Ethylene / 1-butene graft-modified copolymer, polyamide resin composition, and molded products.

Abstract

One embodiment of the present invention provides a graft-modified ethylene / 1-butene copolymer suitable as an impact resistance modifier for engineering plastics such as polyamide, and also provides a polyamide resin composition having an excellent balance between the fluidity and impact resistance of a molded body by using said graft-modified ethylene / 1-butene copolymer.　One embodiment of the present invention provides a graft-modified ethylene / 1-butene copolymer (A) in which an ethylene / 1-butene copolymer (a) that satisfies requirements (a-i) and (a-ii) is graft-modified with a polar compound. The requirements (a-i) and (a-ii) are disclosed in the specification.

Description

Graft-modified ethylene / 1-butene copolymer, polyamide resin composition, and molded article

[0001] One embodiment of the present invention relates to a graft-modified ethylene / 1-butene copolymer, a polyamide resin composition containing the graft-modified ethylene / 1-butene copolymer, and uses thereof.

[0002] Polyamide resins are widely used in the automotive, electrical, and electronic fields, taking advantage of their excellent properties as engineering plastics. Automotive and electrical components used in these fields are often required to have impact resistance due to their functional needs. A known method for imparting impact resistance is to blend a modified polyolefin resin with a polyamide resin (see Patent Documents 1 and 2).

[0003] Polyamide resins are used, for example, in automobile parts, and in recent years, there has been a strong demand for weight reduction to reduce fuel consumption, so there is a demand for thinner walls. However, in general, when the wall thickness of a molded product of polyamide resin is reduced, the impact resistance is rapidly reduced.

[0004] Japanese Patent Application Publication No. 5-32886 Special Publication No. 2021-503022

[0005] The modified polyolefin resins disclosed in Patent Documents 1 and 2 are modified ethylene-propylene polymers. The present inventors have confirmed that polyamide resins containing such polymers cannot simultaneously achieve both fluidity and the impact resistance of molded articles containing the polyamide resin. In other words, it is difficult to improve the impact resistance of molded articles without impairing the fluidity of the polyamide resin, leaving room for improvement. Therefore, the problem to be solved by one embodiment of the present invention is to provide a graft-modified ethylene-1-butene copolymer suitable as an impact modifier for engineering plastics such as polyamide, and to provide a polyamide resin composition using the graft-modified ethylene-1-butene copolymer that has an excellent balance between fluidity and impact resistance of molded articles.

[0006] The present invention has the following aspects: [1] An ethylene / 1-butene copolymer (a) is a graft-modified ethylene / 1-butene copolymer (A) that has been graft-modified with a polar compound, and the ethylene / 1-butene copolymer (a) satisfies the following requirements (ai) and (a-ii): Requirement (ai): A melt flow rate (MFR) measured at 190°C under a load of 2.16 kg in accordance with ASTM D1238 2.16 ) measured at 190°C under a load of 10 kg in accordance with ASTM D1238. 10 ) ratio (MFR 10 / MFR 2.16 ) is in the range of 6.7 to 9.0. 1 The vinyl group content per 100,000 carbon atoms calculated by H-NMR is in the range of 5.0 to 20.0, and the total number of unsaturated bonds is in the range of 40.0 to 200.0.

[0007] [2] The graft-modified ethylene / 1-butene copolymer (A) according to [1], wherein the polar compound is at least one selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and a derivative thereof, a vinyl ester compound, and vinyl chloride.

[0008] [3] The ethylene / 1-butene copolymer (a) is a graft-modified ethylene / 1-butene copolymer (A) that has been graft-modified with a polar compound, and the graft-modified ethylene / 1-butene copolymer (A) satisfies the following requirements (A-i) to (A-v): Requirement (A-i): Melt flow rate (MFR) measured under conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 2.16 ) measured at 190°C under a load of 10 kg in accordance with ASTM D1238. 10 ) ratio (MFR 10 / MFR 2.16) is in the range of 11.5 to 18.0. 1 The vinyl group content per 100,000 carbon atoms calculated by H-NMR is in the range of 5.0 to 20.0, and the total amount of unsaturated bonds is in the range of 40.0 to 200.0. Requirement (A-iii): The amount of graft modification is in the range of 0.1 to 2.0% by mass relative to 100% by mass of the graft-modified ethylene / 1-butene copolymer (A). Requirement (A-iv): The melt flow rate (MFR) measured under conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 is 2.16 Requirement (A-v): The density measured at 25°C in accordance with ASTM D1505 is 850 to 885 kg / m 3 is in the range.

[0009] [4] The graft-modified ethylene / 1-butene copolymer (A) according to [3], wherein the polar compound is at least one selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.

[0010] [5] A polyamide resin composition containing 1 to 50 parts by mass of the graft-modified ethylene / 1-butene copolymer (A) according to any one of [1] to [4] and 50 to 99 parts by mass of a polyamide resin (B) (wherein the total of the graft-modified ethylene / 1-butene copolymer (A) and the polyamide resin (B) is 100 parts by mass).

[0011] [6] The polyamide resin composition according to [5], wherein the polyamide resin (B) is one or more aliphatic polyamide resins selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 612, polyamide 610, and polyamide 1010.

[0012] [7] Pellets containing the polyamide resin composition according to [5] or [6].

[0013] [8] A molded article comprising the polyamide resin composition according to [5] or [6].

[0014] [9] An injection-molded article comprising the polyamide resin composition according to [5] or [6].

[0015]

[10] An automobile part comprising the polyamide resin composition according to [5] or [6].

[0016]

[11] An electronic part comprising the polyamide resin composition according to [5] or [6].

[0017]

[12] An automotive electrical component comprising the polyamide resin composition according to [5] or [6].

[0018] The graft-modified ethylene / 1-butene copolymer (A) obtained in one embodiment of the present invention is suitable as an impact modifier while suppressing a decrease in the fluidity of engineering plastics such as polyamides. Furthermore, a polyamide resin composition containing the graft-modified ethylene / 1-butene copolymer (A) in one embodiment of the present invention has a fluidity suitable for producing molded articles, and the resulting molded articles have high impact resistance even when thin-walled. In other words, the polyamide resin composition has an excellent balance between fluidity and the impact resistance of the molded articles.

[0019] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments and can be implemented with appropriate modifications within the scope of the object of the present invention.

[0020] In this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower and upper limits.

[0021] In this specification, when a numerical range is indicated by "to", the units written before or after the range indicate the same units unless otherwise specified.

[0022] In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment. Furthermore, in the present specification, unless otherwise specified, each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more types.

[0023] In this specification, the content of each component in a composition or each structural unit in a polymer means, when a plurality of substances or structural units corresponding to each component or each structural unit in a polymer are present in the composition, the total content of the corresponding substance present in the composition or each of the plurality of structural units present in the polymer, unless otherwise specified.

