Lubricating oil composition and method for producing the lubricating oil composition

Abstract

To provide a lubricating oil composition having a desired viscosity and excellent water solubility, and a method for producing the lubricating oil composition. [Solution] A lubricating oil composition comprising 1 to 80% by mass of a modified copolymer (A) that satisfies requirements (a-1) to (a-5), and a main chain portion (P) and a graft modified portion (Q) derived from an ethylene-α-olefin copolymer (X), and 10 to 99% by mass of one or more lubricating oil base oils (B) selected from the group consisting of mineral oils and synthetic oils, that satisfies requirements (b-1) and (b-2): (a-1) The content of structural units derived from ethylene in the main chain portion (P) is 10 to 90 mol%; (a-2) Mw determined by GPC is 1,000 to 50,000; (a-3) The content of the modified portion (Q) is 1 to 20% by mass; (a-4) The modified portion (Q) contains one or more primary hydroxyl groups; (a-5) The heat of fusion is substantially not observed in the range of 0 to 300°C in DSC; (b-1) The kinematic viscosity at 100°C is 1 to 10 mm 2 / s;(b-2) The viscosity index is 90 or higher.

Description

[Technical Field]

[0001] The present invention relates to a lubricating oil composition and a method for producing a lubricating oil composition. [Background technology]

[0002] Petroleum products generally exhibit a temperature dependence of viscosity, meaning their viscosity changes significantly with temperature. For example, in lubricating oils used in automobiles, it is preferable for viscosity to be less temperature-dependent from the viewpoint of lubricity and power transmission efficiency. Therefore, certain polymers soluble in the lubricating oil base are used as viscosity modifiers (also called viscosity index improvers) in lubricating oils to reduce the temperature dependence of viscosity. In recent years, OCP (olefin copolymer) has been widely used as a viscosity modifier, and various improvements have been made to OCP, as exemplified in Patent Document 1, to further improve the performance of lubricating oils. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 00 / 34420 [Overview of the project] [Problems that the invention aims to solve]

[0004] It is inevitable that lubricating oil will contain some moisture from the air. When the moisture concentration in the oil increases and water that can no longer dissolve in the lubricating oil separates into free water, it can cause wear, seizing, and rusting of metal parts due to reduced lubrication. For this reason, lubricating oil needs to have a certain degree of water solubility. However, conventional viscosity modifiers such as OCP were inferior in their ability to improve the water solubility of lubricating oils, and there was room for improvement.

[0005] The object of the present invention is to provide a lubricating oil composition having a desired viscosity and excellent water solubility, and a method for producing the lubricating oil composition. [Means for solving the problem]

[0006] The inventors diligently studied to solve the aforementioned problems. As a result, they found that the aforementioned problems can be solved by the following configuration, and thus the present invention was concluded. The following are examples of the configuration of the present invention.

[0007] [1] A lubricating oil composition comprising 1 to 80% by mass of a modified ethylene-α-olefin copolymer (A) that satisfies the following requirements (a-1) to (a-5), and 10 to 99% by mass of a lubricating oil base oil (B) that satisfies the following requirements (b-1) and (b-2), The modified ethylene-α-olefin copolymer (A) comprises a main chain portion (P) derived from the ethylene-α-olefin copolymer (X) and a graft-modified portion (Q). Lubricating oil composition wherein the lubricating oil base oil (B) is one or more base oils selected from the group consisting of mineral oils and synthetic oils: (a-1) The content of structural units derived from ethylene in the main chain portion (P) is 10 to 90 mol% (where the sum of the content of structural units derived from ethylene and structural units derived from α-olefins in the main chain portion (P) is 100 mol%); (a-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (a-3) The content of the graft-modified portion (Q) is 1 to 20% by mass (provided that the total amount of the main chain portion (P) and the graft-modified portion (Q) is 100% by mass). (a-4) The graft-modified region (Q) contains one or more primary hydroxyl groups; (a-5) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C; (b-1) Kinematic viscosity at 100°C is 1-10 mm 2 / s is; (b-2) The viscosity index is 90 or higher.

[0008] [2] The lubricating oil composition according to [1], wherein the graft-modified portion (Q) comprises a structural unit (Qs) derived from one or more carboxylic acid compounds (S) selected from the group consisting of unsaturated carboxylic acids and derivatives thereof containing one or more carbon-carbon unsaturated bonds, and a structural unit (Qt) derived from a reactive compound (T) having two or more functional groups in its molecule that can react with the carboxylic acid compound (S), and having one or more primary hydroxyl groups as functional groups that can react with the carboxylic acid compound (S).

[0009] [3] The lubricating oil composition according to [2], wherein the content of structural units (Qs) derived from the carboxylic acid compound (S) is 30 to 80 mol% (provided that the total of structural units (Qs) derived from the carboxylic acid compound (S) and structural units (Qt) derived from the reactive compound (T) is 100 mol%.

[0010] [4] The lubricating oil composition according to [2] or [3], wherein the reactive compound (T) further comprises one or more amino groups as functional groups that can react with the carboxylic acid compound (S).

[0011] [5] The carboxylic acid compound (S) is one or more compounds selected from the group consisting of maleic acid and maleic anhydride, and the reactive compound (T) is HO-CH2-C j H 2j O k A lubricating oil composition according to any one of [2] to [4], wherein the compound is represented by -NH2 (where j is an integer from 1 to 5 and k is an integer from 0 to 3).

[0012] [6] The proportion of structural units derived from ethylene in the main chain (P) is 30 to 70 mol%, The aforementioned weight-average molecular weight (Mw) is 2,500 to 30,000. The content of the graft-modified portion (Q) is 2.0 to 12% by mass. The lubricating oil composition according to any one of [2] to [5], wherein the content of structural units (Qs) derived from the carboxylic acid compound (S) is 35 to 70 mol%.

[0013] A method for producing a lubricating oil composition as described in any of [7] [2] to [6], The process involves grafting the ethylene-α-olefin copolymer (X) with the carboxylic acid compound (S) to obtain an acid-modified copolymer (Y), The process involves reacting the acid-modified copolymer (Y) with the reactive compound (T) to obtain the modified ethylene-α-olefin copolymer (A), and A method for producing a lubricating oil composition, including the following:

[0014] [8] The method for producing a lubricating oil composition according to [7], further comprising the step of stirring the lubricating oil base oil (B) and the modified ethylene-α-olefin copolymer (A) to obtain a modified ethylene-α-olefin copolymer (A)-containing concentrate (AC).

[0015] A method for producing a lubricating oil composition as described in any of [9] [2] to [6], The process involves grafting the ethylene-α-olefin copolymer (X) with the carboxylic acid compound (S) to obtain an acid-modified copolymer (Y), The process involves reacting the acid-modified copolymer (Y) with the reactive compound (T) in the lubricating oil base oil (B), and further stirring to obtain a concentrate (AC) containing a modified ethylene-α-olefin copolymer (A). A method for producing a lubricating oil composition, including the following:

[0016]

[10] The ethylene-α-olefin copolymer (X) satisfies the following requirements (x-1) to (x-4): A method for producing a lubricating oil composition according to any of [7] to [9], wherein the acid-modified copolymer (Y) satisfies the following requirements (y-1) to (y-3): (x-1) The content of structural units derived from ethylene is 10 to 90 mol% (where the sum of the content of structural units derived from ethylene and structural units derived from α-olefins is 100 mol%); (x-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (x-3) Kinematic viscosity at 100°C is 20-50,000 mm² 2 / s is; (x-4) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C; (y-1) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (y-2) The content of structural units derived from the carboxylic acid compound (S) is 0.1 to 20% by mass (provided that the sum of structural units derived from the carboxylic acid compound (S) and the main chain portion (P) is 100% by mass); (y-3) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C. [Effects of the Invention]

[0017] The lubricating oil composition of the present invention contains a modified copolymer that has an excellent balance between viscosity adjustment ability and water solubility improvement ability, thereby enabling the creation of a lubricating oil composition that has the desired viscosity and excellent water solubility performance. [Modes for carrying out the invention]

[0018] ≪Lubricating oil composition≫ The lubricating oil composition of the present invention (hereinafter also referred to as "this composition") is characterized by comprising 1 to 80% by mass of a modified ethylene-α-olefin copolymer (A) that satisfies predetermined requirements and 10 to 99% by mass of a lubricating oil base oil (B) that satisfies predetermined requirements.

