α-olefin copolymer (C) having a good performance balance in terms of molecular weight control, molecular weight distribution, amorphousness, etc. can be obtained.

[0084] Method (α): A crosslinked metallocene compound (P-1) represented by the following formula (1), and a method including a step of polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst system containing at least one compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the crosslinked metallocene compound (P-1) to form an ion pair.

[0085] Examples of the crosslinked metallocene compound (P) as described above include [dimethylmethylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [dimethylmethylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene(η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene(η 5 -cyclopentadienyl)(η 5-Octamethyl octahydro dibenzofluorenyl)] zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl)(η 5 -tetramethyl octahydro dibenzofluorenyl)] zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -fluorenyl)] zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)] zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)] zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -octamethyl octahydro dibenzofluorenyl)] zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 -tetramethyl octahydro dibenzofluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -fluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -2-methyl-4-tert-butylcyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)] zirconium dichloride, [diphenylmethylene (η 5 -cyclopentadienyl)(η 5-Octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [diphenylmethylene{η 5 -(2-Methyl-4-i-propylcyclopentadienyl)}(η 5 -Octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [diphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -Tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride,

[0086] [Methylphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -Fluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -2,7-Di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -3,6-Di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -Octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -Cyclopentadienyl)(η 5 -Tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride, [Methyl(3-methylphenyl)methylene(η 5 -Cyclopentadienyl)(η 5 -Fluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -Cyclopentadienyl)(η 5 -2,7-Di-tert-butylfluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -Cyclopentadienyl)(η 5-3,6-Di-tert-butylfluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0087] [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -fluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -3,6-di-tert-butylfluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5-(Cyclopentadienyl)(η 5 -Octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [Dicyclohexylsilylene(η 5 -Cyclopentadienyl)(η 5 -Tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride,

[0088] [Ethylene(η 5 -Cyclopentadienyl)(η 5 -Fluorenyl)]zirconium dichloride, [Ethylene(η 5 -Cyclopentadienyl)(η 5 -2,7-Di-tert-butylfluorenyl)]zirconium dichloride, [Ethylene(η 5 -Cyclopentadienyl)(η 5 -3,6-Di-tert-butylfluorenyl)]zirconium dichloride, [Ethylene(η 5 -Cyclopentadienyl)(η 5 -Octamethyl octahydro dibenzofluorenyl)]zirconium dichloride, [Ethylene(η 5 -Cyclopentadienyl)(η 5 -Tetramethyl octahydro dibenzofluorenyl)]zirconium dichloride, Ethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](η 5 -Fluorenyl)zirconium dichloride, Ethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, Ethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, Ethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](Octamethyl octahydro dibenzofluorenyl)zirconium dichloride, Ethylene[η 5-(3-tert-Butyl-5-methylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride,

[0089] Ethylene [η 5 -(3-tert-Butylcyclopentadienyl)(η 5 -Fluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, ethylene [η 5-(3-tert-Butylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)](η 5 -Fluorenyl)zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, ethylene [η 5 -(3-n-Butylcyclopentadienyl)][η 5-(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)zirconium dichloride,

[0090] Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](η 5 -Fluorenyl)zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl)zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](benzofluorenyl)zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](dibenzofluorenyl)zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl)zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, Diphenylmethylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, Diphenylmethylene[η 5-(3-tert-butylcyclopentadienyl)](η 5 -fluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(3,6-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)](benzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)](dibenzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride,

[0091] diphenylmethylene[η 5 -(3-n-butylcyclopentadienyl)](η 5 -fluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-n-butylcyclopentadienyl)][η 5-(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)](octamethyloctahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)](benzofluorenyl)zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)](dibenzofluorenyl)zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)](octahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene [η 5 -(3-n-butylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene [η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](η 5 -fluorenyl)zirconium dichloride, di(p-tolyl)methylene [η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene [η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene [η 5-(3-tert-Butyl-5-methylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butyl-5-methylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride,

[0092] Di(p-tolyl)methylene[η 5 -(3-tert-Butylcyclopentadienyl)](η 5 -Fluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(3,6-Di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butylcyclopentadienyl)][η 5 -(2,7-Di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-Butylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5-(3-tert-butylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)(η 5 -fluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)][η 5 -(3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)][η 5 -(2,7-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)(benzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)(dibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5-(3-n-Butylcyclopentadienyl)(octahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-Butylcyclopentadienyl)(2,7-diphenyl-3,6-di-tert-butylfluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-Butylcyclopentadienyl)][η 5 -(2,7-Dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride and the like can be mentioned.

[0093] Examples of the bridged metallocene compound (P) further include compounds in which the zirconium atom of the above compound is replaced with a hafnium atom or a titanium atom, compounds in which a chloro ligand is replaced with a methyl group, and the like. Incidentally, η 5 -Tetramethyloctahydrodibenzofluorenyl is 4,4,7,7-tetramethyl-(5a,5b,11a,12,12a-η 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group, η 5 -Octamethyloctahydrodibenzofluorenyl is 1,1,4,4,7,7,10,10-octamethyl-(5a,5b,11a,12,12a-η 5 )-1,2,3,4,7,8,9,10-octahydrodibenzo[b,H]fluorenyl group, respectively. The bridged metallocene compound (P) may be used alone or in combination of two or more.

[0094] [Compound (Q)] The compound (Q) according to the present invention is at least one compound selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the bridged metallocene compound (P) to form an ion pair.

[0095] As the organometallic compound (Q-1), specifically, organometallic compounds (Q-1a), (Q-1b), and (Q-1c) of Groups 1, 2, 12, and 13 of the periodic table as described below are used.

