Polyamide resin composition

Abstract

To provide a polyamide resin composition which is excellent in handleability, has an excellent balance among flowability during molding, bleed-out resistance and impact resistance, and contains polyamide, a modified ethylene-α-olefin copolymer and an ethylene-α-olefin copolymer, and a method for producing the same.SOLUTION: A polyamide resin composition contains polyamide (A), an acid-modified ethylene-α-olefin copolymer (B) and an ethylene-α-olefin copolymer (C), and has a continuous phase (α), and a dispersion phase (β) dispersed in the continuous phase (α), wherein the continuous phase (α) contains polyamide (A), and the dispersion phase (β) contains polyamide (A), an acid-modified ethylene-α-olefin copolymer (B) and an ethylene-α-olefin copolymer (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a polyamide resin composition containing a 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] Due to its excellent physical properties, polyamide (nylon) is expected to have a large demand as an engineering plastic. However, in general, the balance between mechanical strength such as impact resistance and rigidity and 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 trying 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 pinholes, 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, an ethylene·α-olefin copolymer with a low molecular weight is a high-viscosity liquid, making it difficult to add to an extruder for kneading with polyamide, and there are problems with handleability as a molding material. Therefore, it is required to provide a polyamide resin composition that contains a low-molecular-weight ethylene·propylene copolymer capable of improving fluidity, has a shape that is easy to add to an extruder, and is excellent in impact resistance when kneaded with polyamide.

[0008] An object of the present invention is to provide a polyamide resin composition containing polyamide, a modified ethylene·α-olefin copolymer, and an ethylene·α-olefin copolymer, which is excellently balanced in handleability, impact resistance, etc., and a method for producing the same.

Means for Solving the Problems

[0009] The present inventors conducted intensive studies to solve the above problems. As a result, a polyamide resin composition containing polyamide (A), a specific modified ethylene·α-olefin copolymer (B), and a specific ethylene·α-olefin copolymer (C) and having a specific dispersion structure has no problem in handleability, and this polyamide resin composition and a molding material obtained by using this polyamide resin composition as a masterbatch are excellently balanced in impact resistance, etc.

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

[15] . [1] A polyamide resin composition containing polyamide (A), an acid-modified ethylene-α-olefin copolymer (B), and an ethylene-α-olefin copolymer (C), having a continuous phase (α) and a dispersed phase (β) dispersed in the continuous phase (α), wherein the continuous phase (α) contains polyamide (A), and the dispersed phase (β) contains polyamide (A), an acid-modified ethylene-α-olefin copolymer (B), and an ethylene-α-olefin copolymer (C) polyamide resin composition (X).

[0011] [2] The dispersed phase (β) has a continuous phase (β1) and a dispersed phase (β2), wherein the continuous phase (β1) contains the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C), and the dispersed phase (β2) contains the polyamide (A) The polyamide resin composition (X) according to [1]. [3] 30 to 98.9% by mass of polyamide (A), 1 to 50% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 0.1 to 50% by mass of an ethylene-α-olefin copolymer (C) (provided that the total of 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 (X) according to [1] or [2]. [4] The acid-modified ethylene-α-olefin copolymer (B) satisfies the following requirements (b-1) to (b-3), and the ethylene-α-olefin copolymer (C) satisfies the following requirements (c-1) and (c-2), The polyamide resin composition (X) according to any one of [1] to [3]; (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) It contains 60 to 95 mol% of structural units derived from ethylene and 5 to 40 mol% of structural units derived from α-olefins having 3 to 8 carbon atoms (however, the total amount of the structural units derived from ethylene and the structural units derived from α-olefins having 3 to 8 carbon atoms is taken as 100 mol%); (b-3) With respect to 100% by mass of the acid-modified ethylene·α-olefin copolymer (B), the structural unit derived from maleic acid or maleic anhydride 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 units derived from ethylene is 20 to 80 mol%, and the content ratio of the structural units derived from α-olefins having 3 to 20 carbon atoms is 20 to 80 mol% (however, the total amount of the structural units derived from ethylene and the structural units derived from α-olefins having 3 to 20 carbon atoms is taken as 100 mol).

[0012] [5] The polyamide resin composition (X) according to any one of [1] to [4], and A polyamide resin composition (Y) containing polyamide (A), or polyamide (A) and an acid-modified ethylene·α-olefin copolymer (B). [6] 40 to 90% by mass of polyamide (A), 0 to 20% by mass of an acid-modified ethylene·α-olefin copolymer (B), and 10 to 60% by mass of the polyamide resin composition (X) according to claim 1, (however, the total amount of polyamide (A), the acid-modified ethylene·α-olefin copolymer (B), and the polyamide resin composition (X) is taken as 100% by mass), containing The polyamide resin composition (Y) according to [5].

[0013] [7] A molded article comprising the polyamide resin composition (X) according to any one of [1] to [4], or the polyamide resin composition (Y) according to [5] or [6]. [8] An interior and exterior automotive trim material comprising the polyamide resin composition (X) according to any one of [1] to [4], or the polyamide resin composition (Y) according to [5] or [6]. [9] An automotive cover member comprising the polyamide resin composition (X) according to any one of [1] to [4], or the polyamide resin composition (Y) according to [5] or [6].

[10] A member for an automotive door comprising the polyamide resin composition (X) according to any one of [1] to [4], or the polyamide resin composition (Y) according to [5] or [6].

[11] An electronic member comprising the polyamide resin composition (X) according to any one of [1] to [4], or the polyamide resin composition (Y) according to [5] or [6].

[0014]

[12] A step of obtaining the polyamide resin composition (X), A step of melt-kneading the polyamide (A), the polyamide resin composition (X), and optionally the acid-modified ethylene·α-olefin copolymer (B). A method for producing a polyamide resin composition (Y) comprising: The step of obtaining the polyamide resin composition (X) comprises: A step of melt-kneading the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C); A step of melt-kneading the polymer mixture obtained by melt-kneading the acid-modified copolymer (B) and the copolymer (C) with the polyamide (A). A method for producing a polyamide resin composition (Y).

[0015]

[13] The production method according to

[12] , 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 (Formula 1), and A method comprising a step of polymerizing ethylene and an α-olefin 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.

[0016] [Chemical formula] [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 simultaneously hydrogen atoms, and Y is a carbon atom or a silicon atom. R 13 and R 14Each is independently a hydrogen atom, a hydrocarbon group or a silicon-containing hydrocarbon group, and they 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. j is an integer from 1 to 4.

[0017]

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

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

[15] 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

[13] .