[0024] <Ethylene / 1-butene copolymer (a)> As a raw material for the graft-modified ethylene / 1-butene copolymer (A) according to one embodiment of the present invention, an ethylene / 1-butene copolymer (a) is used. The ethylene / 1-butene copolymer (a) may also be referred to as component (a). The ethylene / 1-butene copolymer (a) typically satisfies the following requirements (ai) and (a-ii):

[0025] [Requirement (a-i)] The melt flow rate (MFR) measured under the conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 2.16 ) measured at 190°C under a load of 10 kg in accordance with ASTM D1238. 10 ) ratio (MFR 10 / MFR 2.16 ) is in the range of 6.7 to 9.0. 10 / MFR 2.16 is preferably in the range of 6.8 to 8.9, more preferably 6.9 to 8.8, and even more preferably 7.0 to 8.7. 10 / MFR 2.16 When the graft-modified ethylene / 1-butene copolymer (A) produced by graft-modifying the ethylene / 1-butene copolymer (a) with a polar compound is mixed with a polyamide resin to produce a polyamide resin composition, the polyamide resin composition has excellent flowability, and a molded article containing the polyamide resin composition has excellent impact resistance.

[0026] [Requirement (a-ii)] 1The vinyl group content per 100,000 carbon atoms calculated by H-NMR is in the range of 5.0 to 20.0, and the total amount of unsaturated bonds is in the range of 40.0 to 200.0. The vinyl group content is preferably in the range of 5.5 to 17.0, more preferably 6.0 to 14.0, and even more preferably 6.5 to 11.0. The total amount of unsaturated bonds is preferably in the range of 45.0 to 190.0, more preferably 50.0 to 180.0, and even more preferably 55.0 to 170.0. When a polyamide resin composition is produced by blending a graft-modified ethylene-1-butene copolymer (A) produced by graft-modifying an ethylene-1-butene copolymer (a) having a total unsaturated bond content in the above range with a polar compound with a polyamide resin, the polyamide resin composition can give a molded article having excellent flowability and excellent impact resistance.

[0027] The vinyl group content means the number of vinyl double bonds per 100,000 carbon atoms. The total amount of unsaturated bonds means the sum of the number of vinyl double bonds, the number of vinylidene double bonds, the number of di-substituted olefin double bonds, and the number of tri-substituted olefin double bonds per 100,000 carbon atoms. The vinyl group content and the total amount of unsaturated bonds are measured under the conditions described in the Examples section below. 1 It can be calculated by measuring H-NMR.

[0028] <Method for Producing Ethylene / 1-Butene Copolymer (a)> The ethylene / 1-butene copolymer (a) satisfying the requirements (ai) and (a-ii) can be produced by a known method. The ethylene / 1-butene copolymer (a) can be prepared, for example, by copolymerizing ethylene and 1-butene in the presence of a known catalyst capable of polymerizing olefins (e.g., a catalyst containing a solid titanium component and an organometallic compound as its main components, a vanadium-based catalyst comprising a soluble vanadium compound and an alkylaluminum halide compound, or a zirconium-based catalyst comprising a zirconium metallocene compound and an organoaluminum oxycompound). The catalyst is preferably a catalyst containing a metallocene compound as a catalyst component.

[0029] The component (a) preferably satisfies one or more requirements selected from the group consisting of the following requirements (a-iii) to (a-vi), more preferably satisfies two or more requirements, and particularly preferably satisfies all of the requirements:

[0030] [Requirement (a-iii)] MFR 2.16 is in the range of 2.0 to 20.0 g / 10 min. 2.16 The MFR of the ethylene / 1-butene copolymer (a) is preferably in the range of 2.2 to 18.0 g / 10 min, more preferably 2.5 to 16.0 g / 10 min, even more preferably 2.6 to 15.0 g / 10 min, and particularly preferably 3.0 to 14.0 g / 10 min. 2.16 is in the above range, when a polyamide resin composition is produced by mixing a graft-modified ethylene / 1-butene copolymer (A) produced by graft-modifying the ethylene / 1-butene copolymer (a) with a polar compound with a polyamide resin, the polyamide resin composition has excellent flowability, and a molded article containing the polyamide resin composition has excellent impact resistance.

[0031] [Requirement (a-iv)] The content of structural units derived from ethylene is 70 to 95 mol%, and the content of structural units derived from 1-butene is in the range of 5 to 30 mol% (provided that the total content of structural units derived from ethylene and structural units derived from 1-butene is 100 mol%). The content of structural units derived from ethylene is preferably in the range of 73 to 93 mol%, more preferably 76 to 91 mol%, even more preferably 78 to 89 mol%, and particularly preferably 80 to 87 mol%, and the content of structural units derived from 1-butene is preferably in the range of 7 to 27 mol%, more preferably 9 to 24 mol%, even more preferably 11 to 22 mol%, and particularly preferably 13 to 20 mol%.

[0032] The content (mol %) of the structural units derived from each of the comonomers is, for example, 13The content of structural units derived from 1-butene in component (a) is within the above range, and when a polyamide resin composition is produced by blending a graft-modified ethylene / 1-butene copolymer (A) produced by graft-modifying the ethylene / 1-butene copolymer (a) with a polar compound with a polyamide resin, the polyamide resin composition has excellent fluidity, and a molded article containing the polyamide resin composition has excellent impact resistance. The ethylene and 1-butene monomers constituting the ethylene / α-olefin copolymer (a) may be, for example, fossil fuel-derived monomers and / or biomass-derived monomers, and these monomers may be used alone or in combination of two or more.

[0033] [Requirements (a-v)] The density measured at 25°C in accordance with ASTM D1505 is 850 to 885 kg / m 3 The density is preferably in the range of 855 to 882 kg / m 3 , more preferably 860 to 879 kg / m 3 , more preferably 861 to 878 kg / m 3 , particularly preferably 865 to 876 kg / m 3 When the density of the ethylene / 1-butene copolymer (a) is within the above range, in the case where a polyamide resin composition is produced by mixing a graft-modified ethylene / 1-butene copolymer (A) produced by graft-modifying the ethylene / 1-butene copolymer (a) with a polar compound with a polyamide resin, the polyamide resin composition has excellent flowability, and a molded article containing the polyamide resin composition has light weight and excellent impact resistance.

[0034] [Requirements (a-vi)] The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is in the range of 1.2 to 3.5. By using an ethylene / 1-butene copolymer (a) having an Mw / Mn in the above range, when a polyamide resin composition is produced by mixing a graft-modified ethylene / 1-butene copolymer (A) produced by graft-modifying the ethylene / 1-butene copolymer (a) with a polar compound with a polyamide resin, the stickiness of a molded article containing the polyamide resin composition is suppressed.

[0035] <Graft-modified ethylene / 1-butene copolymer (A)> The graft-modified ethylene / 1-butene copolymer (A) according to one embodiment of the present invention is a copolymer in which the ethylene / 1-butene copolymer (a) is graft-modified with a polar compound.

[0036] <Polar Compound> In one embodiment of the present invention, a polar compound is used to graft-modify the ethylene / 1-butene copolymer (a) to produce a graft-modified ethylene / 1-butene copolymer (A). The polar compound is preferably at least one selected from the group consisting of hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids and derivatives thereof, vinyl ester compounds, and vinyl chloride. From the viewpoint of reactivity with polyamide resins, the polar compound is more preferably at least one selected from the group consisting of unsaturated carboxylic acids and derivatives thereof.