[0096] (Q-1a) General formula R a m Al(OR b ) n H p X q An organoaluminum compound represented by (In the formula, R a and R b may be the same as or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is a number where 0 < m ≦ 3, n is a number where 0 ≦ n < 3, p is a number where 0 ≦ p < 3, q is a number where 0 ≦ q < 3, and m + n + p + q = 3.)

[0097] Examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tri(4-methylphenyl)aluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; and compounds represented by the general formula (i-C4H9) x Al y (C5H 10 ) z(wherein x, y, and z are positive numbers, and z ≦ 2x.) Alkenylaluminums such as isoprenylaluminum, alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide, dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide, and dibutylaluminum butoxide, alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, and the general formula R a 2.5 Al(OR b ) 0.5 Partially alkoxylated alkylaluminums having an average composition represented by etc., alkylaluminum aryloxides such as diethylaluminum phenoxide and diethylaluminum (2,6-di-tert-butyl-4-methylphenoxide), dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, and diisobutylaluminum chloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide, partially halogenated alkylaluminums such as ethylaluminum dichloride, dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride, and other partially hydrogenated alkylaluminums, and partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide can be exemplified. Also, the above general formula R a m Al(OR b ) n H p X qCompounds similar to the compound represented by can also be used. For example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom can be mentioned. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2 and the like.

[0098] (Q-1b) Complex alkylates of a Group 1 metal of the periodic table represented by the general formula M 2 AlR a 4 and aluminum. (In the formula, M 2 represents Li, Na or K, and R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)

[0099] Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4 and the like.

[0100] (Q-1c) Dialkyl compounds of a Group 2 or Group 12 metal of the periodic table represented by the general formula R a R b M 3 . (In the formula, R a and R b may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M 3 is Mg, Zn or Cd.)

[0101] As the organoaluminum oxy compound (Q-2), conventionally known aluminoxane can be used as it is. Specifically, compounds represented by the following general formula [III] and compounds represented by the following general formula [IV] can be mentioned.

[0102]

Chemical formula

[0103]

Chemical formula

[0104] Particularly, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more, is used. These aluminoxanes may contain some organic aluminum compounds.

[0105] In the present invention, when copolymerizing ethylene and an α-olefin having 3 or more carbon atoms at a high temperature, a benzene-insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687 can also be applied. Further, an organoaluminum oxy compound described in JP-A-2-167305, an aluminoxane having two or more kinds of alkyl groups described in JP-A-2-24701 and JP-A-3-103407 can also be preferably used. The "benzene-insoluble organoaluminum oxy compound" that may be used in the present invention means a compound in which the Al component dissolved in benzene at 60 °C is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms, and is insoluble or hardly soluble in benzene.

[0106] Further, examples of the organoaluminum oxy compound (Q-2) include modified methylaluminoxane represented by the following general formula [V].

[0107]

Chemical formula

[0108] Methylaluminoxane, which is an example of the organoaluminum oxy compound (Q-2), is easily available and has high polymerization activity, so it is generally used as an activator in olefin polymerization. However, since methylaluminoxane is difficult to dissolve in saturated hydrocarbons, it has been used as a solution of aromatic hydrocarbons such as toluene or benzene, which is environmentally undesirable. For this reason, in recent years, a flexible body of methylaluminoxane has been developed and used as aluminoxane dissolved in saturated hydrocarbons. This modified methylaluminoxane represented by formula [V] is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum, for example, using trimethylaluminum and triisobutylaluminum, as shown in, for example, U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584. Aluminoxane in which Rx is an isobutyl group is commercially available under the trade names MMAO and TMAO in the form of a saturated hydrocarbon solution (see Tosoh Finechem Corporation, Tosoh Research & Technology Review, Vol 47, 55 (2003)).

[0109] Furthermore, examples of the organoaluminum oxy compound (Q-2) also include an organoaluminum oxy compound containing boron represented by the following general formula [VI].

[0110]

Chemical formula

[0111] Compounds (Q-3) that react with the bridged metallocene compound (P) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound" or simply "ionic compound") include, for example, those described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, U.S. Patent No. 5,321,106, etc., such as Lewis acids, ionic compounds, borane compounds, and carborane compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned.

[0112] The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].

[0113] [Chemical formula] In formula [VII], R e+ includes H + , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, etc. R f to R i may be the same as or different from each other, and are substituents selected from hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and are preferably substituted aryl groups.

[0114] Specific examples of the above carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(4-methylphenyl)carbenium cation, and tris(3,5-dimethylphenyl)carbenium cation.

[0115] Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0116] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(4-methylphenyl)phosphonium cation, and tris(3,5-dimethylphenyl)phosphonium cation.

[0117] R e+ Among the above specific examples, carbocation, ammonium cation, etc. are preferred, and particularly triphenylcarbocation, N,N-dimethylanilinium cation, and N,N-diethylanilinium cation are preferred.

[0118] Among the ionizable ionic compounds preferably used in the present invention, examples of the compound containing a carbocation include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis{3,5-di-(trifluoromethyl)phenyl}borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0119] Among the ionized ionic compounds preferably used in the present invention, examples of the compounds containing a trialkyl-substituted ammonium cation include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, trimethylammonium tetrakis(4-methylphenyl)borate, trimethylammonium tetrakis(2-methylphenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(2,4-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate, tri(n-butyl)ammonium tetrakis{4-(trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, tri(n-butyl)ammonium tetrakis(2-methylphenyl)borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(4-methylphenyl)borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl)borate, dioctadecylmethylammonium tetrakis{4-(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, dioctadecylmethylammonium, and the like.

[0120] Among the ionizable ionic compounds preferably used in the present invention, examples of the compounds containing an N,N-dialkylanilinium cation include N,N-dimethylanilinium tetraphenylborate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, N,N-diethylanilinium tetraphenylborate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl}borate, N,N-2,4,6-pentamethylanilinium tetraphenylborate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, and the like.