[0019] The content of the modified ethylene-α-olefin copolymer (A) in this composition is 1 to 80% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, even more preferably 13 to 40% by mass, and particularly preferably 15 to 30% by mass, when the total lubricating oil composition is considered as 100% by mass.

[0020] The content of lubricating oil base oil (B) in this composition is 10 to 99% by mass, preferably 15 to 95% by mass, more preferably 20 to 90% by mass, even more preferably 25 to 87% by mass, and particularly preferably 30 to 85% by mass, when the total lubricating oil composition is considered as 100% by mass.

[0021] The kinematic viscosity of this composition at 100°C is preferably 5 to 50 mmHg. 2 / s, more preferably 6-40mm 2 / s, and more preferably 7-30mm 2 It is / s. The kinematic viscosity of this composition and the copolymer (X) described later at 100°C is measured specifically by the method described in the examples described later.

[0022] [Modified ethylene-α-olefin copolymer (A)] The modified ethylene-α-olefin copolymer (A) (hereinafter also referred to as "modified copolymer (A)") comprises a main chain portion (P) derived from the ethylene-α-olefin copolymer (X) and a graft-modified portion (Q).

[0023] The modified copolymer (A) satisfies the following requirements (a-1) to (a-5). (a-1) The content of structural units derived from ethylene in the main chain (P) is 10 to 90 mol% (where the sum of the content of structural units derived from ethylene and structural units derived from α-olefins in the main chain (P) is 100 mol%). (a-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000. (a-3) The content of the graft-modified portion (Q) is 1 to 20% by mass (provided that the total amount of the main chain portion (P) and the graft-modified portion (Q) is 100% by mass). (a-4) The graft modification region (Q) contains one or more primary hydroxyl groups. (a-5) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C.

[0024] ·Requirements (a-1) The content of structural units derived from ethylene in the main chain portion (P) of the modified copolymer (A) is 10 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, even more preferably 40 to 60 mol%, and particularly preferably 50 to 55 mol%. However, the sum of the content of structural units derived from ethylene and structural units derived from α-olefin in the main chain portion (P) is set to 100 mol%.

[0025] When the content of structural units derived from ethylene is within the aforementioned range, a non-crystalline amorphous copolymer is obtained, making it easy to obtain a modified copolymer (A) with excellent fluidity and compatibility with polar materials. Examples of polar materials include polar solvents such as water, methanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate; polar resins such as polyamides, polyacetals, polyesters, polycarbonates, and polyketones; and various polar additives such as detergent dispersants, friction modifiers, oiliness agents, antioxidants, and rust inhibitors. Since the modified copolymer (A) is more polar than conventional modified ethylene-α-olefin copolymers, using such a modified copolymer (A) in a lubricating oil composition can improve water solubility. In other words, it is expected that the formation of water droplets from moisture mixed in the oil can be suppressed, thereby preventing lubrication failure.

[0026] As used herein, the term "structural unit derived from ethylene" refers to a structural unit corresponding to ethylene, that is, a structural unit represented by -CH2-CH2-. Similarly, the term "structural unit derived from an α-olefin" refers to a structural unit corresponding to an α-olefin, that is, a structural unit represented by -CH2-CRR'-(wherein R and R' are each independently a hydrogen atom or an alkyl group).

[0027] The content of structural units derived from ethylene in the modified copolymer (A) and the ethylene·α-olefin copolymer (X) described below is 13 It can be measured by 13C-NMR, and peak identification and quantification can be performed, for example, according to the method described below and the method described in "Polymer Analysis Handbook" (published by Asakura Shoten, pages 163 to 170). Specifically, the content of structural units derived from ethylene is measured by the method described in the Examples below.

[0028] • Requirement (a-2) The polystyrene-equivalent weight average molecular weight (Mw) of the modified copolymer (A) determined by gel permeation chromatography (GPC) is from 1,000 to 50,000, preferably from 2,000 to 40,000, more preferably from 2,500 to 30,000, still more preferably from 3,000 to 20,000, and particularly preferably from 5,000 to 15,000. When the weight average molecular weight (Mw) is within the above range, the modified copolymer (A) having an appropriate viscosity and excellent viscosity adjusting ability can be easily obtained. Further, when the weight average molecular weight (Mw) is within the above range, the modified copolymer (A) having excellent fluidity and excellent compatibility with polar materials can be easily obtained. By using such a modified copolymer (A) in a lubricating oil composition, the lubricating oil composition can be adjusted to a target viscosity and at the same time, water solubility can be improved.

[0029] Furthermore, the polystyrene-based molecular weight distribution (Mw / Mn) of the modified copolymer (A), determined by gel permeation chromatography (GPC), is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, even more preferably 1.5 to 3.0, and particularly preferably 2.0 to 2.5. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the modified copolymer (A), the ethylene-α-olefin copolymer (X) described later, and the acid-modified copolymer (Y) are specifically measured by the method described in the examples below.

[0030] ·Requirements (a-3) The content of the graft-modified portion (Q) in the modified copolymer (A) is 1.0 to 20% by mass, preferably 1.5 to 15% by mass, more preferably 2.0 to 12% by mass, even more preferably 2.5 to 11% by mass, and particularly preferably 3.0 to 10% by mass. However, the total amount of the main chain portion (P) and the graft-modified portion (Q) is taken as 100% by mass. When the content ratio of the graft-modified region (Q) is within the aforementioned range, it exhibits excellent compatibility with polar materials. The proportion of graft-modified areas (Q) is, specifically, 1 This can be determined by measuring the 1H-NMR spectrum and calculating the area ratio of characteristic peaks (for example, hydrogen atoms bonded to the α-carbon of functional groups such as carbonyl groups and hydroxyl groups). Furthermore, if the molar equivalent of the reactive compound (T) added to the acid-modified copolymer (Y) is equal to or less than the amount of structural units (Qs) derived from the carboxylic acid compound (S), and the reaction rate of the structural units (Qs) derived from the carboxylic acid compound (S) is very high, it can also be calculated using the method described in the examples below.

[0031] ·Requirements (a-4) The graft-modified portion (Q) of the modified copolymer (A) contains one or more primary hydroxyl groups, preferably one or more primary hydroxyl groups and one or more amide or imide groups. When the graft-modified portion (Q) contains one or more of the aforementioned functional groups, it exhibits excellent compatibility with polar materials. Examples of the primary hydroxyl group include -C j H 2j O k Examples of linear substituents include those represented by -CH2-OH (where j is an integer from 1 to 5, and k is an integer from 0 to 3).

[0032] ·Requirements (a-5) In differential scanning calorimetry (DSC) of the modified copolymer (A), the heat of fusion (ΔH) is substantially absent in the range of 0 to 300°C. Here, substantially absent heat of fusion (ΔH) means that no melting peak is observed, or the measured heat of fusion (ΔH) is 1 J / g or less. If the heat of fusion (ΔH) is substantially absent in the range of 0 to 300°C, the modified copolymer (A) refers to an amorphous copolymer that does not have crystalline properties, exhibiting excellent fluidity and compatibility with polar materials. By using such a modified copolymer (A) in a lubricating oil composition, the water solubility can be improved. The heat of fusion (ΔH) of the modified copolymer (A), the ethylene-α-olefin copolymer (X) described later, and the acid-modified copolymer (Y) is specifically measured by the method described in the examples below.