[0037] Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, trimethylolpropane mono(meth)acrylate, tetramethylolethane mono(meth)acrylate, butanediol mono(meth)acrylate, (Meth)acrylic acid esters such as polyethylene glycol mono(meth)acrylate and 2-(6-hydroxyhexanoyloxy)ethyl acrylate; 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2-(meth)acroyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, and 2-butene-1,4-diol.

[0038] Examples of the amino group-containing ethylenically unsaturated compound include alkyl ester derivatives of acrylic acid or methacrylic acid, such as aminoethyl (meth)acrylate, propylaminoethyl (meth)acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth)acrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate; vinylamine derivatives, such as N-vinyldiethylamine and N-acetylvinylamine; allylamine derivatives, such as allylamine, methacrylamine, N-methylacrylamine, N,N-dimethylacrylamide, and N,N-dimethylaminopropylacrylamide; acrylamide derivatives, such as acrylamide and N-methylacrylamide; aminostyrenes, such as p-aminostyrene; 6-aminohexylsuccinimide, and 2-aminoethylsuccinimide.

[0039] Examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate, glycidyl methacrylate, mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, mono- and diglycidyl esters of tetrahydrophthalic acid, mono- and diglycidyl esters of itaconic acid, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (nadic acid), TM ), mono- and diglycidyl esters of endo-cis-bicyclo[2.2.1]hept-5-ene-2-methyl-2,3-dicarboxylic acid (methyl nadic acid TM ), dicarboxylic acid mono- and alkyl glycidyl esters such as mono- and diglycidyl esters of allyl succinic acid (the alkyl group in the case of the monoglycidyl ester has 1 to 12 carbon atoms), alkyl glycidyl esters of p-styrenecarboxylic acid, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, and vinylcyclohexene monoxide.

[0040] Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-chlorostyrene, m-chlorostyrene, p-chloromethylstyrene, 4-vinylpyridine, 2-vinylpyridine, 5-ethyl-2-vinylpyridine, 2-methyl-5-vinylpyridine, 2-isopropenylpyridine, 2-vinylquinoline, 3-vinylisoquinoline, N-vinylcarbazole, and N-vinylpyrrolidone.

[0041] Examples of the vinyl ester compound include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl p-tert-butylbenzoate, vinyl salicylate, and vinyl cyclohexanecarboxylate.

[0042] Examples of the unsaturated carboxylic acid include unsaturated carboxylic acids having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. Examples of the derivatives of the unsaturated carboxylic acids include derivatives of unsaturated carboxylic acids having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms.

[0043] Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid. TM (endo cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid).

[0044] Examples of the derivatives of the unsaturated carboxylic acids include acid halide compounds, ester compounds, imide compounds, acid anhydrides, and ester compounds of the unsaturated carboxylic acids, and specific examples thereof include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

[0045] As the at least one member selected from the group consisting of unsaturated carboxylic acids and derivatives thereof, at least one member selected from the group consisting of unsaturated dicarboxylic acids and acid anhydrides thereof is preferred, and particularly preferred are maleic acid and nadic acid. TM The unsaturated carboxylic acid, which is a monomer constituting the graft-modified ethylene / 1-butene copolymer (A), may be, for example, a fossil fuel-derived monomer and / or a biomass-derived monomer, and these monomers may be used alone or in combination of two or more.

[0046] <Graft-Modified Ethylene / 1-Butene Copolymer (A)> The graft-modified ethylene / 1-butene copolymer (A) usually satisfies one or more requirements selected from the group consisting of the following requirements (A-i) to (A-v), preferably satisfies two or more requirements, and more preferably satisfies all of the requirements:

[0047] [Requirement (A-i)] The melt flow rate (MFR) measured under the conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 2.16 ) measured at 190°C under a load of 10 kg in accordance with ASTM D1238. 10 ) ratio (MFR 10 / MFR 2.16 ) is in the range of 11.5 to 18.0. 10 / MFR 2.16 is preferably in the range of 12.5 to 17.6, more preferably 13.0 to 17.3, and even more preferably 13.5 to 17.0. 10 / MFR 2.16 When the MFR of the graft-modified ethylene / 1-butene copolymer (A) is in the above range, the polyamide resin composition has excellent flowability, and a molded article having excellent impact resistance can be produced. 10 is preferably in the range of 0.1 to 100 g / 10 min, more preferably 0.5 to 90 g / 10 min, even more preferably 1 to 80 g / 10 min, more preferably 2 to 70 g / 10 min, still more preferably 3 to 65 g / 10 min, particularly preferably 4 to 60 g / 10 min, and most preferably 5 to 58 g / 10 min. 10 The graft-modified ethylene / 1-butene copolymer (A) having a molecular weight of 1.0 or less in the above range is easily dispersed in polyamide. Therefore, when a polyamide resin composition is produced by mixing the graft-modified ethylene / 1-butene copolymer (A) with a polyamide resin, the polyamide resin composition has excellent flowability, and a molded article containing the polyamide resin composition has excellent impact resistance.

[0048] [Requirement (A-ii)] 1The vinyl group content per 100,000 carbon atoms calculated by H-NMR is in the range of 5.0 to 20.0, and the total amount of unsaturated bonds is in the range of 40.0 to 200.0. The vinyl group content is preferably in the range of 5.5 to 17.0, more preferably 6.0 to 14.0, and even more preferably 6.5 to 11.0. The total amount of unsaturated bonds is preferably in the range of 45.0 to 190.0, more preferably 50.0 to 180.0, and even more preferably 55.0 to 170.0.

[0049] When a polyamide resin composition is produced by mixing a graft-modified ethylene / 1-butene copolymer (A) having a total unsaturated bond content within the above range with a polyamide resin, the polyamide resin composition can give a molded article having excellent flowability and impact resistance. The vinyl group content and the total unsaturated bond content are determined under the conditions described in the Examples section below. 1 It can be calculated by measuring H-NMR.

[0050] [Requirement (A-iii)] The graft modification amount is in the range of 0.1 to 2.0% by mass, based on 100% by mass of the graft-modified ethylene / 1-butene copolymer (A). The graft modification amount is preferably in the range of 0.3 to 1.7% by mass, more preferably 0.3 to 1.5% by mass, and even more preferably 0.5 to 1.2% by mass. When the graft modification amount of the graft-modified ethylene / 1-butene copolymer (A) is in the above range, the polyamide resin composition has excellent flowability, and molded articles containing the polyamide resin composition have excellent impact resistance. The graft modification amount can be calculated by measuring FT-IR under the conditions described in the Examples section below.