[0121] Among the ionizable ionic compounds preferably used in the present invention, examples of the compounds containing a dialkylammonium cation include di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate, and the like.

[0122] In addition, the ionic compounds exemplified in JP-A-2004-51676 can also be used without limitation. The above ionic compound (Q-3) may be used alone or in combination of two or more.

[0123] Examples of the constitution examples of the catalyst system include, for example, the following [1] to [4]. [1] Containing a bridged metallocene compound (P) and a compound (Q-2) [2] Containing a bridged metallocene compound (P), a compound (Q-1), and a compound (Q-2) [3] Containing a bridged metallocene compound (P), a compound (Q-1), and a compound (Q-3) [4] Containing a bridged metallocene compound (P), a compound (Q-2), and a compound (Q-3)

[0124] The crosslinked metallocene compound (P) and the compounds (Q-1) to (Q-3) may be introduced into the reaction system in any order.

[0125] 〔Support (R)〕 In the present invention, as a constituent component of the olefin polymerization catalyst, a support (R) may be used as necessary.

[0126] The above support (R) is an inorganic or organic compound and is a granular or particulate solid. Among these, as the inorganic compound, a porous oxide, an inorganic chloride, clay, a clay mineral, or an ion-exchangeable layered compound is preferable.

[0127] Specific examples of the porous oxide include SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or a composite or mixture containing these, for example, natural or synthetic zeolite, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc. can be used. Among these, those having SiO2 and / or Al2O3 as the main component are preferable. Such porous oxides have different properties depending on the type and production method, but the support preferably used in the present invention has a particle size of 0.5 to 300 μm, preferably 1.0 to 200 μm, and a specific surface area of 50 to 1000 m 2 / g, preferably 100 to 700 m 2 / g, and a pore volume in the range of 0.3 to 3.0 cm 3 / g. Such a support is used after being calcined at 100 to 1000 °C, preferably 150 to 700 °C, as necessary.

[0128] As the inorganic chloride, MgCl2, MgBr2, MnCl2, MnBr2, etc. are used. The inorganic chloride may be used as it is, or may be used after being pulverized by a ball mill or a vibration mill. Further, after dissolving the inorganic chloride in a solvent such as alcohol, a precipitate obtained by precipitating it into fine particles with a precipitating agent may be used.

[0129] Clay is usually composed mainly of clay minerals. An ion-exchangeable layered compound is a compound having a crystal structure in which the constituent planes are stacked parallel to each other with a weak binding force by an ionic bond or the like, and the contained ions are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Further, these clays, clay minerals, and ion-exchangeable layered compounds are not limited to natural products, and synthetic products can also be used. Examples of the clay, clay mineral, or ion-exchangeable layered compound include clay, clay mineral, and an ion-crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl2 type, a CdI2 type, and the like. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gyrolite clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, ryokite group, palygorskite, kaolinite, nacrite, dickite, halloysite, and the like. Examples of the ion-exchangeable layered compound include crystalline acidic salts of polyvalent metals such as α-Zr(HAsO4)2·H2O, α-Zr(HPO4)2, α-Zr(KPO4)2·3H2O, α-Ti(HPO4)2, α-Ti(HAsO4)2·H2O, α-Sn(HPO4)2·H2O, γ-Zr(HPO4)2, γ-Ti(HPO4)2, γ-Ti(NH4PO4)2·H2O. It is also preferable to subject the clay and clay mineral used in the present invention to chemical treatment. As the chemical treatment, any treatment such as a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure of the clay can be used. Specific examples of the chemical treatment include acid treatment, alkali treatment, salt treatment, organic substance treatment, and the like.

[0130] Ion-exchangeable layered compounds may be layered compounds in a state where the interlayer is expanded by utilizing the ion-exchangeability and exchanging the exchangeable ions between the layers with another large and bulky ion. Such bulky ions play a pillar-like role in supporting the layered structure and are usually called pillars. Further, introducing another substance (guest compound) into the interlayer of the layered compound in this way is called intercalation. Examples of guest compounds include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and metal hydroxide ions such as 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ 、[Fe3O(OCOCH3)6] + and the like. These compounds can be used alone or in combination of two or more. Further, when intercalating these compounds, polymers obtained by hydrolysis polycondensation of metal alkoxides such as Si(OR)4, Al(OR)3, Ge(OR)4 (where R is a hydrocarbon group, etc.), and colloidal inorganic compounds such as SiO2 can also coexist. Examples of pillars include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between the layers.

[0131] Among these, preferred ones are clay or clay minerals, and particularly preferred ones are montmorillonite, vermiculite, pechlorite, teniolite, and synthetic mica. Examples of the organic compound as the carrier (R) include granular or fine particulate solids having a particle size in the range of 0.5 to 300 μm. Specifically, (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene, (co)polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof can be exemplified.

[0132] ​​The usage method and addition order of each component of the overlapping catalyst can be arbitrarily selected. Further, at least two or more of each component in the catalyst may be contacted in advance. The crosslinked metallocene compound (P) (hereinafter also referred to as "component (P)") is usually 10 -9 ~10 -1 mol, preferably 10 -8 ~10 -2 mol per liter of reaction volume.

[0133] The organometallic compound (Q-1) (hereinafter also referred to as "component (b-1)") is used in such an amount that the molar ratio [(Q-1) / M] between component (Q-1) and the transition metal atom (M) in component (P) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

[0134] The organoaluminum oxy compound (Q-2) (hereinafter also referred to as "component (Q-2)") is used in such an amount that the molar ratio [(Q-2) / M] between the aluminum atom in component (Q-2) and the transition metal atom (M) in component (P) is usually 10 to 5,000, preferably 20 to 2,000.