Advantages of the Invention

[0018] According to the present invention, a polyamide resin composition containing a polyamide, a modified ethylene-α-olefin copolymer, and an ethylene-α-olefin copolymer, which is excellently balanced in handleability and impact resistance, etc., and a production method thereof can be provided.

Embodiments for Carrying Out the Invention

[0019] [Polyamide (A)] The polyamide (A) used in the present invention is not particularly limited, and various conventionally known polyamide resins such as aliphatic polyamides, semi-aromatic polyamides, and aromatic polyamides can be used without limitation as long as the effects of the present invention are not impaired. For example, lactam or a melt-moldable polyamide obtained by a polycondensation reaction of a diamine and a dicarboxylic acid can be used. Specific examples of the polyamide (A) include the following polymers.

[0020] (1) Polycondensates of organic dicarboxylic acids having 4 to 12 carbon atoms and organic diamines having 2 to 13 carbon atoms, such as polyhexamethylene adipamide [PA66] which is a polycondensate of hexamethylenediamine and adipic acid, polyhexamethylene azelamide [PA69] which is a polycondensate of hexamethylenediamine and azelaic acid, polyhexamethylene sebacamide [PA610] which is a polycondensate of hexamethylenediamine and sebacic acid, polyhexamethylene dodecanoamide [PA612] which is a polycondensate of hexamethylenediamine and dodecanedioic acid, semi-aromatic polyamides (such as PA6T, PA9T, PA10T, PA11T, PA6I, PA11I, etc.) which are polycondensates of aromatic dicarboxylic acids and aliphatic diamines, semi-aromatic polyamides (such as PAMXD6, etc.) which are polycondensates of aliphatic dicarboxylic acids and aromatic diamines, polybis(4-aminocyclohexyl)methane dodecane which is a polycondensate of bis-p-aminocyclohexylmethane and dodecanedioic acid, and the like.

[0021] Examples of the above organic dicarboxylic acids include adipic acid, pimelic acid, suberic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phenylenedioxydiacetic acid, oxydibenzoic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, biphenyldicarboxylic acid, sebacic acid, dodecanedioic acid, and the like. Examples of the above organic diamines include hexamethylenediamine, octamethylenediamine, nonanediamine, octanediamine, decanediamine, undecanediamine, dodecanediamine, m-xylenediamine, and the like.

[0022] (2) Polycondensates of ω-amino acids, such as polyundecanamide [PA11] which is a polycondensate of ω-aminoundecanoic acid. (3) Ring-opening polycondensates of lactams, such as polycapramide [PA6] which is a ring-opening polycondensate of ε-caprolactam, and poly laurolactam [PA12] which is a ring-opening polycondensate of ω-laurolactam.

[0023] Among the polyamides (A) exemplified above, polyhexamethylene adipamide [PA66], polyhexamethylene azelamide [PA69], polycapramide [PA6], and polylaurin lactam [PA12] are preferred.

[0024] The melting point of the polyamide (A) is preferably 150°C to 320°C, more preferably 150 to 3000°C, and still more preferably 150 to 280°C. The fact that the melting point is below the above upper limit is preferable in that the decomposition and volatilization of the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C) are suppressed during molding.

[0025] In the present invention, as the polyamide (A), two or more kinds of organic dicarboxylic acids, two or more kinds of organic diamines, two or more kinds of ω-amino acids, two or more kinds of lactams can be used. For example, a copolyamide produced from adipic acid, isophthalic acid, and hexamethylenediamine can also be used. Furthermore, blends containing two or more kinds of polyamides, such as a mixture of PA6 and PA66, can also be used.

[0026] [Acid-modified ethylene·α-olefin copolymer (B)] The acid-modified ethylene·α-olefin copolymer (B) of the present invention is a polymer obtained by modifying an unmodified ethylene·α-olefin copolymer with an unsaturated carboxylic acid or a derivative thereof.

[0027] The ethylene·α-olefin copolymer is a polymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin, typically an α-olefin having 3 to 8 carbon atoms. Examples of the α-olefins 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.

[0028] Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endo-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), and the like. Examples of the derivatives of the unsaturated carboxylic acid include acid halide compounds, amide compounds, imide compounds, acid anhydrides, and ester compounds of the unsaturated carboxylic acid. Specifically, maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like are included. Among these, unsaturated dicarboxylic acids and their acid anhydrides are preferred, maleic acid, nadic acid, and their acid anhydrides are more preferred, and maleic acid and maleic anhydride are even more preferred.

[0029] The acid-modified ethylene·α-olefin copolymer (B) used in the present invention preferably satisfies at least one of the following requirements (b-1) to (b-3), and more preferably satisfies all of the following requirements (b-1) to (b-3). (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 from 0.05 to 50 g / 10 min, more preferably from 0.07 to 20 g / 10 min, still more preferably from 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 a molded article excellent in impact resistance can be obtained.

[0030] (b-2) The content ratio of structural units derived from ethylene is 60 to 95 mol%, and the content ratio of structural units derived from an α-olefin having 3 to 8 carbon atoms is 5 to 40 mol% (however, the total amount of structural units derived from ethylene and structural units derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%). In the above, the content ratio of structural units derived from ethylene is preferably 60 to 92 mol%, more preferably 65 to 90 mol%, still more preferably 70 to 88 mol%, particularly preferably 75 to 88 mol%. The content ratio of structural units 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%, 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, making it easy to handle. Furthermore, a molded article obtained from a molding material containing the polyamide resin composition of the present invention is excellent in low-temperature impact resistance and flexibility. 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.

[0031] (b-3) The content (hereinafter simply referred to as the modification amount M) of structural units derived from maleic acid or maleic anhydride with respect to 100% by mass of the acid-modified ethylene-α-olefin copolymer (B) B is 0.1 to 5% by mass. Modification amount M B is preferably 0.2 to 3% by mass, more preferably 0.3 to 2% by mass. The modification amount M B 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, the modification amount M B If it is too large, it is necessary to increase the charged amount of the polar monomer or organic peroxide during modification by the usual modification method. However, in such a modification method, foreign substances such as gels may be mixed into the acid-modified ethylene-α-olefin copolymer (B). The modification amount M B is determined from a calibration curve prepared separately based on the peak intensity at a wave number of 1780 cm-1 attributed to the carbonyl group by FT-IR as described later.

[0032] The acid-modified ethylene-α-olefin copolymer (B) used in the present invention more preferably satisfies the following requirement (b-4).

[0033] (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 is. 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 is. When the density D B is within 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.