[0051] [Requirement (A-iv)] The melt flow rate (MFR) measured under the conditions of 190°C and a load of 2.16 kg in accordance with ASTM D1238 2.16 ) is in the range of 0.01 to 5.00 g / 10 min. 2.16The MFR of the graft-modified ethylene / 1-butene copolymer (A) is preferably in the range of 0.02 to 4.75 g / 10 min, more preferably 0.04 to 4.00 g / 10 min, still more preferably 0.08 to 3.00 g / 10 min, and particularly preferably 0.10 to 2.00 g / 10 min. 2.16 When the viscosity is within the above range, a polyamide resin composition having excellent moldability can be obtained, and a molded article having excellent impact resistance can be produced.

[0052] [Requirement (A-v)] The density measured at 25°C in accordance with ASTM D1505 is 850 to 885 kg / m 3 The density is preferably 858 to 882 kg / m 3 , more preferably 859 to 880 kg / m 3 , more preferably 866 to 879 kg / m 3 , more preferably 870 to 877 kg / m 3 When the density of the graft-modified ethylene / 1-butene copolymer (A) is within the above range, a molded article that is lightweight and has excellent impact resistance even when thin-walled can be produced from a polyamide resin composition containing the graft-modified ethylene / 1-butene copolymer (A) and a polyamide resin.

[0053] In the graft-modified ethylene / 1-butene copolymer (A), the graft position of the polar compound grafted onto the ethylene / 1-butene copolymer (a) is not particularly limited, as long as the polar compound is bonded to any carbon atom in the ethylene / 1-butene copolymer (a).

[0054] <Method for Producing Graft-Modified Ethylene / 1-Butene Copolymer (A)> The graft-modified ethylene / 1-butene copolymer (A) can be obtained by various known production methods, for example, by graft-reacting the ethylene / 1-butene copolymer (a) with the polar compound in the presence of a radical initiator. Examples of methods for producing the graft-modified ethylene / 1-butene copolymer (A) by graft-reacting the ethylene / 1-butene copolymer (a) with the polar compound include the following: (1) A method in which the ethylene / 1-butene copolymer (a) is melted, a polar compound, etc. is added, and graft copolymerization is carried out. (2) A method in which the ethylene / 1-butene copolymer (a) is dissolved in a solvent, a polar compound, etc. is added, and graft copolymerization is carried out.

[0055] In these methods, the amount of the polar compound used is usually 0.010 to 15 parts by mass, preferably 0.010 to 5.0 parts by mass, relative to 100 parts by mass of the ethylene / 1-butene copolymer (a). The amount of the radical initiator used is usually 0.001 to 1.0 part by mass, preferably 0.005 to 0.30 part by mass, relative to 100 parts by mass of the ethylene / 1-butene copolymer (a).

[0056] Examples of the radical initiator that can be used include organic peroxides, azo compounds, and metal hydrides. The radical initiator can be used by directly mixing it with a polar compound (e.g., maleic acid or its anhydride), the unmodified ethylene-1-butene copolymer (a), and other components, or it can be used after dissolving it in a small amount of organic solvent. The organic solvent is not particularly limited as long as it is an organic solvent that can dissolve the radical initiator.

[0057] The reaction temperature in the graft reaction is usually in the range of 70 to 280° C., preferably 80 to 260° C. The reaction time in the graft reaction is usually 0.5 to 15 hours, preferably 1 to 10 hours.

[0058] The graft-modified ethylene / 1-butene copolymer (A) can also be produced by reacting a polar compound with the ethylene / 1-butene copolymer (a) in the presence of a radical initiator without using a solvent, such as an extruder. The reaction without a solvent is usually desirably carried out at a temperature equal to or higher than the melting point of the ethylene / 1-butene copolymer (a) for 0.5 to 10 minutes.

[0059] <Polyamide Resin (B)> The polyamide resin (B), which is the main component of the polyamide resin composition according to one embodiment of the present invention, is not particularly limited, and any of various conventionally known polyamide resins, such as aliphatic polyamides, semi-aromatic polyamides, or aromatic polyamides, can be used without limitation, as long as the effects of the present invention are not impaired. As the polyamide resin (B), for example, an amino acid lactam or a melt-moldable polyamide resin obtained by a polycondensation reaction of an organic diamine and an organic dicarboxylic acid can be used.

[0060] Examples of the organic dicarboxylic acid include organic dicarboxylic acids having 4 to 12 carbon atoms, such as adipic acid, pimelic acid, suberic acid, phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, phenylenedioxydiacetic acid, sebacic acid, and dodecanedioic acid, and organic dicarboxylic acids having 13 or more carbon atoms, such as oxydibenzoic acid, diphenylmethanedicarboxylic acid, diphenylsulfonedicarboxylic acid, and biphenyldicarboxylic acid. Examples of the organic diamine include organic diamines having 2 to 13 carbon atoms, such as hexamethylenediamine, octamethylenediamine, nonanediamine, octanediamine, decanediamine, undecanediamine, and dodecanediamine.

[0061] Examples of the polyamide resin (B) include polycondensates of organic dicarboxylic acids having 4 to 12 carbon atoms and organic diamines having 2 to 13 carbon atoms. Examples of the polycondensates include polyhexamethylene adipamide [polyamide 66], which is a polycondensate of hexamethylene diamine and adipic acid, polyhexamethylene azelamide [polyamide 69], which is a polycondensate of hexamethylene diamine and azelaic acid, polyhexamethylene sebacamide [polyamide 610], which is a polycondensate of hexamethylene diamine and sebacic acid, and polyhexamethylene dodecane [polyamide 611], which is a polycondensate of hexamethylene diamine and dodecanedioic acid. Examples of suitable polyamides include polyamide 612, polydecamethylenesebacamide (polyamide 1010), which is a polycondensation product of decamethylenediamine and sebacic acid, semi-aromatic polyamides (polyamide 6T, polyamide 9T, polyamide 10T, polyamide 11T), which are polycondensation products of aromatic dicarboxylic acids and aliphatic diamines, and polybis(4-aminocyclohexyl)methanedodecane, which is a polycondensation product of bis-p-aminocyclohexylmethane and dodecanedioic acid.

[0062] The polyamide resin (B) also includes a polycondensation product of an ω-amino acid. An example of the polycondensation product of an ω-amino acid is polyundecaneamide [polyamide 11], which is a polycondensation product of ω-aminoundecanoic acid. Furthermore, the polyamide resin (B) also includes a ring-opening polymer of a lactam. An example of the ring-opening polymer of a lactam is polycapramide [polyamide 6], which is a ring-opening polymer of ε-aminocaprolactam, and polylauriclactam [polyamide 12], which is a ring-opening polymer of ε-aminolaurolactam.

[0063] As long as the polyamide resin (B) exhibits thermoplasticity, it may be modified with a small amount of a trivalent or higher polyhydroxy compound such as a triol or tricarboxylic acid, a polycarboxylic acid, etc. From the viewpoint of the balance between the fluidity of the polyamide resin composition and the impact resistance of the molded article, the polyamide resin (B) is preferably one or more aliphatic polyamide resins selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 612, polyamide 610, and polyamide 1010.

[0064] Of the polyamide resins (B), aliphatic polyamides are preferred, and polyhexamethylene adipamide [polyamide 66], polyhexamethylene azelamide [polyamide 69], and polycapramide [polyamide 6] are more preferred.