[0135] The ionic compound (Q-3) (hereinafter also referred to as "component (Q-3)") is used in such an amount that the molar ratio [(Q-3) / M] between component (Q-3) and the transition metal atom (M) in component (P) is usually 1 to 10,000, preferably 1 to 5,000.

[0136] The polymerization temperature is usually -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, and even more preferably 130°C to 200°C. In the polymerization temperature range of the above range, as the temperature increases, the solution viscosity during polymerization decreases, and the removal of the polymerization heat becomes easier. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G), preferably normal pressure to 8 MPa-G.

[0137] The polymerization reaction can be carried out in any of the batch, semi - continuous, or continuous methods. Furthermore, it is also possible to continuously carry out the polymerization in two or more polymerization reactors with different reaction conditions. The molecular weight of the resulting copolymer can be adjusted by changing the hydrogen concentration and polymerization temperature in the polymerization system. Furthermore, it can also be adjusted by the amount of component (Q) used. When adding hydrogen, the appropriate amount is about 0.001 - 5,000 NL per 1 kg of the resulting copolymer.

[0138] The polymerization solvent used in the liquid - phase polymerization method is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon with a boiling point of 50°C - 200°C under normal pressure. Specifically, examples of the polymerization solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Particularly preferred are hexane, heptane, octane, decane, and cyclohexane. The α - olefin itself to be polymerized can also be used as the polymerization solvent. Although aromatic hydrocarbons such as benzene, toluene, and xylene and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can also be used as the polymerization solvent, from the viewpoints of reducing the environmental load and minimizing the impact on human health, their use is not preferred.

[0139] The kinematic viscosity of the ethylene - α - olefin copolymer (C) at 100°C depends on the molecular weight of the polymer. That is, if the molecular weight is high, the viscosity is high, and if the molecular weight is low, the viscosity is low. Therefore, the kinematic viscosity at 100°C can be adjusted by the above - mentioned molecular weight adjustment. Also, the molecular weight distribution (Mw / Mn) of the obtained polymer can be adjusted by removing the low - molecular - weight components of the polymer obtained by a conventionally known method such as vacuum distillation. Furthermore, for the obtained polymer, hydrogenation (hereinafter also referred to as hydrogen addition) may be carried out by a conventionally known method. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.

[0140] The obtained ethylene·α-olefin copolymer (C) may be used alone, or two or more kinds having different molecular weights or different monomer compositions may be combined.

[0141] [Polyamide resin composition] The polyamide resin composition of the present invention contains 30 to 90% by mass of an aliphatic polyamide (A), 1 to 50% by mass of an acid-modified ethylene·α-olefin copolymer (B), and 1 to 50% by mass of an ethylene·α-olefin copolymer (C) (however, the total of the aliphatic polyamide (A), the acid-modified ethylene·α-olefin copolymer (B), and the ethylene·α-olefin copolymer (C) is 100% by mass). The polyamide composition of the present invention preferably contains 35 to 85% by mass of an aliphatic polyamide (A), 5 to 45% by mass of an acid-modified ethylene·α-olefin copolymer (B), and 5 to 40% by mass of an ethylene·α-olefin copolymer (C), more preferably 40 to 80% by mass of an aliphatic polyamide (A), 10 to 40% by mass of an acid-modified ethylene·α-olefin copolymer (B), and 5 to 30% by mass of an ethylene·α-olefin copolymer (C), and still more preferably 40 to 76% by mass of an aliphatic polyamide (A), 15 to 40% by mass of an acid-modified ethylene·α-olefin copolymer (B), and 9 to 25% by mass of an ethylene·α-olefin copolymer (C) (however, the total of the aliphatic polyamide (A), the acid-modified ethylene·α-olefin copolymer (B), and the ethylene·α-olefin copolymer (C) is 100% by mass). The polyamide resin composition mixed with the aliphatic polyamide (A), the acid-modified ethylene·α-olefin copolymer (B), and the ethylene·α-olefin copolymer (C) in such proportions can be handled in a solid state, and further has excellent pelletizing property, bleed-out resistance, and blocking resistance.

[0142] The polyamide resin composition of the present invention may contain additives, fillers, etc. that can be included in the molding materials described later.

[0143] [Method for producing polyamide resin composition] The polyamide resin composition of the present invention can be prepared by melt-mixing, for example, an aliphatic polyamide (A), an acid-modified ethylene-α-olefin copolymer (B), and an ethylene-α-olefin copolymer (C) with additives blended as required by various conventionally known methods. Specifically, after charging and mixing the above components simultaneously or sequentially into, for example, a Henschel mixer, V-type blender, tumbler mixer, ribbon blender, etc., it is obtained by melt-kneading with a single-screw extruder, multi-screw extruder, kneader, Banbury mixer, etc. In particular, when using a device with excellent kneading performance such as a multi-screw extruder, kneader, Banbury mixer, etc., a high-quality polyamide resin composition in which each component is more uniformly dispersed can be obtained. Also, other additives, such as antioxidants, can be added as required at any of these stages.

[0144] A preferred embodiment of the method for producing the polyamide resin composition of the present invention is as follows. A step of melt-kneading 30 to 90% by mass of the above aliphatic polyamide (A) and 1 to 50% by mass of the above acid-modified ethylene-α-olefin copolymer (B), and A step of melt-kneading a polymer mixture (1) containing the aliphatic polyamide (A) and the acid-modified copolymer (B) obtained by the above melt-kneading with 1 to 50% by mass of the above ethylene-α-olefin copolymer (C), A method for producing a polyamide resin composition comprising.