[0034] [Method for producing acid-modified ethylene-α-olefin copolymer (B)] The acid-modified ethylene-α-olefin copolymer (B) used in the present invention can typically be obtained by graft-modifying an unmodified ethylene-α-olefin copolymer (r) with an unsaturated carboxylic acid or its derivative, preferably maleic acid or its anhydride.

[0035] 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%).

[0036] 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 polyamide (A), and the balance between the fluidity and impact resistance of the molding material containing the resulting polyamide resin composition are improved.

[0037] The unmodified ethylene-α-olefin copolymer (r) having the above 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).

[0038] 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 graft-polymerizing an unsaturated carboxylic acid or its derivative, preferably maleic acid or its anhydride, preferably in the presence of a radical initiator.

[0039] The charged amount of the unsaturated carboxylic acid or its derivative (preferably 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 part by mass, preferably 0.005 to 0.30 part by mass, based on 100 parts by mass of the unmodified ethylene-α-olefin copolymer (r).

[0040] As the radical initiator, for example, an organic peroxide, an azo compound, or a metal hydride 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, etc. Examples of the azo compound include azobisisobutyronitrile, dimethyl azoisobutyrate, etc.

[0041] The radical initiator can be used by mixing it directly with maleic acid or its anhydride, the unmodified ethylene-α-olefin copolymer (r), and other components added as required, or it can also be used after being dissolved in a small amount of organic solvent. The organic solvent is not particularly limited as long as it can dissolve the radical initiator.

[0042] The graft modification with maleic acid or its anhydride can be carried out by a conventionally known method. For example, a method is included in which the unmodified ethylene-α-olefin copolymer (r) is dissolved in an organic solvent, and then an unsaturated carboxylic acid or its derivative (preferably maleic acid or its anhydride), a radical initiator, etc. are added to the solution, and the reaction is carried out at a temperature of 70 to 200 °C, preferably 80 to 190 °C, for 0.5 to 15 hours, preferably 1 to 10 hours.

[0043] Alternatively, a modified product can also be produced by reacting an unsaturated carboxylic acid or its derivative (preferably 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.

[0044] [Ethylene-α-olefin copolymer (C)] The ethylene-α-olefin copolymer (C) of the present invention is an unmodified ethylene-α-olefin copolymer, which is different from the acid-modified ethylene-α-olefin copolymer (B), and is a polymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin, typically an α-olefin having 3 to 20 carbon atoms. 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 and the like. 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 preferable, and propylene is particularly preferable, in terms of easy availability. 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 both biomass-derived monomers and fossil fuel-derived monomers may be used. The ethylene-α-olefin copolymer (C) may be used alone or in combination of two or more.

[0045] The ethylene-α-olefin copolymer (C) used in the present invention preferably satisfies at least one of the following requirements (c-1) and (c-2), and more preferably satisfies all of the following requirements (c-1) and (c-2).

[0046] (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 fluidity during molding may deteriorate. That is, when Mw is within the above 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.

[0047] 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.

[0048] 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 (monodisperse polystyrene) with a known molecular weight. The GPC measurement can be specifically carried out by the method described in the following examples.

[0049] (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%).

[0050] In the ethylene·α-olefin copolymer (C) used in the present invention, the structural unit derived from ethylene is preferably 30 to 75 mol%, more preferably 35 to 65 mol%, still more preferably 40 to 60 mol%, and the structural unit derived from an α-olefin having 3 to 20 carbon atoms is 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 large or too small, the compatibility with the acid-modified ethylene·α-olefin copolymer (B) deteriorates, and 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 and the molding material containing the resin composition of the present invention may decrease.

[0051] The ethylene content of the ethylene·α-olefin copolymer (C) 13 can be measured by the C-NMR method, and 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).

[0052] The ethylene·α-olefin copolymer (C) used in the present invention preferably further satisfies at least one of the following requirements (c-3), (c-4), and (c-5).

[0053] (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) has a kinematic viscosity at 100 °C of preferably 15 to 3,000 mm 2 / s, more preferably 30 to 2500 mm 2 / s, still more preferably 50 to 1000 mm2 / s, particularly preferably 70 to 500 mm 2 / s. When the kinematic viscosity at 100°C of the ethylene·α-olefin copolymer (C) 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 article 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. 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 article obtained from the molding material containing the polyamide resin composition and the impact resistance of the obtained molded article are excellently balanced.

[0054] (c-4) - In the temperature range of 100°C to 150°C, no melting point is observed as measured by differential scanning calorimetry (DSC). 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, the non-observation of the melting point (Tm) means that the heat of fusion (ΔH) (unit: J / g) measured by differential scanning calorimetry (DSC) is not substantially measured. The non-substantial measurement of the heat of fusion (ΔH) 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 the heat of fusion (ΔH) of the ethylene·α-olefin polymer were determined by performing differential scanning calorimetry (DSC) measurement and analyzing the DSC curve with reference to JIS K7121 when cooling to -100°C and then heating to 150°C at a heating rate of 10°C / min. The non-observation of the melting point is preferable in terms of facilitating addition to a kneader such as an extruder, which is mixed with the polyamide (A) and the acid-modified ethylene·α-olefin copolymer (B).

[0055] (c-5) The density D measured in accordance with JIS K2249 of the ethylene·α-olefin copolymer (C) C is 820 to 910 kg / m 3 and the difference |D B -D B | between the density D C measured in accordance with ASTM D1505 of the ethylene·α-olefin copolymer (B) and the density D 3 is 50 kg / m

[0056] or less. The density D C is 820 to 910 kg / m 3 , preferably 830 to 900 kg / m 3 . Also, the difference |D C -D B | between the density D B and the density D C of the acid-modified ethylene·α-olefin copolymer (B) is preferably 50 kg / m 3 or less, more preferably 40 kg / m 3 or less. 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 polyamide (A). When the difference between the density D C and the density D B is within the above range, the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C) are likely to be compatible. Therefore, the dispersed phase is likely to contain the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C). Moreover, during melt-kneading, the effect of reducing the viscosity of the acid-modified ethylene·α-olefin copolymer (B) by the ethylene·α-olefin copolymer (C) is exerted, and it is considered that the dispersibility of the copolymer (B) is improved. As a result, it is considered that the fluidity during molding of the molding material containing the polyamide resin composition of the present invention and the impact resistance of the molded article can be easily improved in a well-balanced manner.

[0057] [Method for producing 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. Examples of such methods include those described in International Publication No. 2000 / 34420, Japanese Patent Application Laid-Open No. 62-121710, International Publication No. 2004 / 29062, Japanese Patent Application Laid-Open No. 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 is preferable because it can reduce the chlorine content of the resulting copolymer and the amount of 1,1’ or 2,2’-bonding (inversion) of the α-olefin monomer.