[0033] <Main chain part (P)> The modified copolymer (A) contains a main chain portion (P) derived from the ethylene-α-olefin copolymer (X). Examples of α-olefins constituting the ethylene-α-olefin copolymer (X) include α-olefins other than ethylene that have 3 or more carbon atoms, preferably α-olefins having 3 to 20 carbon atoms, and more preferably α-olefins having 3 to 10 carbon atoms.

[0034] Specifically, α-olefins include linear α-olefins such as 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, and 1-eicosene; 3-methyl-1-pentene, 4-methyl-1-pentene, 8-methyl-1-nonene, 7-methyl-1-decene, and 6-methyl-1-pentene. Examples include branched α-olefins such as 1-undecene and 6,8-dimethyl-1-decene, with propylene,1-butene,1-pentene,1-hexene,1-heptene,1-octene,1-nonene,1-decene,3-methyl-1-pentene,4-methyl-1-pentene, and8-methyl-1-nonene being preferred, propylene,1-butene,1-pentene,1-hexene, and3-methyl-1-pentene being more preferred, propylene and1-butene being even more preferred, and propylene being particularly preferred. The ethylene-α-olefin copolymer (X) may contain one type of α-olefin alone, or it may contain two or more types.

[0035] The ethylene-α-olefin copolymer (X) preferably satisfies the following requirements (x-1) to (x-4). (x-1) The content of structural units derived from ethylene is 10 to 90 mol% (where the sum of the content of structural units derived from ethylene and structural units derived from α-olefins is 100 mol%). (x-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000. (x-3) The kinematic viscosity at 100°C is 20 to 50,000 mm². 2 It is / s. (x-4) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C.

[0036] ·Requirements (x-1) The content of structural units derived from ethylene in the ethylene-α-olefin copolymer (X) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%. However, the sum of the content of structural units derived from ethylene and structural units derived from α-olefin in the main chain (P) is set to 100 mol%. If the content of ethylene-derived structural units in the ethylene-α-olefin copolymer (X) is within the aforementioned range, a modified copolymer (A) in which the content of ethylene-derived structural units is within the aforementioned range can be easily obtained.

[0037] ·Requirements (x-2) The weight-average molecular weight (Mw) of the ethylene-α-olefin copolymer (X), as determined by gel permeation chromatography (GPC), is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, even more preferably 2,500 to 30,000, and particularly preferably 3,000 to 20,000. If the weight-average molecular weight (Mw) of the ethylene-α-olefin copolymer (X) is within the aforementioned range, a modified copolymer (A) having a weight-average molecular weight (Mw) within the aforementioned range can be easily obtained.

[0038] Furthermore, the molecular weight distribution (Mw / Mn) of the ethylene-α-olefin copolymer (X) as determined by gel permeation chromatography (GPC) is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, and even more preferably 1.5 to 3.0.

[0039] ·Requirements (x-3) The kinematic viscosity of the ethylene-α-olefin copolymer (X) at 100°C is preferably 20 to 50,000 mm². 2 / s, more preferably 40~3,500mm 2 / s, more preferably 60-2,500 mm 2 / s, particularly preferably 100-1,000 mm 2It is / s. If the kinematic viscosity of the ethylene-α-olefin copolymer (X) at 100°C is within the aforementioned range, the resulting modified copolymer (A) exhibits excellent fluidity. The kinematic viscosity at 100°C is specifically measured by the method described in the examples below.

[0040] ·Requirements (x-4) In differential scanning calorimetry (DSC) of ethylene-α-olefin copolymer (X), the heat of fusion (ΔH) is substantially absent in the range of 0 to 300°C. Here, substantially absent heat of fusion (ΔH) means that no fusion peak is observed, or the measured heat of fusion (ΔH) is 1 J / g or less. If the heat of fusion (ΔH) of the ethylene-α-olefin copolymer (X) is substantially absent in the 0-300°C range, a modified copolymer (A) in which the heat of fusion (ΔH) is substantially absent in the 0-300°C range can be easily obtained.

[0041] <Graft degeneration area (Q)> The modified copolymer (A) contains a graft-modified region (Q). The graft-modified portion (Q) preferably contains a structural unit (Qs) derived from one or more carboxylic acid compounds (S) selected from the group consisting of unsaturated carboxylic acids containing one or more carbon-carbon unsaturated bonds and their derivatives, and a structural unit (Qt) derived from a reactive compound (T) having two or more functional groups in its molecule that can react with the carboxylic acid compounds (S). The carboxylic acid compound (S) and the reactive compound (T) can each be used individually or in combination of two or more.

[0042] The content of structural units (Qs) derived from the carboxylic acid compound (S) is preferably 30 to 80 mol%, preferably 35 to 70 mol%, and more preferably 40 to 60 mol%. However, the total of structural units (Qs) derived from the carboxylic acid compound (S) and structural units (Qt) derived from the reactive compound (T) is set to 100 mol%.

[0043] The proportion of structural units (Qs) derived from carboxylic acid compounds (S) is, specifically, 1 This can be determined by measuring the 1H-NMR spectrum and calculating the area ratio of characteristic peaks (for example, hydrogen atoms bonded to the α-carbon of functional groups such as carbonyl groups and hydroxyl groups). Furthermore, if the molar equivalent of the reactive compound (T) added to the acid-modified copolymer (Y) is equal to or less than the amount of structural units (Qs) derived from the carboxylic acid compound (S), and the reaction rate of the structural units (Qs) derived from the carboxylic acid compound (S) is very high, it can also be calculated using the method described in the examples below.

[0044] The reactive compound (T) has two or more functional groups in its molecule that can react with the carboxylic acid compound (S). Examples of functional groups that can react with the carboxylic acid compound (S) include hydroxyl groups, amino groups, and mercapto groups, with hydroxyl groups and amino groups being preferred. Furthermore, the reactive compound (T) has one or more primary hydroxyl groups as functional groups that can react with the carboxylic acid compound (S).

[0045] The reactive compound (T) preferably has one or more primary hydroxyl groups in addition to one or more amino groups as a functional group that can react with the carboxylic acid compound (S). Since amino groups have high reactivity with the carboxylic acid compound (S) and the resulting amides and imides are also highly stable, using a reactive compound (T) that has one or more primary hydroxyl groups in addition to one or more amino groups makes it easy to obtain a modified copolymer (A) with excellent stability.

[0046] When the carboxylic acid compound (S) is a dicarboxylic acid such as maleic acid or maleic anhydride, or its anhydride, among unsaturated carboxylic acids containing one or more carbon-carbon unsaturated bonds as described later, the amino group contained in the reactive compound (T) is preferably a primary amino group. When a dicarboxylic acid reacts with a primary amino group, a more stable cyclic imide is produced, and a modified copolymer (A) with excellent stability can be easily obtained.

[0047] Reactive compounds (T) include dihydric or higher alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, and pentaerythritol; HO-CH2-C j H 2j O k Examples include compounds represented by -NH2 (where j is an integer from 1 to 5, and k is an integer from 0 to 3).

[0048] Among them, the reactive compound (T) is HO-CH2-C j H 2j O k It is preferable that the compound is represented by -NH2, and examples of amino alcohols include 2-aminoethanol (ethanolamine), 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 2-amino-1-propanol, 3-amino-2-methylpropanol, 2-amino-1-butanol, 3-amino-1-butanol, 2-amino-2-methyl-1-propanol, 2-amino-1,3-propanediol (serinol), 2-amino-2-methyl-1,3-propanediol, 2-(2-aminoethoxy)-1,3-propanediol, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-(2-aminoethoxy)ethanol, and 2-(2-(2-aminoethoxy)ethoxy)ethanol.

[0049] Examples of unsaturated carboxylic acids containing one or more carbon-carbon unsaturated bonds include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid. TM (Endosys-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid) is one example.