[0145] Another preferred embodiment of the method for producing the polyamide resin composition of the present invention is as follows. A step of melt-kneading 1 to 50% by mass of the above acid-modified ethylene-α-olefin copolymer (B) and 1 to 50% by mass of the above ethylene-α-olefin copolymer (C), and A step of melt-kneading a polymer mixture (2) containing the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) obtained by the above melt-kneading with 30 to 90% by mass of the above aliphatic polyamide (A), A method for producing a polyamide resin composition comprising.

[0146] Among the preferred embodiments of the method for producing these polyamide resin compositions, a polymer mixture (2) containing an acid-modified ethylene-α-olefin copolymer (B) and an ethylene-α-olefin copolymer (C) is first prepared by melt-kneading, and then the polymer mixture (2) and an aliphatic polyamide (A) are melt-kneaded to produce the polyamide resin composition. The polyamide resin composition obtained by this method for producing the latter polyamide resin composition tends to have less bleeding out derived from the ethylene-α-olefin copolymer (C), and a molded article molded from a molding material containing this polyamide resin composition tends to have excellent impact resistance.

[0147] [Resin Composition for Masterbatch, Molding Material] The polyamide resin composition of the present invention thus obtained can be used as a molding material as it is, but it is also a preferred embodiment to use it as a resin composition for a masterbatch as other components in other thermoplastic resins, etc., that is, for use as a molding material. When the polyamide resin composition of the present invention is used as a masterbatch, although it contains an ethylene-α-olefin copolymer (C) which is a liquid oligomer, it is excellent in pelletizability, bleed-out resistance, and blocking resistance, so it can be handled as a solid, for example, a solid such as a pellet, rod, or plate, and has excellent handleability. When the polyamide resin composition of the present invention is used as a resin composition for a masterbatch, the molding material may further contain a thermoplastic resin (D). The thermoplastic resin (D) may be used alone or in combination of two or more. When the polyamide resin composition of the present invention is used as a resin composition for a masterbatch, as the thermoplastic resin (D), it is a preferred form to include the above-mentioned aliphatic polyamide (A), or an aliphatic polyamide (A) and an acid-modified ethylene-α-olefin copolymer (B). The polyamide resin composition of the present invention, and a molding material in which the polyamide resin composition of the present invention is used as a masterbatch and contains an aliphatic polyamide (A) or an aliphatic polyamide (A) and an acid-modified ethylene-α-olefin copolymer (B) as a thermoplastic resin (D) has excellent fluidity during molding, and a molded article molded from the molding material containing the polyamide resin composition tends to have excellent impact resistance.

[0148] [Additives] In the polyamide resin composition of the present invention and the molding material when the polyamide resin composition of the present invention is used as a masterbatch composition, within a range not impairing the object of the present invention, other rubbers, antioxidants, heat stabilizers, weather stabilizers, slip agents, antiblocking agents, crystal nucleating agents, pigments, hydrochloric acid absorbers, copper damage preventives, etc. may be contained as additives as necessary. These additives are usually contained in an amount of 0.01 to 10 parts by mass, preferably 0.01 to 5 parts by mass, based on 100 parts by mass in total of the aliphatic polyamide (A), ethylene-α-olefin copolymer (B), ethylene-α-olefin copolymer (C) contained in the molding material, and the thermoplastic resin (D) added as necessary.

[0149] [Filler] Further, the polyamide resin composition of the present invention and the molding material when the polyamide resin composition of the present invention is used as a masterbatch composition may contain a filler. Examples of the filler include fillers such as fibrous fillers, granular fillers, and plate-like fillers. Specific examples of the fibrous filler include glass fiber, carbon fiber, aramid fiber, etc. Preferred examples of the glass fiber include chopped strands having an average fiber diameter of 6 to 14 μm. Specific examples of the granular or plate-like filler include calcium carbonate, mica, glass flake, glass balloon, magnesium carbonate, silica, talc, clay, pulverized products of carbon fiber and aramid fiber, etc. Note that these fillers are not included in the above additives.

[0150] These fillers are usually contained in an amount of 1 to 200 parts by mass, preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, based on 100 parts by mass in total of the aliphatic polyamide (A), ethylene-α-olefin copolymer (B), ethylene-α-olefin copolymer (C) and, if necessary, the thermoplastic resin (D) contained in the molding material. Such a filler-containing molding material is useful for applications where it is desired to further improve the mechanical strength of the resulting molded article, or for applications where a molded article having a controlled linear expansion rate (molding shrinkage rate) is required.

[0151] [Molded article] The molded article of the present invention is obtained by molding a molding material containing the above-described polyamide resin composition. When the polyamide resin composition of the present invention is used as a molding material as it is, it may be molded into various molded articles by known molding methods. When the polyamide resin composition of the present invention is used as a resin composition for a masterbatch, the molded article is, for example, a step of melt-kneading a mixture obtained by dry-blending a thermoplastic resin (D), additives and fillers, if necessary, with a resin composition for a masterbatch containing the polyamide resin composition, and a step of molding the resin composition (3) obtained by the melt-kneading. It can be produced by a production method including The method of dry-blending is not particularly limited, and a conventionally known method can be used. Examples of known blending methods include a method of putting each component to be a molding material into a bag and shaking it by hand, and a method of blending each component to be a molding material using a V blender, a ribbon blender, a tumbler blender, a Henschel mixer, or the like. The shape of the resin composition for a masterbatch to be used is not limited, and it may be in powder form or pellet form. From the viewpoints of ease of handling, miscibility of each component during melt-kneading and molding, and appearance of the resulting molded article, the shape of the resin composition for a masterbatch is preferably in pellet form. As a molding method for obtaining a molded article from a molding material containing the polyamide resin composition of the present invention, for example, injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calender molding, foam molding, etc. can be mentioned.