[0058] 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 bridged 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 bridged metallocene compound (P) to form an ion pair.

[0059] [Chemical formula]

[0060] [Bridged metallocene compound (P)] The bridged metallocene compound (P) is represented by the above formula [I]. Y, M, R 1 ~R 14 、Q, n and j will be described below.

[0061] (Y, M, R 1 ~R14 , Q, n, and j) Y is a Group 14 atom, for example, a carbon atom, a silicon atom, a germanium atom, or a tin atom, preferably a carbon atom or a silicon atom, more preferably a carbon atom.

[0062] M is a titanium atom, a zirconium atom, or a hafnium atom, preferably 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 may be the same or different from each other. Also, R 1 to R 12 adjacent substituents up to may be bonded to each other to form a ring or may not be bonded to each other.

[0063] 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.

[0064] 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.

[0065] 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 with 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.

[0066] 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.

[0067] 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 azulenyl 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 with 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 with 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.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] Examples of the oxygen-containing group include a hydroxyl group; a group in which the -CH2- structural unit in the above-described hydrocarbon group, silicon-containing group, or nitrogen-containing group having 1 to 20 carbon atoms is replaced with an oxygen atom or a carbonyl group; or a group in which the -CH3 structural unit is replaced with an oxygen atom bonded to a hydrocarbon group having 1 to 20 carbon atoms, such as a methoxy group, ethoxy group, t-butoxy group, phenoxy group, trimethylsiloxy group, methoxyethoxy group, hydroxymethyl group, methoxymethyl group, ethoxymethyl group, t-butoxymethyl group, 1-hydroxyethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, n-2-oxabutylene group, n-2-oxapentylene group, n-3-oxapentylene group, aldehyde group, acetyl group, propionyl group, benzoyl group, trimethylsilylcarbonyl group, carbamoyl group, methylaminocarbonyl group, carboxy group, methoxycarbonyl group, carboxymethyl group, ethoxycarboxymethyl group, carbamoylmethyl group, furanyl group, pyranyl group, etc. Among them, the methoxy group is preferable as the oxygen-containing group.

[0073] Examples of the halogen atom include fluorine, chlorine, bromine, iodine, etc., which are Group 17 elements. Examples of the halogen-containing group include a group in which a hydrogen atom is replaced with a halogen atom in the above-described hydrocarbon group, silicon-containing group, nitrogen-containing group, or oxygen-containing group having 1 to 20 carbon atoms, such as a trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] R 13 and R 14 are atoms or substituents 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.

[0078] 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.

[0079] 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 heterocyclic aromatic compounds.

[0080] 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.

[0081] Among them, R 13 and R 14 The crosslinked metallocene compound (P) in which either one or both of them are each independently an aryl group is preferred, and the crosslinked metallocene compound (P) in which both are independently an aryl group is more preferred.

[0082] In particular, the crosslinked metallocene compound (P) in which both R 13 and R 14 are independently aryl groups has high polymerization activity for the copolymerization of ethylene and α-olefin. By using this crosslinked metallocene compound (P), the polymerization selectively stops by introducing hydrogen to the molecular end, so the unsaturated bonds of 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.

[0083] 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).

[0084]

Chemical formula

[0085] Compared with the compound in which n in the above formula [I] is an integer of 2 to 4, the crosslinked metallocene compound (P-1) has a simplified production process, a reduced production cost, and thus the advantage that the production cost of the ethylene·α-olefin copolymer (C) can be reduced by using this crosslinked metallocene compound (P-1).

[0086] 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 is copolymerized with one or more monomers selected from α-olefins having 3 to 20 carbon atoms 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) can be obtained.

[0087] 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 combined with 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.

[0088] Also in the bridged metallocene compound (P-1), R 13 and R 14The crosslinked metallocene compound (P-1) in which one or both of them are aryl groups is preferred, and the crosslinked metallocene compound (P-1) in which both are independently aryl groups is more preferred. 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 R 2 or R 3 is a saturated hydrocarbon group having 4 carbon atoms is even more preferred.

[0089] 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.

[0090] Method (α): 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 the crosslinked metallocene compound (P-1) represented by the following formula (1), and 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.

[0091]

Chemical formula

[0092] 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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dimethylmethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [cyclohexylidene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylmethylene{η 5 -(2-Methyl-4-i-propylcyclopentadienyl)}(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylmethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0093] [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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methylphenylmethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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,

[0094] [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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [diphenylsilylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [bis(3-methylphenyl)silylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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)(η5 -3,6-di-tert-butylfluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dicyclohexylsilylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,

[0095] [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 -octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [ethylene(η 5 -cyclopentadienyl)(η 5 -tetramethyloctahydrodibenzofluorenyl)]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)(octamethyloctahydrodibenzofluorenyl)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,

[0096] 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)(octamethyloctahydrodibenzsfluorenyl)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,

[0097] 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[η5 -(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,

[0098] 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,

[0099] 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.

[0100] 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, and compounds in which the chloro ligand is replaced with a methyl group. 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.

[0101] [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.

[0102] 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.

[0103] (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 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 0 < m ≦ 3, n is 0 ≦ n < 3, p is 0 ≦ p < 3, q is 0 ≦ q < 3, and m + n + p + q = 3.)

[0104] 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, trisec-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; 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 represented by, 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, partially alkoxylated alkylaluminums having an average composition represented by the general formula R a 2.5 Al(OR b ) 0.5 and the like, 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, partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, and ethylaluminum ethoxybromide, and the like can be exemplified. Further, in 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.

[0105] (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.)

[0106] Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4 and the like.

[0107] (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 as 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.)

[0108] 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.

[0109]

Chemical formula

[0110]

Chemical formula

[0111] Particularly, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more, is used. These aluminoxanes may be mixed with a small amount of an organoaluminum compound.

[0112] In the present invention, when copolymerizing ethylene with 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, etc. 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.

[0113] Further, examples of the organoaluminum oxy compound (Q-2) include modified methylaluminoxane represented by the following general formula [V].

[0114]

Chemical formula

[0115] Methylaluminoxane, which is an example of the organoaluminum oxy compound (Q-2), is easily available and has high polymerization activity, and thus is generally used as an activator in the polymerization of polyolefins. 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 an aluminoxane dissolved in saturated hydrocarbons. This modified methylaluminoxane represented by the 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. The 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)).