[0050] Examples of derivatives of unsaturated carboxylic acids include acid halide compounds, amide compounds, imide compounds, acid anhydrides, and ester compounds of the aforementioned unsaturated carboxylic acids. Specifically, examples include maleyl chloride, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, methyl acrylate, methyl methacrylate, monomethyl maleate, dimethyl maleate, diethyl fumarate, dimethyl itaconicate, diethyl citraconicate, tetrahydrophthalic anhydride, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and glycidyl maleate.

[0051] As for the carboxylic acid compound (S), among these, unsaturated dicarboxylic acids and their derivatives containing one or more carbon-carbon unsaturated bonds are preferred, because the functional groups contained in the graft-modified portion (Q) of the modified copolymer (A) become more stable imides. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, and nadic acid. The carboxylic acid compound (S) is more preferably one or more compounds selected from the group consisting of maleic acid and maleic anhydride, in that it is less likely to produce by-products such as homopolymers in the reaction to produce the acid-modified copolymer (Y) described later.

[0052] [Method for producing modified copolymer (A)] The modified copolymer (A) satisfies the above requirements (a-1) to (a-4). The method for producing the modified copolymer (A) is not particularly limited as long as it can solve the problems of the present invention and does not impair the technical effects of the present invention, but for example, a method of graft modification of ethylene-α-olefin copolymer (X) is one example. Specifically, for example, the modified copolymer (A) in one embodiment can be obtained by a manufacturing method comprising the steps of graft-modifying an ethylene-α-olefin copolymer (X) with a carboxylic acid compound (S) to obtain an acid-modified copolymer (Y) (hereinafter also referred to as "step (S1)") and reacting the acid-modified copolymer (Y) with a reactive compound (T) to obtain a modified copolymer (A) (hereinafter also referred to as "step (S2-1)").

[0053] In another embodiment, the product can be obtained by a manufacturing method comprising step (S1) and step (hereinafter also referred to as "step (S2-2)"), in which a reactive compound (T) is reacted with the acid-modified copolymer (Y) in a lubricating oil base oil (B), and further stirring is performed to obtain a concentrate (AC) containing a modified ethylene-α-olefin copolymer (A).

[0054] <Process (S1)> Step (S1) yields an acid-modified copolymer (Y) obtained by graft-modifying an ethylene-α-olefin copolymer (X) with a carboxylic acid compound (S).

[0055] The acid-modified copolymer (Y) can be produced by modifying the ethylene-α-olefin copolymer (X) by various conventionally known methods described in Japanese Patent Publication No. 61-126120 and Japanese Patent No. 2593264, for example, by the methods (1) and (2) below. (1) A method of modifying an ethylene-α-olefin copolymer (X) by charging it into an extruder, batch reactor, etc., and adding a carboxylic acid compound (S) to be reacted with. (2) A method of denaturing an ethylene-α-olefin copolymer (X) by dissolving it in a solvent and adding a carboxylic acid compound (S).

[0056] The amount of carboxylic acid compound (S) used is preferably 1.0 to 20 parts by mass, more preferably 1.5 to 15 parts by mass, even more preferably 2.0 to 10 parts by mass, and particularly preferably 2.5 to 8 parts by mass, per 100 parts by mass of ethylene-α-olefin copolymer (X).

[0057] In either method (1) or (2) described above, it is preferable to carry out graft copolymerization in the presence of one or more radical initiators in order to efficiently graft the carboxylic acid compound (S).

[0058] Examples of radical initiators include organic peroxides and azo compounds. Examples of organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexine, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene. Examples of azo compounds include azobisisobutyronitrile and dimethylazoisobutyrate.

[0059] Among these, dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexine, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and 1,4-bis(tert-butylperoxyisopropyl)benzene are particularly preferred.

[0060] The amount of radical initiator used is typically 0.001 to 10 parts by mass, preferably 0.01 to 8 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of ethylene-α-olefin copolymer (X). Furthermore, the amount of radical initiator used is typically 0.005 to 0.4 moles, preferably 0.01 to 0.35 moles, more preferably 0.05 to 0.3 moles, even more preferably 0.05 to 0.25 moles, and particularly preferably 0.1 to 0.2 moles, per mole of the carboxylic acid compound (S) added.

[0061] Furthermore, in order to accelerate the reaction, the reaction may be carried out in the presence of one or more elements selected from the group consisting of metals or metal salts, inorganic acids, organic acids, etc., in addition to the radical initiator. Examples of metals or metal salts include manganese acetate, cobalt acetate, manganese chloride, nickel oxide, and copper; examples of inorganic acids include hydrochloric acid and nitric acid; and examples of organic acids include formic acid, acetic acid, oxalic acid, malonic acid, maleic acid, tartaric acid, malic acid, adipic acid, and citric acid.

[0062] The reaction temperature in the aforementioned denaturation reaction is typically 20 to 350°C, preferably 60 to 300°C, more preferably 100 to 250°C, even more preferably 120 to 200°C, and particularly preferably 140 to 180°C. Furthermore, when denaturation is carried out using a reactive gas, the reaction pressure is preferably atmospheric pressure to 5 MPa. The modified copolymer produced by the above method may be further modified. For example, the method described in Japanese Patent Publication No. 2008-508402 may be used.

[0063] When maleic acid and maleic anhydride are used as the carboxylic acid compound (S), the acid value of the acid-modified copolymer (Y) (according to JIS K 2501:2003) is usually 1 to 200 mg KOH / g, preferably 5 to 150 mg KOH / g, more preferably 10 to 100 mg KOH / g, even more preferably 15 to 80 mg KOH / g, and particularly preferably 20 to 60 mg KOH / g.

[0064] The acid-modified copolymer (Y) preferably satisfies the following requirements (y-1) to (y-3). (y-1) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000. (y-2) The content of structural units derived from carboxylic acid compounds (S) is 0.1 to 20% by mass (where the total of structural units derived from carboxylic acid compounds (S) and structural units derived from the main chain (P) is 100% by mass). (y-3) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C.

[0065] • Requirements (y-1) The weight-average molecular weight (Mw) of the acid-modified copolymer (Y), determined by gel permeation chromatography (GPC), is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 3,000 to 30,000, even more preferably 4,000 to 20,000, and particularly preferably 5,000 to 15,000. If the weight-average molecular weight (Mw) of the acid-modified copolymer (Y) is within the aforementioned range, a modified copolymer (A) having a weight-average molecular weight (Mw) within the aforementioned range can be easily obtained.

[0066] Requirements (y-2) The content of structural units derived from the carboxylic acid compound (S) in the acid-modified copolymer (Y) is 0.1 to 20% by mass, preferably 0.5 to 15% by mass, more preferably 1.0 to 10% by mass, even more preferably 1.2 to 8.0% by mass, and particularly preferably 1.5 to 6.0% by mass. However, the total of structural units derived from the carboxylic acid compound (S) and the main chain portion (P) is set to 100% by mass. When the content of structural units derived from carboxylic acid compounds (S) is within the aforementioned range, the resulting modified copolymer (A) exhibits excellent compatibility with polar materials.

[0067] Furthermore, the polystyrene-based molecular weight distribution (Mw / Mn) of the acid-modified copolymer (Y), determined by gel permeation chromatography (GPC), is preferably 1.0 to 5.0, more preferably 1.2 to 4.0, even more preferably 1.5 to 3.0, and particularly preferably 1.7 to 2.5.

[0068] Requirements (y-3) In differential scanning calorimetry (DSC) of the acid-modified copolymer (Y), the heat of fusion (ΔH) is substantially absent in the range of 0 to 300°C. Here, substantially absent heat of fusion (ΔH) means that no melting peak is observed, or the measured heat of fusion (ΔH) is 1 J / g or less. If the heat of fusion (ΔH) of the acid-modified copolymer (Y) is substantially undetectable in the range of 0 to 300°C, then a modified copolymer (A) in which the heat of fusion (ΔH) is substantially undetectable in the range of 0 to 300°C can be easily obtained.