[0152] The molding material containing the polyamide resin composition of the present invention, and the molded article obtained from the molding material can be used for various applications. For example, the molding material containing the polyamide resin composition of the present invention, and the molded article obtained from the molding material are used as various members used in vehicles such as automobiles, railway vehicles (vehicles in general), aircraft fuselages (fuselages in general), ships and hulls (hulls in general), bicycles (bicycle bodies in general), etc., and electronic members used in electronic products. Examples of members for automobiles include automobile interior and exterior materials, automobile cover members, automobile door members, engine members, electrical components, etc.

Examples

[0153] Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The raw material components used in the examples and comparative examples are as follows. [Aliphatic polyamide (A)] In the following examples and comparative examples, the following commercially available products were used as the aliphatic polyamide (A). A-1: Polyamide 6 (PA6), Amilan CM1007 manufactured by Toray Industries, Inc.

[0154] [Acid-modified ethylene·α-olefin copolymer (B)] The measurement methods for various physical properties of the acid-modified ethylene·α-olefin copolymer (B) are as follows. <mfr> The measurement was carried out under the conditions of 190 °C and a load of 2.16 kg in accordance with ASTM D1238.

[0155] <Content of the skeleton derived from maleic acid or maleic anhydride> The content of the skeleton derived from maleic acid or maleic anhydride was determined from a calibration curve prepared separately based on the peak intensity at the wavenumber 1780 cm -1 attributed to the carbonyl group by FT-IR.

[0156] [Production of acid-modified ethylene·α-olefin copolymer (B)] The production method of the acid-modified ethylene·α-olefin copolymer (B) used in the examples is shown below.

[0157] [Production Example 1] Production of maleic anhydride-modified ethylene·1-butene copolymer (B-1) Ethylene·1-butene copolymer (r-1) (density 861 kg / m 3 , MFR (190 °C, 2.16 kg) 0.5 g / 10 min, ethylene content ratio 80 mol%, 1-butene content ratio 20 mol%) 10 kg, and a solution prepared by dissolving 110 g of maleic anhydride and 6 g of 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexene in 80 g of acetone were blended in a Henschel mixer.

[0158] Next, the obtained blend was charged into the hopper of a twin-screw extruder with a screw diameter of 30 mm and L / D = 42, and extruded into strands at a resin temperature of 260 °C and an extrusion rate of 7 kg / h. Then, after water cooling, it was pelletized to obtain maleic anhydride graft-modified ethylene·1-butene copolymer (B-1).

[0159] The MFR (190 °C, 2.16 kg load) of the obtained copolymer (B-1) was 0.6 g / 10 min, and the density D B was 866 kg / m 3 , and the maleic anhydride graft amount measured after extracting unreacted maleic anhydride with acetone was 0.99% by mass.

[0160] [Ethylene·α-olefin copolymer (C)] The measuring methods for various physical properties of the ethylene·α-olefin copolymer (C) are as follows. <Weight average molecular weight (Mw), Mw / Mn> The molecular weight (Mw) and Mw / Mn of the ethylene·α-olefin copolymer (C) were determined by the following high-speed GPC measuring device. High-speed GPC measuring device: HLC8320GPC manufactured by Tosoh Corporation Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, liquid chromatography grade) Column: Two TSKgel Super Multipore HZ-M columns manufactured by Tosoh Corporation connected in series Sample concentration: 5 mg / mL Mobile phase flow rate: 0.35 mL / min Measurement temperature: 40 °C Standard sample for calibration curve: Standard polystyrene PStQuick MP-M manufactured by Tosoh Corporation

[0161] <Ethylene content (mol%)> The ethylene content of the ethylene·α-olefin copolymer (C) was measured using a JNM-ECP500 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., with an ortho-dichlorobenzene / heavy benzene (80 / 20 vol%) mixed solvent as the solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 °C, and 13 C (125 MHz), single pulse proton decoupling as the sequence, a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, an integration number of 10,000 or more, and a chemical shift reference value of 27.50 ppm were adopted for the measurement.

[0162] The ethylene content of the ethylene·α-olefin copolymer (C) was measured as described above. 13 Based on the reports of "Polymer Analysis Handbook" (published by Asakura Shoten, P163 - 170), G.J. Ray (Macromolecules, 10, 773 (1977)), J.C. Randall (Macromolecules, 15, 353 (1982)), K. Kimura (Polymer, 25, 4418 (1984)), etc., it was determined from the 13C - NMR spectrum.

[0163] <Kinematic viscosity at 100 °C> The kinematic viscosity at 100 °C (100 °C kinematic viscosity) was measured and calculated by the method described in JIS K2283.

[0164] [Production of ethylene - α - olefin copolymer (C)] The production method of the ethylene - α - olefin copolymer (C) used in the examples is shown below.

[0165] [Production Example 1] Production of ethylene - propylene copolymer (C - 1) 760 mL of heptane and 120 g of propylene were charged into a 2 L stainless - steel autoclave that had been sufficiently purged with nitrogen. After raising the temperature inside the system to 150 °C, hydrogen at 0.85 MPa and ethylene at 0.19 MPa were supplied to make the total pressure 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, [diphenylmethylene(η 5 -3 - n - butylcyclopentadienyl)(η 5 0.0002 mmol of [2,7 - bis(tert - butyl)fluorenyl]zirconium dichloride and 0.002 mmol of N,N - dimethylanilinium tetrakis(pentafluorophenyl)borate were pressured in with nitrogen, and polymerization was initiated by setting the stirring rotation speed to 400 rpm. Then, only ethylene was continuously supplied to maintain the total pressure at 3 MPaG, and polymerization was carried out at 150 °C for 5 minutes. After stopping the polymerization by adding a small amount of ethanol to the system, unreacted ethylene, propylene, and hydrogen were purged. The obtained polymerization solution was washed 3 times with 1000 mL of 0.2 mol / L hydrochloric acid and then 3 times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained polymer was dried at 80 °C under reduced pressure for 24 hours to obtain an ethylene - propylene copolymer (C - 1). The Mw of this ethylene - propylene copolymer (C - 1) was 5,100, Mw / Mn was 1.7, the ethylene content ratio was 49.5 mol%, the kinematic viscosity at 100 °C was 145 mm 2 / s, and the melting point (melting peak) was not observed. The density D C was 846 kg / m 3 . That is, the difference |D C −D B | between the density D B of this and the density D C of the ethylene - α - olefin copolymer (B - 1) was 20 kg / m 3 .