[0116] Furthermore, examples of the organoaluminum oxy compound (Q-2) also include an organoaluminum oxy compound containing boron represented by the following general formula [VI].

[0117]

Chemical formula

[0118] Compounds (Q-3) that react with the crosslinking 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, US Patent No. 5321106, etc., such as Lewis acids, ionic compounds, borane compounds, and carborane compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned.

[0119] The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].

[0120] [Chemical formula] In formula [VII], R e+ is, for example, 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.

[0121] 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.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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.

[0127] Among the ionized ionic compounds preferably used in the present invention, examples of the compounds containing N,N-dialkylanilinium cations 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.

[0128] Among the ionized ionic compounds preferably used in the present invention, examples of the compounds containing dialkylammonium cations include di-n-propylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetraphenylborate, and the like.

[0129] In addition, the ionic compounds exemplified by 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.

[0130] Examples of the configuration 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)

[0131] The crosslinked metallocene compound (P) and the compounds (Q-1) to (Q-3) may be introduced into the reaction system in any order.

[0132] [Support (R)] In the above method (α), as a constituent component of the catalyst, a support (R) may be used as necessary.

[0133] 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.

[0134] 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, such as 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.

[0135] 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 precipitant may be used.

[0136] 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, such as an ionic bond, 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 naturally occurring ones, and synthetic products can also be used. Further, examples of the clay, clay mineral, or ion-exchangeable layered compound include clay, clay mineral, and ion-crystalline compounds 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, umo group, montmorillonite group, vermiculite, ryokudai stone 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 minerals 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, and organic substance treatment.

[0137] Ion-exchangeable layered compounds may be layered compounds in a state where the interlayer is expanded by utilizing ion-exchangeability and exchanging the exchangeable ions between layers with another large and bulky ion. Such bulky ions play a supporting 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.), 13 O4(OH) 24 7+ 、[Zr4(OH) 14 2+ 、[Fe3O(OCOCH3)6] + and metal hydroxide ions such as these. These compounds are 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. Further, examples of the pillar include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between layers.

[0138] 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, or (co)polymers produced mainly from vinylcyclohexane or styrene, and modified products thereof can be exemplified.

[0139] ​​The usage method and the 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 the reaction volume.

[0140] 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 the component (Q-1) and the transition metal atom (M) in the component (P) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

[0141] 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 the component (Q-2) and the transition metal atom (M) in the component (P) is usually 10 to 5,000, preferably 20 to 2,000.

[0142] 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 the component (Q-3) and the transition metal atom (M) in the component (P) is usually 1 to 10,000, preferably 1 to 5,000.

[0143] 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.

[0144] 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 in the polymerization system and the polymerization temperature. 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.

[0145] 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. It is also possible to use the α - olefin itself to be polymerized 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 perspectives of reducing the environmental load and minimizing the impact on human health, their use is not preferred.

[0146] 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.

[0147] 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.

[0148] [Polyamide resin composition (X)] The polyamide resin composition (X) of the present invention contains a polyamide (A), an acid-modified ethylene-α-olefin copolymer (B), and an ethylene-α-olefin copolymer (C). It has a continuous phase (α) and a dispersed phase (β) dispersed in the continuous phase (α). The continuous phase (α) contains the polyamide (A). The dispersed phase (β) contains the polyamide (A), the acid-modified ethylene-α-olefin copolymer (B), and the ethylene-α-olefin copolymer (C). With a polyamide resin composition (X) having such a phase structure, a polyamide resin composition excellent in impact resistance can be obtained.

[0149] The dispersed phase (β) has a continuous phase (β1) and a dispersed phase (β2). It is preferable that the continuous phase (β1) contains the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C), and the dispersed phase (β2) contains the polyamide (A). When the dispersed phase (β) has such a phase structure, a polyamide resin composition having more excellent impact resistance can be easily obtained.

[0150] From the viewpoint of easily forming the above-described phase structure, the polyamide resin composition of the present invention preferably contains 30 to 98.9% by mass of the polyamide (A), 1 to 50% by mass of the acid-modified ethylene-α-olefin copolymer (B), and 0.1 to 50% by mass of the ethylene-α-olefin copolymer (C) (however, the total of the 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 30 to 90% by mass of polyamide (A), 5 to 45% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 1 to 45% by mass of an ethylene-α-olefin copolymer (C). More preferably, it contains 35 to 85% by mass of polyamide (A), 10 to 40% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 5 to 40% by mass of an ethylene-α-olefin copolymer (C). Particularly preferably, it contains 40 to 80% by mass of 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). Most preferably, it contains 40 to 70% by mass of 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 polyamide (A), acid-modified ethylene-α-olefin copolymer (B), and ethylene-α-olefin copolymer (C) is 100% by mass). The polyamide resin composition mixed with polyamide (A), acid-modified ethylene-α-olefin copolymer (B), and ethylene-α-olefin copolymer (C) in such proportions can be handled in a solid state and is further excellent in pelletizability, bleed-out resistance, and blocking resistance. Also, a molded article obtained from the polyamide resin composition (X) in which each component is blended in such proportions or the polyamide resin composition (Y) described below containing this polyamide resin (X) is extremely excellent in impact resistance.

[0151] The polyamide resin composition (X) of the present invention may contain additives, fillers, etc. that can be contained in the polyamide resin composition (Y) described below.

[0152] [Method for Producing Polyamide Resin Composition (X)] The polyamide resin composition of the present invention can be prepared by melt-mixing, for example, polyamide (A), acid-modified ethylene / α-olefin copolymer (B), ethylene / α-olefin copolymer (C), and additives blended as required by various conventionally known methods. Specifically, each of the above components is charged and mixed simultaneously or sequentially, for example, into a Henschel mixer, V-type blender, tumbler mixer, ribbon blender, etc., and then melt-kneaded using 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 (X) 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.

[0153] A preferred embodiment of the method for producing the polyamide resin composition (X) of the present invention is as follows. A step of melt-kneading the above polyamide (A) and the above acid-modified ethylene / α-olefin copolymer (B), and A step of melt-kneading the polymer mixture (1) containing the polyamide (A) and the acid-modified copolymer (B) obtained by the above melt-kneading and the above ethylene / α-olefin copolymer (C), A method for producing a polyamide resin composition (X) including the above steps.

[0154] Another preferred embodiment of the method for producing the polyamide resin composition (X) of the present invention is as follows. A step of melt-kneading the above acid-modified ethylene / α-olefin copolymer (B) and the above ethylene / α-olefin copolymer (C), and A step of melt-kneading the polymer mixture (2) containing the acid-modified copolymer (B) and the ethylene / α-olefin copolymer (C) obtained by the above melt-kneading and the above polyamide (A), A method for producing a polyamide resin composition (X) including the above steps.