[0069] <Process (S2-1)> In step (S2-1), the acid-modified copolymer (Y) reacts with the reactive compound (T) to obtain the modified copolymer (A). Specifically, the carboxyl group or its derivative group derived from the carboxylic acid compound (S) present in the acid-modified copolymer (Y) is reacted with a functional group of the reactive compound (T) that can react with the carboxylic acid compound (S).

[0070] The amount of reactive compound (T) used is preferably 0.1 to 2 moles, more preferably 0.5 to 1.5 moles, even more preferably 0.7 to 1.3 moles, and particularly preferably 0.8 to 1.2 moles, per mole of carboxyl groups or their derivative groups derived from the carboxylic acid compound (S) in the acid-modified copolymer (Y).

[0071] One method for forming bonds (e.g., ester bonds, amide bonds, imide bonds) by reacting a carboxyl group or its derivative group derived from a carboxylic acid compound (S) in an acid-modified copolymer (Y) with a functional group (e.g., a hydroxyl group or an amino group) in a reactive compound (T) is, for example, by adding the reactive compound (T) to the acid-modified copolymer (Y) and heating it.

[0072] Furthermore, if the reaction rate of the reaction is to be further improved, methods such as connecting to a nitrogen bubbling and / or reduced pressure system to intentionally remove the water produced in the reaction and shift the equilibrium of the condensation reaction toward the formation of ester bonds, amide bonds, and imide bonds can be used. In particular, when an unsaturated dicarboxylic acid and its derivatives are used as the carboxylic acid compound (S), and a compound having one or more primary hydroxyl groups in addition to a primary amino group is used as the reactive compound (T), if the reaction is stopped at the amide stage, the intermolecular interactions due to hydrogen bonding of the carboxyl and amide groups increase to an extreme degree, and the modified copolymer (A) may become so viscous that it is difficult to handle. Therefore, it is preferable to intentionally remove water and use a method that facilitates the formation of imides.

[0073] In step (S2-1), the reaction temperature is usually 100 to 200°C, preferably 110 to 190°C, more preferably 120 to 180°C, and the reaction time is usually 1 minute to 20 hours, preferably 1.5 minutes to 10 hours, more preferably 2.0 minutes to 5 hours. Furthermore, the reaction atmosphere is preferably under an inert gas atmosphere, at normal pressure or under reduced pressure.

[0074] Even when using the above method (step (S2-1)), the modified copolymer (A) may still become so viscous that it is difficult to handle, requiring a long time for weighing and dissolution in the lubricating oil base. In such cases, it is preferable to use the manufacturing method described as step (S2-2), in which the modified copolymer (A) is synthesized in the lubricating oil base (B).

[0075] <Process (S2-2)> In step (S2-2), the acid-modified copolymer (Y) and the reactive compound (T) react in the lubricating oil base oil (B) to synthesize the modified copolymer (A), and a concentrate (AC) containing the modified copolymer (A) is obtained. Here, "concentrate containing modified copolymer (A)" refers to a concentrate of modified copolymer (A) using lubricating oil base oil (B) as a medium. The modified copolymer (A) contained in the concentrate may become modified copolymer (A') upon concentration. The weight-average molecular weight (Mw) of the modified copolymer (A'), determined by gel permeation chromatography (GPC), is 1,000 to 50,000, preferably 3,000 to 40,000, more preferably 4,000 to 30,000, and even more preferably 5,000 to 20,000.

[0076] The modified copolymer (A)-containing concentrate obtained in step (S2-2) is specifically prepared by reacting the carboxyl group or its derivative group derived from the carboxylic acid compound (S) of the acid-modified copolymer (Y) with the functional group of the reactive compound (T) that can react with the carboxylic acid compound (S) in the lubricating oil base oil (B) to synthesize the modified copolymer (A), which is then stirred and concentrated.

[0077] The amount of reactive compound (T) used is preferably 0.1 to 2 moles, more preferably 0.5 to 1.5 moles, even more preferably 0.7 to 1.3 moles, and particularly preferably 0.8 to 1.2 moles, per mole of carboxyl groups or derivative groups derived from the carboxylic acid compound (S) in the acid-modified copolymer (Y).

[0078] One method for forming bonds (e.g., ester bonds, amide bonds, imide bonds) by reacting a carboxyl group or its derivative group derived from a carboxylic acid compound (S) in an acid-modified copolymer (Y) with a functional group (e.g., a hydroxyl group or an amino group) in a reactive compound (T) is, for example, by adding the reactive compound (T) to the acid-modified copolymer (Y) and heating it.

[0079] Furthermore, if the reaction rate of the reaction is to be further improved, methods such as connecting to a nitrogen bubbling and / or reduced pressure system to intentionally remove the water produced in the reaction and shift the equilibrium of the condensation reaction toward the formation of ester bonds, amide bonds, and imide bonds can be used. In particular, when an unsaturated dicarboxylic acid and its derivatives are used as the carboxylic acid compound (S), and a compound having one or more primary hydroxyl groups in addition to a primary amino group is used as the reactive compound (T), if the reaction is stopped at the amide stage, the intermolecular interactions due to hydrogen bonding of the carboxyl and amide groups increase to an extreme degree, and the modified copolymer (A) may become so viscous that it is difficult to handle. Therefore, it is preferable to intentionally remove water and use a method that facilitates the formation of imides.

[0080] In step (S2-2), the reaction temperature for the step in which the acid-modified copolymer (Y) and the reactive compound (T) are reacted is usually 20 to 200°C, preferably 25 to 180°C, more preferably 30 to 160°C, and even more preferably 35 to 140°C. The reaction time is usually 5 minutes to 20 hours, preferably 10 minutes to 10 hours, more preferably 15 minutes to 7 hours, and even more preferably 20 minutes to 5 hours. Furthermore, the reaction atmosphere is preferably under atmospheric pressure or reduced pressure, and more preferably under reduced pressure, in order to suppress oxidative degradation due to the heat during the reaction.

[0081] Furthermore, in order to remove the generated water while the reaction proceeds, the temperature, atmosphere, and reaction pressure (degree of reduced pressure) may be arbitrarily changed during step (S2-2). The reaction temperature during the step in which the reaction proceeds while removing water is usually 100 to 200°C, preferably 105 to 170°C, more preferably 110 to 150°C, and the reaction time is usually 10 minutes to 20 hours, preferably 20 minutes to 10 hours, more preferably 30 minutes to 5 hours.

[0082] Furthermore, the reaction atmosphere may be either an atmospheric atmosphere or an inert gas atmosphere, but an inert gas atmosphere is preferred in order to suppress oxidative degradation due to heat during the reaction. In addition, the reaction pressure is usually 200 mmHg or less, preferably 150 mmHg or less under reduced pressure. Moreover, in order to create gas flow and improve the efficiency of water removal, the atmosphere may also be one in which a small amount of inert gas is circulated, in which case the reaction pressure is preferably 40 mmHg or more, preferably 50 mmHg or more under reduced pressure.

[0083] <Method for producing ethylene-α-olefin copolymer (X)> The method for producing the ethylene-α-olefin copolymer (X) is not particularly limited, but one example is a method using a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound (for example, the same compound as the organometallic compound (N-1a) described later) as described in Japanese Patent Publication No. 2-1163 and Japanese Patent Publication No. 2-7998. Alternatively, as a method for producing the copolymer with high polymerization activity, a catalyst system consisting of a metallocene compound such as zirconocene and an organoaluminum oxy compound (aluminoxane) as described in Japanese Patent Publication No. 61-221207, Japanese Patent Publication No. 7-121969 and Japanese Patent No. 2796376 may be used, which is more preferable because it can reduce the chlorine content of the resulting copolymer and the 2,1-insertion of α-olefin.