[0166] [Production Example 2] Production of ethylene - propylene copolymer (C - 2) 760 mL of heptane and 120 g of propylene were charged into a 2 - L stainless - steel autoclave that had been sufficiently purged with nitrogen. After raising the temperature inside the system to 150 °C, hydrogen at 0.85 MPa and ethylene at 0.19 MPa were supplied to make the total pressure 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene(η 5 -cyclopentadienyl)(η 5 0.0002 mmol of [(2,7-di-tert-butylfluorenyl)]zirconium dichloride and 0.002 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate were pressured in with nitrogen, and polymerization was initiated by setting the stirring speed to 400 rpm. Thereafter, only ethylene was continuously supplied to maintain the total pressure at 3 MPaG, and polymerization was carried out at 150 °C for 5 minutes. Polymerization was stopped by adding a small amount of ethanol to the system, and unreacted ethylene, propylene, and hydrogen were purged. The obtained polymerization solution was washed three times with 1000 mL of 0.2 mol / L hydrochloric acid and then three times with 1000 mL of distilled water, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude ethylene-propylene copolymer.

[0167] Into a 1 L stainless steel autoclave, 100 mL of a hexane solution of a 0.5 mass% Pd / alumina catalyst and 500 mL of a 30 mass% hexane solution of the obtained crude ethylene-propylene copolymer were added. After sealing the autoclave, nitrogen substitution was carried out. Then, while stirring, the temperature was raised to 140 °C, the inside of the system was hydrogen-substituted, and then the pressure was increased to 1.5 MPa with hydrogen and a hydrogenation reaction was carried out for 15 minutes. After filtering the reaction solution to remove the hydrogenation catalyst, the solvent was distilled off under reduced pressure and dried at 80 °C under reduced pressure for 24 hours to obtain an ethylene-propylene copolymer (C-2). The Mw of this ethylene-propylene copolymer (C-2) was 5,200, Mw / Mn was 1.7, the ethylene content was 48.5 mol%, the kinematic viscosity at 100 °C was 152 mm 2 / s, and the melting point (melting peak) was not observed. The density D C was 846 kg / m 3 . That is, the difference |D C −D B | between the density D B of this ethylene-propylene copolymer (C-2) and the density D C of the ethylene-α-olefin copolymer (B-1) was 20 kg / m 3 .

[0168] [Optional component] The following commercially available products were used. D-1: Phenolic antioxidant, Irganox 1010 manufactured by BASF Japan D-2: Phosphorus-based processing stabilizer, Irgafos 168 manufactured by BASF Japan Ltd.

[0169] [Examples 1 - 7, Comparative Examples 1, 2] An aliphatic polyamide (A-1), an acid-modified ethylene-α-olefin copolymer (B-1), ethylene-α-olefin copolymers (C-1) and (C-2), optional components (D-1) and (D-2) were melt-kneaded in the formulation described in Table 1 using a twin-screw extruder (manufactured by Parker Corporation, screw diameter: 25 mm, cylinder consists of a total of 6 blocks from C1 to C6) (cylinder temperature: 250 °C, screw rotation speed: 200 rpm, total discharge rate: 6 kg / h). The strands extruded from the die were introduced into a pelletizer to obtain pellets of the polyamide composition. The raw materials were supplied from the following locations of the extruder.

[0170] Kneading method A Aliphatic polyamide (A): Supplied from C4 Acid-modified ethylene-α-olefin copolymer (B): Supplied from the hopper Ethylene-α-olefin copolymer (C): Supplied from C2 Optional component: Supplied from the hopper

[0171] Kneading method B Aliphatic polyamide (A): Supplied from the hopper Acid-modified ethylene-α-olefin copolymer (B): Supplied from the hopper Ethylene-α-olefin copolymer (C): Supplied from C3 Optional component: Supplied from the hopper

[0172] The pelletizability was evaluated based on the following criteria when introducing the strands into the pelletizer. ○: There were no problems with the stability and hardness of the strands, and they could be pelletized stably. ×: There were problems with the stability and / or hardness of the strands, and they could not be pelletized stably.

[0173] The bleed-out resistance was evaluated according to the following criteria by directly touching the obtained strands or pellets by hand. ○: No oil bleed-out was confirmed. △: Slight oil bleed-out was confirmed. ×: Significant oil bleed-out was confirmed.

[0174] The blocking resistance was evaluated according to the following criteria by collecting the obtained pellets in a polyethylene bag and shaking them. ○: No pellet blocking was confirmed. △: Pellet blocking was confirmed. ×: Significant pellet blocking was confirmed.

[0175] The evaluation results are shown in Table 1.

[0176] In Comparative Example 1, the strands frequently broke, making it difficult to stably introduce the strands into the pelletizer. Also, significant oil bleed-out was confirmed. Furthermore, blocking between the pellets was confirmed due to the oil bleeding out from the pellets.