[0155] Among the preferred embodiments of the method for producing these polyamide resin compositions (X), a polymer mixture (2) containing an acid-modified copolymer (B) and an ethylene·α-olefin copolymer (C) is first prepared by melt-kneading, and then the polymer mixture (2) and polyamide (A) are melt-kneaded to produce the polyamide resin composition (X). The polyamide resin composition obtained by this production method of the latter polyamide resin composition (X) tends to have less bleeding out derived from the ethylene·α-olefin copolymer (C). Also, a molded article obtained from this polyamide resin composition (X) or a polyamide resin composition (Y) described later containing this polyamide resin (X) tends to have excellent impact resistance. Although the detailed reason is unknown, in the polyamide resin composition produced via the polymer mixture (2), the acid-modified copolymer (B) and the ethylene·α-olefin copolymer (C) are integrated, and in the continuous phase (α) containing polyamide (A), a dispersed phase (β) containing the acid-modified copolymer (B), the ethylene·α-olefin copolymer (C), and a part of polyamide (A) is likely to be dispersed in a relatively uniform state to form a dispersed phase structure. Also, in this dispersed phase (β), a multiple dispersed phase structure having a continuous phase (β1) containing the acid-modified copolymer (B) and the ethylene·α-olefin copolymer (C) and a dispersed phase (β2) containing polyamide (A) is likely to be formed. This phase structure is presumed to contribute to the above-described properties.

[0156] [Polyamide resin composition (Y)] The above-described polyamide resin composition (X) can be used as it is to form a molded article. Also, the obtained polyamide resin product (X) can be used as a masterbatch and mixed with other components such as other thermoplastic resins to form a molding material, and a molded article can be produced from this molding material. In this case, a preferred embodiment is to use a polyamide resin composition (X) and a polyamide resin composition (Y) containing polyamide (A) or polyamide (A) and an acid-modified ethylene·α-olefin copolymer (B).

[0157] The polyamide resin composition (Y) preferably contains 40 to 90% by mass of polyamide (A), 0 to 20% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 10 to 60% by mass of the polyamide resin composition (X), more preferably 45 to 85% by mass of polyamide (A), 0 to 15% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 15 to 55% by mass of the polyamide resin composition (X), still more preferably 50 to 80% by mass of polyamide (A), 0 to 10% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 20 to 50% by mass of the polyamide resin composition (X), and particularly preferably 55 to 75% by mass of polyamide (A), 0 to 10% by mass of an acid-modified ethylene-α-olefin copolymer (B), and 22 to 45% by mass of the polyamide resin composition (X). By containing each component in such a quantitative ratio, the polyamide resin composition (Y) easily forms a phase structure having a continuous phase (α') containing polyamide (A) and a dispersed phase (β) containing polyamide (A), an acid-modified ethylene-α-olefin copolymer (B), and an ethylene-α-olefin copolymer (C) dispersed in the continuous phase (α'). Further, the dispersed phase (β) easily forms a multiple dispersed phase structure having a continuous phase (β1) containing an acid-modified ethylene-α-olefin copolymer (B) and an ethylene-α-olefin copolymer (C) and a dispersed phase (β2) containing polyamide (A) dispersed in the continuous phase (β1).

[0158] The polyamide resin composition (X) and the polyamide resin composition (Y) of the present invention are excellent in fluidity during molding and also excellent in impact resistance. This is presumably due to the fact that the polyamide resin composition (X) and the polyamide resin composition (Y) contain an acid-modified ethylene-α-olefin copolymer (B) and an ethylene-α-olefin copolymer (C) and form the multiple dispersed phase structure as described above. Although the details are unknown, for example, the following mechanism is conceivable.

[0159] In the dispersed phase (β), there is a low elastic modulus ethylene·α-olefin copolymer part (the skeleton part of the ethylene·α-olefin copolymer derived from both the acid-modified ethylene·α-olefin copolymer (B) and the ethylene·α-olefin copolymer (C)). When this dispersed phase (β) is widely dispersed in the polyamide resin composition, when an impact is applied, the stress of the impact tends to concentrate on this ethylene·α-olefin copolymer part, and by generating crazes around this ethylene·α-olefin copolymer part, it becomes easier to absorb impact energy; Also, the ethylene·α-olefin copolymer part existing on the crack propagation stops the crack propagation and absorbs the energy that should have been used for crack growth by craze generation; Furthermore, the site derived from the unsaturated carboxylic acid or its derivative (preferably maleic acid or its anhydride) contained in the acid-modified ethylene·α-olefin copolymer (B) improves the compatibility with the polyamide (A), the dispersed particle size of the dispersed phase (β) becomes smaller, and the number of dispersed phases (β) and the area of the phase interface between the continuous phase (α) and the dispersed phase (β) increase, thereby absorbing more energy; And since the site derived from the unsaturated carboxylic acid or its derivative (preferably maleic acid or its anhydride) reacts with the terminal amino groups contained in the polyamide (A) and chemically binds firmly, the energy required for craze generation becomes larger; In addition, since the crystallinity of the polyamide (A) is lowered by the above reaction, it is presumed that it becomes easier to absorb impact energy. In particular, for the phase structure described above, among others, when the polyamide resin composition (X) or the polyamide resin composition (Y) has a multiple dispersed phase structure in which the dispersed phase (β) is present in the continuous phase (α) or the continuous phase (α'), and further this dispersed phase (β) has a continuous phase (β1) and a dispersed phase (β2) dispersed in the continuous phase (β1), as the number of dispersed phases increases, there are two interfaces between the continuous phase (α) and the dispersed phase (β) and between the continuous phase (β1) and the dispersed phase (β2) in the dispersed phase (β), and as the area of the phase interface increases, it is presumed that there are many dispersed phase·interfaces that absorb the stress when an impact is applied, and there is a tendency to exhibit high impact resistance.

[0160] [Additive] In the polyamide resin compositions (X) and (Y) of the present invention, additives such as other rubbers, antioxidants, heat stabilizers, weather stabilizers, slip agents, antiblocking agents, crystal nucleating agents, pigments, hydrochloric acid absorbers, and copper corrosion inhibitors may be included as necessary within a range not impairing the object of the present invention. 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 polyamide (A), ethylene-α-olefin copolymer (B), and ethylene-α-olefin copolymer (C) contained in the polyamide resin compositions (X) and (Y).