[0065] The polyamide resin (B) may be, for example, a polyamide resin produced from adipic acid, isophthalic acid, and hexamethylenediamine, or a blend of two or more polyamide resins, such as a mixture of polyamide 6 and polyamide 66. The raw material for the polyamide resin (B) may be either a fossil fuel-derived raw material or a biomass-derived raw material. Furthermore, a fossil fuel-derived raw material and a biomass-derived raw material may be used in combination.

[0066] The number average molecular weight (Mn) of the polyamide resin (B) measured by GPC is preferably in the range of 15,000 to 27,000, more preferably 17,000 to 25,000, and particularly preferably 19,000 to 23,000. The spiral flow of the polyamide resin (B) measured with an injection molding machine is preferably greater than 600 mm, more preferably greater than 625 mm, and particularly preferably greater than 650 mm. For polyamide 66, the spiral flow measured under conditions of a dissolution temperature of 290°C and an injection pressure of 900 Bar is preferably within the above range, and for polyamide 6, the spiral flow measured under conditions of a dissolution temperature of 260°C and an injection pressure of 900 Bar is preferably within the above range. By using a polyamide resin (B) having a number average molecular weight (Mn) and spiral flow within the above ranges, the polyamide resin composition tends to exhibit the fluidity inherent to the polyamide resin (B), and the fluidity is not significantly impaired even when mixed with the graft-modified ethylene-1-butene copolymer (A). As a result, the fluidity of the polyamide resin composition and the impact resistance of a molded article containing the polyamide resin composition are well balanced and excellent.

[0067] <Polyamide Resin Composition> A polyamide resin composition according to one embodiment of the present invention preferably contains 50 to 99 parts by mass of the polyamide resin (B) and 1 to 50 parts by mass of the graft-modified ethylene-1-butene copolymer (A), relative to 100 parts by mass of the total content of the polyamide resin (B) and the graft-modified ethylene-1-butene copolymer (A). The polyamide resin composition more preferably contains 65 to 97 parts by mass of the polyamide resin (B) and 3 to 35 parts by mass of the graft-modified ethylene-1-butene copolymer (A), and particularly preferably contains 80 to 95 parts by mass of the polyamide resin (B) and 5 to 20 parts by mass of the graft-modified ethylene-1-butene copolymer (A).

[0068] When the content of the polyamide resin (B) and the content of the graft-modified ethylene-1-butene copolymer (A) in the polyamide resin composition are within the above ranges, the molded article of the polyamide resin composition has high impact resistance even when the molded article is thinned. The reason why the flowability of the polyamide resin composition and the impact resistance of the molded article are well balanced and excellent is presumed to be as follows.

[0069] That is, the ethylene / 1-butene copolymer (a) usually has an MFR falling within a specific range. 10 / MFR 2.16 and thus has long chain branches. Furthermore, the ethylene-1-butene copolymer (a) typically has a vinyl group content and a total unsaturated bond content within specific ranges. Therefore, a graft-modified ethylene-1-butene copolymer (A) using the ethylene-1-butene copolymer (a) has a viscosity ratio close to that of the polyamide resin (B), which facilitates dispersion of the graft-modified ethylene-1-butene copolymer (A) in the polyamide resin composition. Furthermore, since the graft-modified ethylene-1-butene copolymer (A) is grafted with a polar compound, it has high compatibility with the polyamide resin (B). Therefore, it is presumed that the graft-modified ethylene-1-butene copolymer (A) is further facilitated to be dispersed in the polyamide resin composition, resulting in a well-balanced and excellent flowability of the polyamide resin composition and impact resistance of the molded article.

[0070] <Other Components> The polyamide resin composition according to one embodiment of the present invention may further contain components other than the polyamide resin (B) and the graft-modified ethylene-1-butene copolymer (A), as long as the purpose of the present invention is not impaired. That is, the polyamide resin composition according to one embodiment of the present invention may contain additives such as weather resistance stabilizers, heat resistance stabilizers, ultraviolet absorbers, infrared absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, lubricants, pigments, dyes, plasticizers, antioxidants, hydrochloric acid absorbers, antioxidants, crystal nucleating agents, antifungal agents, antibacterial agents, flame retardants, organic fillers, mold release agents, surfactants, and softeners, as needed, as long as the purpose of the present invention is not impaired. These additives may be contained alone, or multiple additives may be contained. Furthermore, the polyamide resin composition according to one embodiment of the present invention may also contain other polymers as long as the purpose of the present invention is not impaired.

[0071] <Method for Producing Polyamide Resin Composition> The polyamide resin composition according to one embodiment of the present invention can be produced by a known method for producing a resin composition, which involves melt-kneading or the like, by sequentially or simultaneously mixing the polyamide resin (B), the graft-modified ethylene / 1-butene copolymer (A), and any other components as raw materials.

[0072] <Uses> The polyamide resin composition according to one embodiment of the present invention has excellent flowability, and the resulting molded articles have high impact resistance even when thin-walled. Therefore, the polyamide resin composition can be used to produce various pellets and molded articles.

[0073] <Pellets> One embodiment of the present invention is pellets containing the polyamide resin composition. The pellets have, for example, a spherical, cylindrical, lenticular, or cubic shape. The pellets can be produced by known pelletizing methods. Examples of methods for producing the pellets include a method in which the polyamide resin (B), the graft-modified ethylene-1-butene copolymer (A), and any other components are uniformly melt-mixed, extruded using an extruder, and then hot-cut or strand-cut to produce spherical, cylindrical, or lenticular pellets. In this case, cutting may be performed either in water or in an air stream. Cubic pellets can also be obtained, for example, by uniformly mixing the components, forming them into a sheet using a roll, or the like, and then using a sheet pelletizer. The pellets preferably have a length of 3 cm or less at their longest point.

[0074] The pellets can be used, for example, to produce a molded product, preferably a molded product by melt molding, which can be performed by any melt molding method, such as compression molding, injection molding, or extrusion molding.

[0075] <Injection-molded article> One embodiment of the present invention is an injection-molded article containing the polyamide resin composition. The injection-molded article can be obtained by injection molding the polyamide resin composition by a commonly used method.

[0076] The injection-molded article of one embodiment of the present invention can be used in a wide range of applications, from household items such as daily necessities and recreational uses to general industrial and industrial products. Examples of uses for the injection-molded article include parts or components for various items such as home appliances, communication equipment, electrical and electronic equipment, automobiles, other vehicles, ships, aircraft, building materials, civil engineering materials, agricultural materials, power tools, food containers, films, sheets, and fibers. The injection-molded article can be particularly suitable for use as an automobile part or component. The injection-molded article can also be suitable for use as a part for gasoline-powered vehicles, hybrid vehicles (HVs), plug-in hybrid vehicles (PHVs), electric vehicles (EVs), fuel cell vehicles (FCVs), and the like. The injection-molded article can also be suitable for use as a part for electric motorcycles.