[0177] In Comparative Example 2, the strands were too flexible, making it difficult to cut the strands with the pelletizer. No oil bleed-out was confirmed. However, significant pellet blocking was confirmed because of the high tack and adhesiveness on the surface of the strand and pellet.

[0178]

Table 1

Claims

1. 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66, 1 to 50% by mass of an acid-modified ethylene / α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3), 1 to 50% by mass of an ethylene / α-olefin copolymer (C) satisfying the following requirements (c-1) and (c-2), A polyamide resin composition containing; (However, the total of the aliphatic polyamide (A), the acid-modified ethylene / α-olefin copolymer (B), and the ethylene / α-olefin copolymer (C) is 100% by mass.) (b-1) The melt flow rate (MFR) measured at 190 °C and a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The content of the structural unit derived from maleic acid or maleic anhydride in 100% by mass of the acid-modified ethylene / α-olefin copolymer (B) is in the range of 0.1 to 5% by mass; (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 100 mol%).

2. In the above requirement (c-1), the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 2,000 to 10,000, In the above requirement (c-2), the content ratio of the structural unit derived from ethylene is 35 to 65 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 35 to 65 mol%, The polyamide resin composition according to Claim 1.

3. 40 to 80% by mass of the aliphatic polyamide (A), 10 to 40% by mass of the acid-modified ethylene / α-olefin copolymer (B), 5 to 30% by mass of the ethylene-α-olefin copolymer (C); The polyamide resin composition according to claim 1, comprising (wherein the total of the aliphatic polyamide (A), the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C) is 100% by mass).

4. A resin composition for masterbatch comprising the polyamide resin composition according to any one of claims 1 to 3.

5. A molded article comprising the polyamide resin composition according to any one of claims 1 to 3.

6. An interior and exterior automotive material comprising the polyamide resin composition according to any one of claims 1 to 3.

7. An automotive cover member comprising the polyamide resin composition according to any one of claims 1 to 3.

8. An automotive door member comprising the polyamide resin composition according to any one of claims 1 to 3.

9. An electronic member comprising the polyamide resin composition according to any one of claims 1 to 3.

10. 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66, and 1 to 50% by mass of an acid-modified ethylene-α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3), and a step of melt-kneading; A step of melt-kneading a polymer mixture (1) containing the aliphatic polyamide (A) and the acid-modified copolymer (B) obtained by the melt-kneading and 1 to 50% by mass of an ethylene-α-olefin copolymer (C) satisfying the following requirements (c-1) and (c-2); A method for producing a polyamide resin composition comprising; (b-1) The melt flow rate (MFR) measured at 190 ° C. and a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The content of the structural unit derived from maleic acid or maleic anhydride is in the range of 0.1 to 5% by mass with respect to 100% by mass of the acid-modified ethylene-α-olefin copolymer (B); The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%).

11. A step of melt-kneading 1 to 50% by mass of an acid-modified ethylene / α-olefin copolymer (B) satisfying the following requirements (b-1) to (b-3) and 1 to 50% by mass of an ethylene / α-olefin copolymer (C) satisfying the following requirements (c-1) and (c-2); A step of melt-kneading a polymer mixture (2) containing the acid-modified copolymer (B) and the ethylene / α-olefin copolymer (C) obtained by the above melt-kneading and 30 to 90% by mass of one or more aliphatic polyamides (A) selected from the group consisting of polyamide 6 and polyamide 66; A method for producing a polyamide resin composition comprising; (b-1) The melt flow rate (MFR) measured at 190 °C under a load of 2.16 kg is 0.01 to 100 g / 10 min; (b-2) The content ratio of the structural unit derived from ethylene is 60 to 95 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 8 carbon atoms is taken as 100 mol%); (b-3) The content ratio of the structural unit derived from maleic acid or maleic anhydride is in the range of 0.1 to 5% by mass with respect to 100% by mass of the acid-modified ethylene / α-olefin copolymer (B); (c-1) The weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is 500 to 50,000; (c-2) The content ratio of the structural unit derived from ethylene is 20 to 80 mol%, and the content ratio of the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is taken as 100 mol%).

12. The production method according to claim 10 or 11, wherein the ethylene / α-olefin copolymer (C) is an ethylene / α-olefin copolymer (C) produced by the following method (α); Method (α): a crosslinked metallocene compound (P-1) represented by the following formula (1), and a method comprising a step of polymerizing ethylene and an α-olefin having 3 to 20 carbon atoms in the presence of a catalyst system containing at least one compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the crosslinked metallocene compound (P-1) to form an ion pair. 【Chemical 1】 (In formula (1), R １ , R ２ , R ３ , R ４ , R ５ , R ８ , R ９ and R １２ are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and a plurality of adjacent groups may be linked to each other to form a ring structure. R ６ and R １１ are the same group as each other and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group. R ７ and R １０ are the same group as each other and are a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group. R ６ and R ７ may be bonded to a hydrocarbon having 2 to 3 carbon atoms to form a ring structure. R １０ and R １１ may be bonded to a hydrocarbon having 2 to 3 carbon atoms to form a ring structure. R ６ , R ７ , R １０ and R １１ are not hydrogen atoms at the same time, and Y is a carbon atom or a silicon atom. R １３ and R １４ are each independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and may be linked to each other to form a ring structure, M is a titanium atom, a zirconium atom or a hafnium atom, Q is independently a halogen atom, a hydrocarbon group, an anionic ligand or a neutral ligand capable of coordinating to a lone pair of electrons, and j is an integer of 1 to 4.) **Claim 13** In the formula (1), R １３ and R １４ The production method according to claim 12, wherein either one or both of them are aryl groups. **Claim 14** In the formula (1), R １３ and R １４ are both aryl groups, and either R ２ or R ３ is a saturated hydrocarbon group having 4 carbon atoms. The production method according to claim 12.

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