[0084] Furthermore, reducing the 2,1-insertion of α-olefins allows for a further reduction of ethylene chains within the copolymer molecule, thereby suppressing the intramolecular crystallinity of ethylene. As a result, the ethylene-α-olefin copolymer (X) becomes an amorphous copolymer with good fluidity. This characteristic allows for the production of compositions with good processability. The amount of 2,1-insertion of α-olefins is determined according to the method described in Japanese Patent Publication No. 7-145212. 13 The concentration is determined by analysis of 1C-NMR measurements, preferably less than 1%, more preferably 0-0.5%, and more preferably 0-0.1%. It is particularly preferable that no peaks are observed in the range of 15.0-17.5 ppm.

[0085] In particular, by using the following methods, an ethylene-α-olefin copolymer (X) with a good balance of performance in terms of molecular weight control, molecular weight distribution, and amorphousness can be obtained.

[0086] In one embodiment, the ethylene-α-olefin copolymer (X) can be produced by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst comprising, for example, a crosslinked metallocene compound (L) (hereinafter also referred to as "compound (L)") and at least one compound (N) selected from the group consisting of an organometallic compound (N-1), an organoaluminum oxy compound (N-2), and a compound (N-3) that reacts with the crosslinked metallocene compound (L) to form an ion pair.

[0087] • Cross-linked metallocene compound (L) A crosslinked metallocene compound (L) that can be used in the production of an ethylene-α-olefin copolymer (X) has a structure represented by the following formula [I].

[0088] [ka]

[0089] (Y, M, R 1 ~R 14 , Q, n and j) Y is a group 14 atom, and examples include carbon atoms, silicon atoms, germanium atoms, and tin atoms, preferably carbon atoms or silicon atoms, and more preferably carbon atoms. M is a titanium atom, a zirconium atom, or a hafnium atom, preferably a zirconium atom.

[0090] R 1 ~R 12 R is an atom or substituent selected from the group consisting of a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom, and a halogen-containing group, and each may be the same or different.1 From R 12 Two or more adjacent substituents among them may be bonded to each other to form a ring, or they may not be bonded to each other.

[0091] Examples of hydrocarbon groups having 1 to 20 carbon atoms include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms, chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms, cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms, alkylene groups having 1 to 20 carbon atoms, and arylene groups having 6 to 20 carbon atoms.

[0092] Examples of alkyl groups having 1 to 20 carbon atoms include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl groups, and branched saturated hydrocarbon groups such as isopropyl, isobutyl, s-butyl, tert-butyl, tert-amyl, neopentyl, 3-methylpentyl, 1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl, 1,1-dimethyl-2-methylpropyl, 1-methyl-1-isopropyl-2-methylpropyl, and cyclopropylmethyl groups. The number of carbon atoms in the alkyl group is preferably 1 to 6.

[0093] Examples of cyclic saturated hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, 1-adamantyl, and 2-adamantyl groups, as well as groups in which the hydrogen atoms of a cyclic saturated hydrocarbon group are replaced by hydrocarbon groups having 1 to 17 carbon atoms, such as 3-methylcyclopentyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-cyclohexylcyclohexyl, and 4-phenylcyclohexyl groups. The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 5 to 11.

[0094] Examples of chain-like unsaturated hydrocarbon groups having 2 to 20 carbon atoms include alkenyl groups such as the ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), and 1-methylethenyl group (isopropenyl group), and alkynyl groups such as the ethynyl group, 1-propynyl group, and 2-propynyl group (propargyl group). The number of carbon atoms in the chain-like unsaturated hydrocarbon group is preferably 2 to 4.

[0095] Examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms include cyclic unsaturated hydrocarbon groups such as cyclopentadienyl, norborneyl, phenyl, naphthyl, indenyl, azurenyl, phenanthryl, and anthracenyl groups; groups in which the hydrogen atoms of a cyclic unsaturated hydrocarbon group are replaced by hydrocarbon groups having 1 to 15 carbon atoms, such as 3-methylphenyl (m-tolyl), 4-methylphenyl (p-tolyl), 4-ethylphenyl, 4-tert-butylphenyl, 4-cyclohexylphenyl, biphenylyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, and 2,4,6-trimethylphenyl (mesityl); and groups in which the hydrogen atoms of a linear or branched saturated hydrocarbon group are replaced by cyclic saturated or cyclic unsaturated hydrocarbon groups having 3 to 19 carbon atoms, such as benzyl and cumyl groups. The number of carbon atoms in the cyclic unsaturated hydrocarbon group is preferably 6 to 10.

[0096] Examples of alkylene groups having 1 to 20 carbon atoms include methylene, ethylene, dimethylmethylene (isopropylidene), ethylmethylene, methylethylene, and n-propylene. The alkylene group preferably has 1 to 6 carbon atoms.

[0097] Examples of arylene groups having 6 to 20 carbon atoms include o-phenylene groups, m-phenylene groups, p-phenylene groups, and 4,4'-biphenylene groups. The number of carbon atoms in the arylene group is preferably 6 to 12.

[0098] Examples of silicon-containing groups include alkylsilyl groups such as trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, and triisopropylsilyl, which are hydrocarbon groups having 1 to 20 carbon atoms in which carbon atoms are replaced by silicon atoms; arylsilyl groups such as dimethylphenylsilyl, methyldiphenylsilyl, and tert-butyldiphenylsilyl; pentamethyldisilanyl; and trimethylsilylmethyl. The number of carbon atoms in alkylsilyl groups is preferably 1 to 10, and the number of carbon atoms in arylsilyl groups is preferably 6 to 18.

[0099] Examples of nitrogen-containing groups include amino groups and, in the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms or silicon-containing groups, groups in which the =CH- structural unit is replaced by a nitrogen atom, groups in which the -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 the -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 dimethylamino group, diethylamino group, N-morpholinyl group, dimethylaminomethyl group, cyano group, pyrrolidinyl group, piperidinyl group, pyridinyl group, and nitro group. Dimethylamino group and N-morpholinyl group are preferred as nitrogen-containing groups.

[0100] Oxygen-containing groups include hydroxyl groups, the aforementioned hydrocarbon groups with 1 to 20 carbon atoms, silicon-containing groups, or nitrogen-containing groups in which the -CH2- structural unit is replaced by an oxygen atom or a carbonyl group, or where the -CH3 structural unit is replaced by an oxygen atom to which a hydrocarbon group with 1 to 20 carbon atoms is bonded, such as methoxy groups, ethoxy groups, tert-butoxy groups, phenoxy groups, trimethylsiloxy groups, methoxyethoxy groups, hydroxymethyl groups, methoxymethyl groups, ethoxymethyl groups, tert-butoxymethyl groups, and 1-hydroxyethyl groups. Examples of oxygen-containing groups include 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, carboxyl group, methoxycarbonyl group, carboxymethyl group, ethocarboxymethyl group, carbamoylmethyl group, furanyl group, and pyranyl group. Methoxymethyl group is preferred as the oxygen-containing group.

[0101] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, which are elements of Group 17. Examples of halogen-containing groups include trifluoromethyl, tribromomethyl, pentafluoroethyl, and pentafluorophenyl groups, which are hydrocarbon groups, silicon-containing groups, nitrogen-containing groups, or oxygen-containing groups having 1 to 20 carbon atoms, in which a hydrogen atom is substituted by a halogen atom.

[0102] Q is selected from halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, anionic ligands, and neutral ligands that can coordinate with lone pairs of electrons, in the same or different combinations. Details of halogen atoms and hydrocarbon groups 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 in the hydrocarbon group is preferably 1 to 7.

[0103] Examples of anionic ligands include alkoxy groups such as methoxy groups, tert-butoxy groups, and phenoxy groups; carboxylate groups such as acetates and benzoates; and sulfonate groups such as mesylates and tosylates.

[0104] Examples of neutral ligands that can coordinate with a lone pair of electrons include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, and ether compounds such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0105] j is an integer between 1 and 4, preferably 2. n is an integer from 1 to 4, preferably 1 or 2, and more preferably 1. R 13 and R 14 R is an atom or substituent selected from the group consisting of hydrogen atoms, hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, substituted aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and each may be the same or different. 13 and R 14 These elements may be bonded to each other to form a ring, or they may not be bonded to each other.