[0161] [Filler] Further, the polyamide resin compositions (X) and (Y) of the present invention 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, and aramid fiber. 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 flakes, glass balloons, magnesium carbonate, silica, talc, clay, and pulverized products of carbon fiber and aramid fiber. Note that these fillers are not included in the above additives.

[0162] 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 of the polyamide (A), ethylene-α-olefin copolymer (B), and ethylene-α-olefin copolymer (C) contained in the polyamide resin compositions (X) and (Y). Such a filler-containing polyamide resin composition 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.

[0163] [Method for Producing Polyamide Resin Composition (Y)] The polyamide resin composition (Y) can be produced, for example, by melt-kneading the polyamide resin composition (X), polyamide (A), or polyamide (A) and acid-modified ethylene-α-olefin copolymer (B), and other components such as additives and fillers added as required. Among them, the step of obtaining the polyamide resin composition (X), The step of melt-kneading polyamide (A) and the polyamide resin composition (X), and optionally the acid-modified ethylene-α-olefin copolymer (B), including The step of obtaining the above-described polyamide resin composition (X) is The step of melt-kneading the acid-modified ethylene-α-olefin copolymer (B) and the ethylene-α-olefin copolymer (C), The step of melt-kneading the polymer mixture (2) obtained by melt-kneading the acid-modified copolymer (B) and the copolymer (C) with polyamide (A), is preferred. The method for producing the polyamide resin composition (Y) is preferred.

[0164] [Molded Article] The molded article of the present invention can be obtained by molding the polyamide resin composition (X) or the polyamide resin composition (Y) by a known molding method. Examples of the molding method for obtaining the molded article of the present invention include injection molding, extrusion molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, calender molding, foam molding, and the like.

[0165] The polyamide resin composition (X), polyamide resin composition (Y), and molded article of the present invention can be used in various applications. For example, the polyamide resin composition (X), polyamide resin composition (Y), and molded article 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 (frames in general), etc., and electronic components used in electronic products. Examples of automotive members include automotive interior and exterior materials, automotive cover members, automotive door members, engine members, electrical components, etc.

Examples

[0166] 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. [Polyamide (A)] In the following examples and comparative examples, the following commercially available products were used as polyamide (A). A-1: Polyamide 6 (PA6), Amilan CM1007 manufactured by Toray Industries, Inc.

[0167] [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.

[0168] <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.

[0169] [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.

[0170] [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 80 mol%, 1-butene content 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.

[0171] 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 in a strand form at a resin temperature of 260 °C and an extrusion rate of 7 kg / hour. Then, after water cooling, it was pelletized to obtain maleic anhydride graft-modified ethylene·1-butene copolymer (B-1).

[0172] The MFR (190 °C, 2.16 kg load) of the obtained copolymer (B-1) was 0.6 g / 10 min, the density was 866 kg / m3, and the maleic anhydride graft amount measured after extracting unreacted maleic anhydride with acetone was 0.99 mass%.

[0173] [Ethylene·α-olefin copolymer (C)] The measurement 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

[0174] <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, 13C (125 MHz) as the observed nucleus, 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.

[0175] The ethylene content of the ethylene-α-olefin copolymer (C) was determined 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. from the 13C-NMR spectrum measured as described above.

[0176] <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.

[0177] [Production of ethylene·α-olefin copolymer (C)] The production method of the ethylene·α-olefin copolymer (C) used in the examples is shown below.

[0178] [Production Example 2] 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 sufficiently purged with nitrogen. After raising the temperature inside the system to 150 °C, the total pressure was set to 3 MPaG by supplying 0.85 MPa of hydrogen and 0.19 MPa of ethylene. Next, 0.4 mmol of triisobutylaluminum, 0.0002 mmol of [diphenylmethylene(η 5 -3-n-butylcyclopentadienyl)(η 5 -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 rotation speed to 400 rpm. Thereafter, the total pressure was maintained at 3 MPaG by continuously supplying only ethylene, and polymerization was carried out at 150 °C for 5 minutes. After stopping the polymerization by adding a small amount of ethanol into the system, 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. 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 was. That is, the density D C and the density D of the ethylene·α-olefin copolymer (B-1) B and the difference |D B −D C | was 20 kg / m 3 .

[0179] [Production Example 3] 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 sufficiently purged with nitrogen, and the temperature inside the system was raised to 150°C. Then, hydrogen at 0.85 MPa and ethylene at 0.19 MPa were supplied to set the total pressure to 3 MPaG. Next, 0.4 mmol of triisobutylaluminum, 5 [methylphenylmethylene(η 5 -cyclopentadienyl)(η

[0180] 5 -cyclopentadienyl)(η 5 -2,7-di-tert-butylfluorenyl)]zirconium dichloride at 0.0002 mmol, and N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate at 0.002 mmol were injected under nitrogen pressure, 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 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.Into an autoclave made of stainless steel with an internal volume of 1 L, 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 performed. Next, while stirring, the temperature was raised to 140 °C, the inside of the system was replaced with hydrogen, 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 by filtration, 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%, and 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 and the density D C of the ethylene-α-olefin copolymer (B-1) was 20 kg / m 3 .

[0181] [Optional component] The following commercially available products were used. D-1: Phenolic antioxidant, Irganox 1010 manufactured by BASF Japan Ltd. D-2: Phosphorus-based processing stabilizer, Irgafos 168 manufactured by BASF Japan Ltd.

[0182] [Production Examples 4 to 8] Polyamide (A-1), 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 compounded as described in Table 1 and melt-kneaded using a twin-screw extruder (manufactured by Parker Corporation, screw diameter: 25 mm, cylinder with 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 resin composition. The raw materials were supplied from the following locations of the extruder. The obtained pellets of the polyamide resin composition were dried under reduced pressure at 80 °C for 24 hours.