[0077] The automotive parts or members include a wide range of parts or members, including interior parts or members such as door trim, door modules, instrument panels, center panels, roof panels, tailgate panels, accelerator and brake pedals, vertical exterior panels such as doors, fenders, and tailgates, horizontal exterior panels such as hoods and roofs, engine compartment members such as air intakes, front-end modules, and fan shrouds, and automotive electrical parts, including wire harness connectors, cable connectors, lamp sockets, on-board sensor switches, combination switches, batteries, motor mounts, power modules, converters, capacitors, insulators, motor terminal blocks, and electric compressors.

[0078] Hereinafter, one embodiment of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The components used in the following examples and comparative examples are as follows.

[0079] <Ethylene / 1-butene copolymer (a)> To produce the graft-modified ethylene / 1-butene copolymer (A), the ethylene / 1-butene copolymers (a-1) to (a-11) and (a'-1) polymerized using a metallocene catalyst were used.

[0080] Production Example 1 Production of Ethylene / 1-Butene Copolymer (a-1) To one supply port of a continuous polymerization reactor having an internal volume of 130 L and equipped with a stirring blade, a hexane solution of triisobutylaluminum as a cocatalyst was supplied at a rate of 12 mmol / hr, a hexane solution of bis(4-methylphenyl)methylene(cyclopentadienyl)(1,2,3,4,7,8,9,10-octahydro-1,1,4,4,7,7,10,10-octamethyldibenzo(b,h)fluoren-12-yl)zirconium dichloride as a main catalyst was supplied at a rate of 0.0082 mmol / hr, and a hexane slurry solution of modified methylaluminoxane was supplied at a rate of 0.034 mmol / hr. Normal hexane was continuously supplied so that the total rate of the catalyst solution and dehydrated and purified normal hexane to be used as a polymerization solvent was 37.3 L / hr.

[0081] At the same time, ethylene was continuously fed to another feed port of the polymerization reactor at a rate of 6.6 kg / hr, 1-butene at a rate of 8.1 kg / hr, and hydrogen at a rate of 110 NL / hr, and continuous solution polymerization was carried out under the conditions of a polymerization temperature of 155°C, a total pressure of 2.5 MPaG, and a residence time of 0.5 hours. The normal hexane / toluene mixed solution of ethylene-1-butene copolymer produced in the polymerization reactor was continuously discharged through an outlet provided on the side of the polymerization reactor, and the jacket was opened at a rate of 3 kg / cm so that the normal hexane solution of ethylene-1-butene copolymer was heated to 130°C. 2 It led to a steam-heated connecting pipe.

[0082] The normal-hexane solution of ethylene-1-butene copolymer, maintained at approximately 200°C in a steam-jacketed connecting pipe, was continuously fed to a flash tank by adjusting the aperture of a pressure control valve provided at the end of the connecting pipe so as to maintain a pressure of approximately 2.5 MPaG. A feed port for injecting methanol, a catalyst deactivator, was attached immediately after the pressure control valve. Methanol was injected at a rate of approximately 11 L / hr and merged with the normal-hexane solution of ethylene-1-butene copolymer. During transfer to the flash tank, the solution temperature and the aperture of the pressure control valve were set so as to maintain the pressure in the flash tank at approximately 0.05 MPaG and the temperature of the vapor portion in the flash tank at approximately 200°C. The solution was then passed through a single-screw extruder with a die temperature set to 170°C. The strands were cooled in a water bath and cut with a pellet cutter to obtain ethylene-1-butene copolymer (a-1) as pellets. The yield was 8.2 kg / 2 hr.

[0083] Production Example 2: Production of ethylene / 1-butene copolymer (a-2) An ethylene / 1-butene copolymer (a-2) was produced in the same manner as in Production Example 1, except that the supply rate of 1-butene was adjusted to 7.5 kg / hr.

[0084] Production Example 3: Production of ethylene / 1-butene copolymer (a-3) An ethylene / 1-butene copolymer (a-3) was produced in the same manner as in Production Example 1, except that the supply rate of 1-butene was adjusted to 7.4 kg / hr.

[0085] Production Example 4 Production of Ethylene / 1-Butene Copolymer (a-4) An ethylene / 1-butene copolymer (a-4) was produced in the same manner as in Production Example 1, except that bis(4-methylphenyl)methylene(cyclopentadienyl)(1,2,3,4,7,8,9,10-octahydro-1,1,4,4,7,7,10,10-octamethyldibenzo(b,h)fluoren-12-yl)zirconium dimethyl and triphenylcarbenium tetrakis(pentafluorophenyl)borate were used as the main catalysts, and the feed rates of 1-butene and ethylene were adjusted to 9.8 kg / hr, 6.9 kg / hr, and the polymerization temperature was 130°C.

[0086] Production Example 5 Production of Ethylene / 1-Butene Copolymer (a-5) An ethylene / 1-butene copolymer (a-5) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 6.4 kg / hr, the supply rate of ethylene was 5.0 kg / hr, and the polymerization temperature was 160°C.

[0087] Production Example 6 Production of Ethylene / 1-Butene Copolymer (a-6) An ethylene / 1-butene copolymer (a-6) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 9.4 kg / hr, the supply rate of ethylene was 6.6 kg / hr, and the polymerization temperature was 150°C.

[0088] Production Example 7 Production of Ethylene / 1-Butene Copolymer (a-7) An ethylene / 1-butene copolymer (a-7) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 9.1 kg / hr, the supply rate of ethylene was 6.4 kg / hr, and the polymerization temperature was 150°C.

[0089] Production Example 8 Production of Ethylene / 1-Butene Copolymer (a-8) An ethylene / 1-butene copolymer (a-8) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 8.7 kg / hr, the supply rate of ethylene was 6.2 kg / hr, and the polymerization temperature was 150°C.

[0090] Production Example 9 Production of Ethylene / 1-Butene Copolymer (a-9) An ethylene / 1-butene copolymer (a-9) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 8.8 kg / hr, the supply rate of ethylene was 6.4 kg / hr, and the polymerization temperature was 140°C.

[0091] Production Example 10: Production of ethylene / 1-butene copolymer (a-10) An ethylene / 1-butene copolymer (a-10) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 9.8 kg / hr, the supply rate of ethylene was 5.9 kg / hr, and the polymerization temperature was 140°C.

[0092] <Production Example 11: Production of ethylene / 1-butene copolymer (a-11)> An ethylene / 1-butene copolymer (a-11) was produced in the same manner as in Production Example 4, except that the supply rate of 1-butene was 9.4 kg / hr, the supply rate of ethylene was 5.8 kg / hr, and the polymerization temperature was 140°C.

[0093] <Ethylene / 1-butene copolymer (a'-1)> ENGAGE 7447 (manufactured by The Dow Chemical Company) was used as the ethylene / 1-butene copolymer (a'-1).

[0094] The physical properties of the ethylene / 1-butene copolymer (a) were evaluated by the following physical property measurement methods. The evaluation results are shown in Table 1.