[0106] Details regarding hydrocarbon groups with 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups are as described above. Examples of aryl groups include those derived from aromatic compounds, such as phenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenantrenyl, tetracerenyl, chrysenyl, pyrenyl, indenyl, azurenyl, pyrrolyl, pyridyl, furanyl, and thiophenyl groups, although these overlap somewhat with the previously mentioned examples of cyclic unsaturated hydrocarbon groups with 3 to 20 carbon atoms.

[0107] Examples of the aforementioned aromatic compounds include aromatic hydrocarbons and heterocyclic aromatic compounds such as benzene, naphthalene, anthracene, phenanthrene, tetracene, chrysene, pyrene, indene, azulene, pyrrole, pyridine, furan, and thiophene.

[0108] Examples of substituted aryl groups include those that partially overlap with the examples of cyclic unsaturated hydrocarbon groups having 3 to 20 carbon atoms mentioned above, but also include groups in which one or more hydrogen atoms of the aryl group are substituted by at least one substituent selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, aryl groups, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups. Specifically, these include 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-(trimethylsilyl)phenyl group, and 4-(trimethylsilyl)phenyl group. Examples include the minophenyl 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, and 2-(6-methyl)pyridyl group.

[0109] Among them, R 13 and R 14 Compound (L) in which one or both of the groups are independently aryl groups is preferred, and compound (L) in which both are independently aryl groups is more preferred.

[0110] In particular, R 13 and R 14Compound (L), in which both are independently aryl groups, exhibits high polymerization activity for copolymerization of ethylene and α-olefins. By using compound (L), polymerization is selectively terminated by introducing hydrogen to the molecular ends, resulting in fewer unsaturated bonds in the resulting ethylene-α-olefin copolymer (X). Therefore, a highly saturated and heat-resistant ethylene-α-olefin copolymer (X) can be obtained with a simpler hydrogenation operation, or even without hydrogenation, resulting in cost advantages. Furthermore, the ethylene-α-olefin copolymer (X) obtained from compound (L) has a controlled molecular weight distribution due to its high random copolymerizability.

[0111] In compound (L) represented by the above formula [I], n is preferably 1. Such a crosslinked metallocene compound (hereinafter also referred to as "compound (L-1)") is represented by the following general formula [II].

[0112] [ka] In equation [II], Y, M, R 1 ~R 14 Q and j have the same signs as in the above formula [1].

[0113] Compared to compounds in formula [I] where n is an integer between 2 and 4, compound (L-1) has a simplified manufacturing process and reduced manufacturing costs, and consequently, the use of this cross-linked metallocene compound (L-1) reduces the manufacturing cost of ethylene-α-olefin copolymer (X).

[0114] In the compound (L) represented by formula [I] and the compound (L-1) represented by formula [II], it is even more preferable that M is a zirconium atom. When copolymerizing ethylene with one or more monomers selected from the group consisting of α-olefins having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing the above-mentioned crosslinked metallocene compound in which M is a zirconium atom, the polymerization activity is higher and the production cost of the ethylene-α-olefin copolymer (X) is reduced compared to when M is a titanium atom or a hafnium atom.

[0115] As for compound (L), [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 (η)(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, [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(η5 -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, [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)(η 5 [-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, [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)](octamethyloctahydrodibenzfluorenyl)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, 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)](octamethyloctahydrodibenzfluorenyl)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)](octamethyloctahydrodibenzfluorenyl)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)][η5 -(2,7-dimethyl-3,6-di-tert-butylfluorenyl)] zirconium dichloride, 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)](octamethyloctahydrodibenzfluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](benzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](dibenzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](octahydrodibenzofluorenyl)zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5 -(2,7-diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5 -(2,7-dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, diphenylmethylene[η 5 -(3-tert-butylcyclopentadienyl)](η 5-Fluorenyl) zirconium dichloride, diphenylmethylene [η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(3,6-di-tert-butylfluorenyl)] zirconium dichloride, diphenylmethylene [η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-di-tert-butylfluorenyl)] zirconium dichloride, diphenylmethylene [η 5 -(3-tert-butylcyclopentadienyl)](octamethyloctahydrodibenzfluorenyl)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, 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)](octamethyloctahydrodibenzfluorenyl)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-tril)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)](octamethyloctahydrodibenzfluorenyl)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, 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)](octamethyloctahydrodibenzfluorenyl)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[η5 -(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[η5-(3-n-butylcyclopentadienyl)] (octamethyloctahydrodibenzfluorenyl) 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 Examples include (2,7-dimethyl-3,6-di-tert-butylfluorenyl) zirconium dichloride.

[0116] Examples of compound (L) 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. Note that the constituent part of the example compound (L) is 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]represents the fluorenyl group, respectively. Compound (L) may be used alone or in combination of two or more types.

[0117] ·Compound (N) Compound (N) is at least one compound selected from the group consisting of organometallic compounds (N-1), organoaluminum oxy compounds (N-2), and compounds (N-3) that react with cross-linked metallocene compounds (L) to form ion pairs. Specifically, the organometallic compounds (N-1a), (N-1b), and (N-1c) from groups 1, 2 and 12, and 13 of the periodic table, as listed below, are used as organometallic compounds (N-1a), (N-1b), and (N-1c).

[0118] (N-1a) General formula R a m Al(OR b ) n H p X q An organoaluminum compound represented by the formula (wherein R a and R bmay be the same or different from each other, and represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms; X represents a halogen atom; m is a number satisfying 0<m≦3, n is a number satisfying 0≦n<3, p is a number satisfying 0≦p<3, q is a number satisfying 0≦q<3, and m+n+p+q=3.). Examples of such compounds include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum; tri-branched alkylaluminum such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminum such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminum such as triphenylaluminum and tri(4-methylphenyl)aluminum; dialkylaluminum hydride such as diisopropylaluminum hydride and diisobutylaluminum hydride; the general formula (i-C4H9) x Al y (C5H 10 ) z (wherein x, y and z are positive numbers, and z≦2x) alkenylaluminum such as isoprenylaluminum represented by; alkylaluminum alkoxide such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; the general formula R a 2.5 Al(OR b ) 0.5Examples include partially alkoxylated alkylaluminum having an average composition represented by the above formula R, alkylaluminum allyloxides 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, partially halogenated alkylaluminum such as ethylaluminum sesquichloride, butylaluminum sesquichloride, and ethylaluminum sesquibromide, and alkylaluminum dihalides 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 alkylaluminum, partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, and ethylaluminum ethoxybromide. a m Al(OR b ) n H p X q Compounds similar to those represented by can also be used, for example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2.

[0119] (N-1b) General formula M 2 AlR a A complex alkylate of a Group 1 metal of the periodic table represented by 4 and aluminum (wherein M is the first metal in the formula). 2 R represents Li, Na, or K. a This represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of such compounds include LiAl(C2H5)4 and LiAl(C7H 15 Examples include 4.

[0120] (N-1c) General formula R a R b M 3 Dialkyl compounds of Group 2 or Group 12 metals of the periodic table represented by (wherein R, R) a and R b These 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, M 3 (It is Mg, Zn, or Cd.) Conventionally known aluminoxanes can be used as organoaluminum oxy compounds (N-2). Specifically, examples include compounds represented by the following general formula [III] and compounds represented by the following general formula [IV].

[0121] [ka] In formulas [III] and [IV], R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.

[0122] In particular, methyl aluminoxanes in which R is a methyl group, and n is preferably 3 or more, more preferably 10 or more, are used. These aluminoxanes may contain some organoaluminum compounds.