[0183] Kneading method A Polyamide (A-1): Supplied from C4 Acid-modified ethylene-α-olefin copolymer (B-1): Supplied from the hopper Ethylene-α-olefin copolymer (C): Supplied from C2 Optional component: Supplied from the hopper

[0184] Kneading method B Polyamide (A-1): Supplied from the hopper Acid-modified ethylene-α-olefin copolymer (B-1): Supplied from the hopper Ethylene-α-olefin copolymer (C): Supplied from C3 Optional component: Supplied from the hopper

[0185] The pellets of the polyamide resin composition obtained in Production Examples 4 to 8 were observed for their phase structure using an atomic force microscope (AFM) Cypher ES manufactured by Oxford Instruments. The cantilever used was OMCL-AC160TSA manufactured by Olympus, and the AC mode (tapping mode) was selected. The confirmed structures were classified as follows. X structure: It has a continuous phase (α) containing polyamide (A) and a dispersed phase (β) containing polyamide (A), an acid-modified ethylene·α-olefin copolymer (B), and an ethylene·α-olefin copolymer (C) dispersed in the continuous phase (α), and the dispersed phase (β) has a multiple dispersed phase structure having a continuous phase (β1) containing an acid-modified ethylene·α-olefin copolymer (B) and an ethylene·α-olefin copolymer (C) and a dispersed phase (β2) containing polyamide (A) dispersed in the continuous phase (β1). Y structure: It has a continuous phase (α) containing polyamide (A) and a dispersed phase (β) containing an acid-modified ethylene·α-olefin copolymer (B) and an ethylene·α-olefin copolymer (C) dispersed in the continuous phase (α) (the dispersed phase (β) does not have a dispersed phase (β2) containing polyamide (A)). The results are shown in Table 1.

[0186] [Examples 1 to 3, Comparative Examples 1 to 6] The polyamide resin compositions, polyamide (A-1), acid-modified ethylene·α-olefin copolymer (B-1), ethylene·α-olefin copolymer (C-2), optional components (D-1) and (D-2) obtained in Production Examples 4 to 8 were melt-kneaded with a twin-screw extruder (manufactured by Parker Corporation, screw diameter: 25 mm, cylinder has a total of 6 blocks from C1 to C6) at the formulations described in Table 1 (cylinder temperature: 250 °C, screw rotation speed: 200 rpm, total discharge amount: 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 parts of the extruder. The obtained pellets of the polyamide resin composition were dried under reduced pressure at 80 °C for 24 hours.

[0187] Kneading method Polyamide compositions of Production Examples 4 to 8: Supplied from the hopper Polyamide (A-1): Supplied from the hopper Acid-modified ethylene·α-olefin copolymer (B-1): Supplied from the hopper Ethylene·α-olefin copolymer (C-2): Supplied from C3 Optional component: Supplied from a hopper

[0188] The pellets of the obtained polyamide resin composition were observed for their phase structure in the same manner as the pellets of Production Examples 4 to 8, and evaluated by the same classification.

[0189] Subsequently, injection molding was performed using the obtained pellets (injection molding machine: NN100 manufactured by Niigata Machine Co., Ltd., cylinder temperature: 245 °C, injection pressure: 117.7 MPa, mold temperature: 80 °C) to prepare test pieces for physical property tests.

[0190] The Charpy impact strength of the injection molded product was measured and calculated by the method described in JIS K7111.

[0191] The evaluation results are shown in Table 2.

[0192]

Table 1

[0193]

Table 2

Claims

1. A polyamide resin composition containing polyamide (A), an acid-modified ethylene / α-olefin copolymer (B), and an ethylene / α-olefin copolymer (C), having a continuous phase (α) and a dispersed phase (β) dispersed in the continuous phase (α), wherein the continuous phase (α) contains polyamide (A), and the dispersed phase (β) contains polyamide (A), an acid-modified ethylene / α-olefin copolymer (B), and an ethylene / α-olefin copolymer (C). Polyamide resin composition (X).

2. The dispersed phase (β) has a continuous phase (β1) and a dispersed phase (β2), wherein the continuous phase (β1) contains the acid-modified ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C), and the dispersed phase (β2) contains the polyamide (A). The polyamide resin composition (X) according to Claim 1.

3. 30 to 98.9% by mass of polyamide (A), 1 to 50% by mass of an acid-modified ethylene / α-olefin copolymer (B), and 0.1 to 50% by mass of an ethylene / α-olefin copolymer (C) (however, the total of 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 (X) according to Claim 1.

4. The acid-modified ethylene / α-olefin copolymer (B) satisfies the following requirements (b-1) to (b-3), and the ethylene / α-olefin copolymer (C) satisfies the following requirements (c-1) and (c-2). The polyamide resin composition (X) according to Claim 1; (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) It 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 (however, the total amount of the structural units derived from ethylene and the structural units derived from an α-olefin having 3 to 8 carbon atoms is 100 mol%); (b-3) The structural units derived from maleic acid or maleic anhydride are 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%).

5. The polyamide resin composition (X) according to claim 1, and A polyamide resin composition (Y) containing polyamide (A) or polyamide (A) and an acid-modified ethylene / α-olefin copolymer (B).

6. 40 to 90% by mass of polyamide (A), 0 to 20% by mass of an acid-modified ethylene / α-olefin copolymer (B), and 10 to 60% by mass of the polyamide resin composition (X) according to claim 1, (however, the total amount of polyamide (A), acid-modified ethylene / α-olefin copolymer (B), and polyamide resin composition (X) is 100% by mass), The polyamide resin composition (Y) according to claim 5.

7. A molded article containing the polyamide resin composition (X) according to any one of claims 1 to 4, or the polyamide resin composition (Y) according to claim 5 or 6.

8. An interior and exterior automotive material containing the polyamide resin composition (X) according to any one of claims 1 to 4, or the polyamide resin composition (Y) according to claim 5 or 6.

9. An automotive cover member containing the polyamide resin composition (X) according to any one of claims 1 to 4, or the polyamide resin composition (Y) according to claim 5 or 6.

10. A member for an automotive door containing the polyamide resin composition (X) according to any one of claims 1 to 4, or the polyamide resin composition (Y) according to claim 5 or 6.

11. An electronic member containing the polyamide resin composition (X) according to any one of claims 1 to 4, or the polyamide resin composition (Y) according to claim 5 or 6.

12. The step of obtaining a polyamide resin composition (X), and The step of melt-kneading the polyamide (A), the polyamide resin composition (X), and optionally an acid-modified ethylene / α-olefin copolymer (B), A method for producing a polyamide resin composition (Y), The step of obtaining the polyamide resin composition (X) is A step of melt-kneading the acid-modified ethylene / α-olefin copolymer (B) and the ethylene / α-olefin copolymer (C); A step of melt-kneading a polymer mixture obtained by melt-kneading the acid-modified copolymer (B) and the copolymer (C) with the polyamide (A), and the method for producing a polyamide resin composition (Y) includes the above steps. A method for producing a polyamide resin composition (Y).

13. The production method according to claim 12, 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 (Formula 1), and A method including a step of polymerizing ethylene and an α-olefin 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.]

14. In the formula (1), R １３ and R １４ The production method according to claim 13, wherein either one or both of them are aryl groups.

15. 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 13.

Images