[0095] [MFR 2.16 , MFR 10 and MFR 10 / MFR 2.16 The melt flow rate (MFR) was measured according to ASTM D1238 under the conditions of 190°C and 2.16 kg load, and 190°C and 10 kg load. 2.16 and MFR 10 ) was measured, and MFR 10 / MFR 2.16 was calculated.

[0096] [Density] Measured at 25°C in accordance with ASTM D1505.

[0097] [Content (Composition) of Structural Units Derived from Comonomers] The content of structural units derived from comonomers was measured using a nuclear magnetic resonance (NMR) measurement device (JNM GX-400 model, manufactured by JEOL Ltd.). 0.35 g of a sample was dissolved in 2.0 mL of hexachlorobutadiene by heating. This solution was filtered through a glass filter (G2), and then 0.5 mL of deuterated benzene was added. The solution was placed in an NMR tube with an inner diameter of 10 mm and heated at 120°C. 13 C-NMR measurement was carried out. The number of accumulations was set to 8000 or more. 13 The contents (mol %) of structural units derived from ethylene and structural units derived from 1-butene in the ethylene-1-butene copolymer were quantified by C-NMR spectroscopy.

[0098] [Vinyl group content, vinylidene group content, total unsaturated bond content] 0.35 g of a sample was dissolved in 2.0 mL of hexachlorobutadiene by heating. After filtering the solution through a glass filter (G2), 0.5 mL of deuterated benzene was added, and the solution was placed in an NMR tube with an inner diameter of 10 mm and heated at 120°C. 1 H-NMR measurement was carried out. The number of accumulations was set to 100 or more. 1 The vinyl group content, vinylidene group content, and total unsaturated bond content (number / 100,000 carbons) in the ethylene-1-butene copolymer were determined by H-NMR spectroscopy. 1 The H-NMR measurement was carried out using a nuclear magnetic resonance (NMR) measurement device (manufactured by JEOL Ltd., JNM GX-400 model).

[0099] In addition, 1 In the H-NMR spectrum, signals derived from double bonds are observed, including signals derived from vinyl double bonds, vinylidene double bonds, disubstituted olefin double bonds, and trisubstituted olefin double bonds. From the integrated intensity of each signal, the vinyl group content, vinylidene group content, and the total amount of unsaturated bonds, which is the total amount of vinyl double bonds, vinylidene double bonds, disubstituted olefin double bonds, and trisubstituted olefin double bonds, were quantified. The double bond amount was quantified using the signal peak positions and quantification formula described in JP 2022-142958 A.

[0100] [Molecular weight distribution (Mw / Mn)] Gel permeation chromatography (GPC) was performed to determine the polystyrene-equivalent molecular weight Mw / Mn of each fraction. i-PSt Next, M i-PSt , [η] i-PSt ×M i-PSt = [η] i-EPR ×M i-EPR , [η] i-PSt = 1.37 x 10 -4 ×M i-PSt 0.686 , and [η] i-EPR = 7.2 x 10 -4 ×M i-EPR 0.667 Using the formula, the EPR-converted molecular weight M i-EPRThe molecular weight distribution (Mw / Mn) was calculated using the EPR-converted molecular weight.

[0101] Gel permeation chromatography (GPC) measurements were performed using a Waters gel permeation chromatograph Alliance GPC-2000 under the following conditions: Separation columns: two TSKgel GNH6-HT columns, two TSKgel GNH6-HTL columns; Column size: diameter 7.5 mm, length 300 mm; Column temperature: 140°C; Mobile phase: o-dichlorobenzene (Fujifilm Wako Pure Chemical Industries, Ltd.); Antioxidant: BHT (Takeda Pharmaceutical Co., Ltd.) 0.025% by mass; Flow rate: 1.0 mL / min; Sample concentration: 15 mg / 10 mL; Sample injection volume: 500 μL; Detector: differential refractometer; Standard polystyrene: molecular weights Mw<1000 and Mw>4×10 6 For the region where Mw is 1000 or less, the following is used: 6 For areas where

[0102]

[0103] <Graft-modified ethylene / 1-butene copolymer (A)> Graft-modified ethylene / 1-butene copolymers (A-1) to (A-11) and (A'-1) obtained by the following production method were used as the graft-modified ethylene / 1-butene copolymer (A). The physical properties of the graft-modified ethylene / 1-butene copolymer (A) were evaluated using the physical property measurement methods described above and the method for measuring the amount of graft modification described below. The evaluation results are shown in Table 2.

[0104] [Graft-modified ethylene / 1-butene copolymer (A-1)] 10 kg of ethylene / 1-butene copolymer (a-1), 100 g of maleic anhydride (MAH), and 5 g of 2,5-dimethyl-2,5-di-(t-butylperoxy)-3-hexyne (manufactured by NOF Corporation, trade name Perhexyne 25B) were dissolved in acetone and blended. The resulting blend was then charged into the hopper of a twin-screw extruder with a screw diameter of 25 mm and L / D = 42, and extruded into strands at a resin temperature of 250°C, a screw rotation speed of 150 rpm, and a throughput of 7 kg / hr. The resulting strands were thoroughly cooled and then granulated to obtain graft-modified ethylene / 1-butene copolymer (A-1).

[0105] [Graft-modified ethylene / 1-butene copolymer (A-2)] A graft-modified ethylene / 1-butene copolymer (A-2) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-2) was used.

[0106] [Graft-modified ethylene / 1-butene copolymer (A-3)] A graft-modified ethylene / 1-butene copolymer (A-3) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-3) was used.

[0107] [Graft-modified ethylene / 1-butene copolymer (A-4)] A graft-modified ethylene / 1-butene copolymer (A-4) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-4) was used.

[0108] [Graft-modified ethylene / 1-butene copolymer (A-5)] A graft-modified ethylene / 1-butene copolymer (A-5) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-5) was used.

[0109] [Graft-modified ethylene / 1-butene copolymer (A-6)] A graft-modified ethylene / 1-butene copolymer (A-6) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-6) was used.

[0110] [Graft-modified ethylene / 1-butene copolymer (A-7)] A graft-modified ethylene / 1-butene copolymer (A-7) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-7) was used.

[0111] [Graft-modified ethylene / 1-butene copolymer (A-8)] A graft-modified ethylene / 1-butene copolymer (A-8) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1) described above, except that the ethylene / 1-butene copolymer (a-8) was used.

[0112] [Graft-modified ethylene / 1-butene copolymer (A-9)] A graft-modified ethylene / 1-butene copolymer (A-9) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1), except that the ethylene / 1-butene copolymer (a-9) was used.

[0113] [Graft-modified ethylene / 1-butene copolymer (A-10)] A graft-modified ethylene / 1-butene copolymer (A-10) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1).

[0114] [Graft-modified ethylene / 1-butene copolymer (A-11)] A graft-modified ethylene / 1-butene copolymer (A-11) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1) described above, except that the ethylene / 1-butene copolymer (a-11) was used.

[0115] [Graft-modified ethylene / 1-butene copolymer (A'-1)] A graft-modified ethylene / 1-butene copolymer (A'-1) was obtained in the same manner as in the preparation of the graft-modified ethylene / 1-butene copolymer (A-1) described above, except that the ethylene / 1-butene copolymer (a'-1) was used.

[0116] [Graft Modification Amount] The graft modification amount (maleic anhydride modification amount (mass%)) of the graft-modified ethylene-1-butene copolymers (A-1) to (A-11) and (A'-1) was measured by FT-IR at a wave number of 1780 cm assigned to the carbonyl group. -1 The peak intensity was calculated from a separately prepared calibration curve.

[0117]

[0118] <Polyamide Resin (B)> The following polyamide resins (B-1) and (B-2) were used as the polyamide resin (B). [Polyamide Resin (B-1)] Polyamide 66 (manufactured by Toray Industries, Inc., Amilan CM3007, spiral flow (melting temperature: 290°C, injection pressure: 900 Bar), over 700 mm) [Polyamide Resin (B-2)] Polyamide 6 (manufactured by Toray Industries, Inc., Amilan CM1007, spiral flow (melting temperature: 260°C, injection pressure: 900 Bar), over 700 mm)

[0119] A dry blend was prepared by mixing 10 parts by mass of the graft-modified ethylene-1-butene copolymer (A-1) and 90 parts by mass of the polyamide resin (B-1), which was polyamide 66, using a Henschel mixer. Next, this dry blend was charged into the main inlet of a twin-screw extruder (L / D=40, 30 mmφ) set at 285°C, and extruded at a screw rotation speed of 180 rpm and a discharge rate of 15 kg / hr to prepare pellets of a polyamide resin composition.

[0120] The resulting polyamide resin composition pellets were dried at 100°C for 24 hours, and then injection molded to prepare test pieces for physical property tests. The physical properties of the polyamide resin composition were evaluated by the following test methods. The evaluation results are shown in Table 3.

[0121] [Physical Property Tests] (1) Charpy Impact Test Under the following test conditions, a hammer was swung down from the back of the notch of a fixed test specimen, and the impact strength was determined from the swing angle of the hammer after the test specimen broke and the lift angle of the hammer before the test. (Test Conditions) Test temperature: 23°C / -40°C, hammer capacity: 4J, lift angle: 149.9, test specimen: notched, remaining width 8mm, width 4mm

[0122] (2) Flowability Using an injection molding machine with a cylinder temperature of 290°C, an injection pressure of 100 MPa, a mold temperature of 80°C, and a mold clamping force of 50 tonnes, each sample was injection molded into a mold having a semicircular spiral groove of 3.8 mm diameter, and the flow distance (spiral flow length) was measured.

[0123] [Examples 2 to 17, Comparative Examples 1 to 4] Production of pellets of polyamide resin compositions, drying, preparation of test pieces, and evaluation of physical properties were carried out in the same manner as in Example 1, except that the compositions of the graft-modified ethylene / 1-butene copolymer (A) and the polyamide resin (B) in Example 1 were changed as shown in Tables 3 to 5. The results of the evaluations are shown in Tables 3 to 5.

[0124] [Examples 18 to 28, Comparative Examples 5 to 7] Production of pellets of polyamide resin compositions, drying, preparation of test pieces, and evaluation of physical properties were carried out in the same manner as in Example 1, except that the set temperature of the twin-screw extruder was changed to 245°C, the compositions of the graft-modified ethylene-1-butene copolymer (A) and the polyamide resin (B) were changed as shown in Tables 4 and 5, and the cylinder temperature in the flowability evaluation was changed to 245°C. The evaluation results are shown in Tables 4 and 5.

[0125]

[0126]

[0127]

Claims

DEPCT691. Graft modified ethylene / 1-butene copolymer (A) obtained by grafting ethylene / 1-butene copolymer (a) with a polar compound in which ethylene / 1-butene copolymer (a) satisfies the following requirements (ai) and (a-ii): Requirement (ai): Ratio (MFR10 / MFR2.16) of melt flow rate (MFR10) measured under conditions of 190°C and The 10 kg actuation force according to ASTMD1238 per melt flow rate (MFR2.16) was measured under 190°C and the 2.16 kg actuation force according to ASTMD1238 was in the range of 6.7 to 9.0; and specifications (a-ii): the amount of vinyl groups was in the range of 5.0 to 20.0 groups and the total amount of unsaturated bonds was in the range of 40.0 to 200.0 bonds per 100,000 carbon atoms when calculated by 1H-NMR2.Ethylene / 1-butene grafted copolymer (A) under claim 1, in which at least one polar compound is selected from the group of ethylene unsaturated compounds with hydroxyl groups, ethylene unsaturated compounds with amino groups, ethylene unsaturated compounds with epoxy groups, aromatic vinyl compounds, unsaturated carboxylic acids and their derivatives, vinyl esters and vinyl chlorides.

3. Ethylene / 1-butene grafted copolymer (A) obtained by grafting of ethylene / 1-butene copolymer. Mor(a) with polar compounds in which the grafted modified ethylene / 1-butene copolymer(A) conforms to the following specifications (Ai) to (Av): Specification (Ai): The ratio (MFR10 / MFR2.16) of the melt flow rate (MFR10) measured under 190°C and a force of 10 kg according to ASTMD1238 to the melt flow rate (MFR2.16) measured under 190°C and a force of 2.16 kg according to ASTMD1238 is in the range of 11.5 to 18.0; Specification (A-ii): The amount of vinyl groups is in the range of 5.0 to 20.0 groups and the total amount of unsaturated bonds is in the range of 40.0 to 200.0 bonds per 100,000 carbon atoms when calculated by 1H-NMR; Specification (A-iii): Amount of graft modification is in the range of 0.1 to 2.0% by mass compared to 100% by mass of graft-modified ethylene / 1-butene copolymer (A); Specification (A-iv): Melt flow rate (MFR2.16) measured according to ASTMD1238 under conditions of 190 °C and applied force 2.16 kg is in the range of 0.01 to 5.00 g / 10 min; and Specification (Av): Density measured according to ASTMD1505 under conditions of 25 °C is in the range of 850 to 885 kg / m³.

4. Ethylene / 1-butene Graft-modified butene copolymer (A) under Reputation 3, in which at least one polar compound is selected from the group of unsaturated carboxylic acids and their derivatives; 5. Polyamide resin composition consisting of 1 to 50 parts by mass of ethylene / 1-butene graft-modified copolymer (A) under any one of Reputations 1 to 4 and 50 to 99 parts by mass of polyamide resin (B), compared to 100 parts by mass of the total of ethylene / 1-butene graft-modified copolymer (A) and polyamide resin (B); 6.Polyamide resin components under claim 5, where polyamide resin (B) is one or more types of aliphatic polyamide resins selected from a group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 612, polyamide 610 and polyamide 10107. Pellets incorporating polyamide resin components under claim 58. Molded products incorporating polyamide resin components under claim 59. Injection molded objects incorporating polyamide resin components under claim 510. Automotive components incorporating polyamide resin components under claim 511. Electronic components incorporating polyamide resin components under claim 512. Electrical components for automotive incorporating polyamide resin components under claim 5;