[0123] In the present invention, when copolymerizing ethylene with α-olefins having 3 or more carbon atoms at high temperatures, benzene-insoluble organoaluminum oxy compounds, such as those exemplified in Japanese Patent Publication No. 2-78687, can also be used. Furthermore, organoaluminum oxy compounds described in Japanese Patent Publication No. 2-167305, aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 2-24701 and Japanese Patent Publication No. 3-103407 can also be suitably used. The "benzene-insoluble organoaluminum oxy compounds" used in the present invention are compounds in which the Al component that dissolves in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms, and are insoluble or sparingly soluble in benzene.

[0124] Furthermore, examples of organoaluminum oxy compounds (N-2) include modified methylaluminoxanes represented by the following general formula [V].

[0125] [ka] In formula [V], Rx is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are independent integers greater than or equal to 2.

[0126] Methylaluminoxane, an example of an organoaluminum oxy compound (N-2), is readily available and possesses high polymerization activity, making it commonly used as an activator in olefin polymerization. However, because methylaluminoxane is difficult to dissolve in saturated hydrocarbons, it has been used as a solution of environmentally undesirable aromatic hydrocarbons such as toluene or benzene. Therefore, in recent years, a flexible body of methylaluminoxane has been developed and is used as an aluminoxane dissolved in saturated hydrocarbons. This modified methylaluminoxane, represented by formula [V], is prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum, as shown in, for example, U.S. Patent No. 4,960,878 and U.S. Patent No. 5,041,584, for example, using trimethylaluminum and triisobutylaluminum. Aluminoxanes with Rx being an isobutyl group are commercially available in the form of saturated hydrocarbon solutions under the trade names MMAO and TMAO (see Tosoh Finechem Corporation, Tosoh Research & Technology Review, Vol 47, 55 (2003)).

[0127] Furthermore, as organoaluminum oxy compounds (N-2), organoaluminum oxy compounds containing boron represented by the following general formula [VI] can also be mentioned.

[0128] [ka] In formula [VI], R c R represents a hydrocarbon group with 1 to 10 carbon atoms. d These may be the same or different from each other, and represent a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

[0129] Examples of the compound (N-3) that reacts with a bridged metallocene compound (L) to form an ion pair (hereinafter sometimes abbreviated as "ionized ionic compound" or simply "ionic compound") include Lewis acids, ionic compounds, borane compounds and carborane compounds described in Japanese National Publication No. 1-501950, Japanese National Publication No. 1-502036, Japanese Unexamined Patent Publication No. 3-179005, Japanese Unexamined Patent Publication No. 3-179006, Japanese Unexamined Patent Publication No. 3-207703, Japanese Unexamined Patent Publication No. 3-207704, U.S. Patent No. 5321106, and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0130] The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].

[0131]

Chemical Formula

[0132] In formula [VII], R e+ is H + , a carbenium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation, a ferrocenium cation having a transition metal, and the like. R f to R i may be the same or different from each other, and are substituents selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a nitrogen-containing group, an oxygen-containing group, a halogen atom and a halogen-containing group, and are preferably substituted aryl groups.

[0133] Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(4-methylphenyl)carbenium cation, and tris(3,5-dimethylphenyl)carbenium cation.

[0134] 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.

[0135] 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.

[0136] R e+ , among the above specific examples, carbenium cations, ammonium cations and the like are preferable, and triphenylcarbenium cation, N,N-dimethylanilinium cation and N,N-diethylanilinium cation are particularly preferable.

[0137] Among the ionized ionic compounds that are preferably used, examples of the compound containing a carbenium cation 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.

[0138] Among the ionized ionic compounds that are preferably used, compounds containing a trialkyl-substituted ammonium cation include triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tri(n-butyl)ammonium tetraphenyl borate, 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, and tri(n-butyl)ammonium tetrakis(4-(trifluorophenyl) Examples include di(n-butyl)ammonium tetrakis{3,5-di(trifluoromethyl)phenyl} borate, di(n-butyl)ammonium tetrakis(2-methylphenyl) borate, dioctadecylmethylammonium tetraphenyl 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, and dioctadecylmethylammonium.

[0139] Examples of ionized ionic compounds that are preferably used include N,N-dialkylanilinium cation-containing compounds such as N,N-dimethylanilinium tetraphenyl borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl} borate, N,N-diethylanilinium tetraphenyl borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis{3,5-di(trifluoromethyl)phenyl} borate, N,N-2,4,6-pentamethylanilinium tetraphenyl borate, and N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl) borate.

[0140] Examples of ionized compounds that are preferably used include di-n-propylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate, which contain dialkylammonium cations.

[0141] In addition, ionic compounds exemplified in Japanese Patent Publication No. 2004-51676 can also be used without limitation. The above ionic compound (N-3) may be used alone or in mixtures of two or more. But that's fine.

[0142] Examples of the configuration of the catalyst system include, for example, the following (1) to (4). (1) Compound (L) and compound (N-2) (Contains two compounds: (L), (N-1), and (N-2) (3) Compound (L), Compound (N-1), and Compound (N-3) (4) Compound (L), Compound (N-2), and Compound (N-3) Compound (L) and compounds (N-1) to (N-3) can be introduced into the reaction system in any order.

[0143] Carrier(R) A support (R) may be used as a component of the olefin polymerization catalyst, if necessary. The carrier (R) is an inorganic or organic compound, in the form of a granular or fine-particle solid. Among these, porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds are preferred as inorganic compounds.

[0144] Specifically, porous oxides such as SiO2, Al2O3, MgO, ZrO, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures containing these, such as natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, SiO2-TiO2-MgO, etc., can be used. Of these, those mainly composed of SiO2 and / or Al2O3 are preferred.

[0145] The properties of such porous oxides vary depending on the type and manufacturing method, but the preferred carrier 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 m². 2 / g, preferably 100-700m 2 It is in the range of / g, and the pore volume is 0.3-3.0 cm³. 3 It is in the range of / g. Such carriers are used after being calcined at 100-1000°C, preferably 150-700°C, as needed.

[0146] Examples of inorganic chlorides used include MgCl2, MgBr2, MnCl2, and MnBr2. These inorganic chlorides may be used as is, or they may be ground using a ball mill or vibration mill before use. Alternatively, the inorganic chlorides may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0147] Clay is typically composed mainly of clay minerals. Ion-exchangeable layered compounds are compounds with a crystalline structure in which the constituent surfaces are stacked parallel to each other by weak bonding forces, such as ionic bonds, and the ions they contain are exchangeable. Most clay minerals are ion-exchangeable layered compounds. Furthermore, these clays, clay minerals, and ion-exchangeable layered compounds can be derived not only from natural sources but also from synthetic materials.

[0148] Furthermore, examples of clay, clay minerals, or ion-exchangeable layered compounds include clay, clay minerals, and ionic crystalline compounds having layered crystalline structures such as hexagonal close-packed type, antimony type, CdCl2 type, and CdI2 type. Examples of such clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, and halloysite. Examples of ion-exchangeable layered compounds 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, and γ-Ti(NH4PO4)2·H2O.

[0149] It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0150] The ion-exchange layered compound may be a layered compound in an expanded interlayer state obtained by utilizing ion exchange properties to exchange exchangeable ions between layers with another large bulky ion. Such bulky ions play the role of pillars supporting the layered structure, and are generally referred to as pillars. Additionally, introducing another substance (guest compound) between the layers of a layered compound in this manner 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 (wherein R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 7+ , [Zr4(OH) 14 2+ , [Fe3O(OCOCH3)6] + and other metal hydroxide ions. These compounds may be used singly or in combination of two or more thereof.

[0151] When intercalating these compounds, polymers obtained by hydrolytic polycondensation of metal alkoxides such as Si(OR)4, Al(OR)3 and Ge(OR)4 (wherein R is a hydrocarbon group, etc.) and colloidal inorganic compounds such as SiO2 can also coexist. Examples of pillars include oxides formed by heating and dehydrating after intercalating the above metal hydroxide ions between layers.

[0152] Among these, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, pectolite, taeniolite and synthetic mica. Examples of the organic compound as the carrier (R) include granular or particulate solids with a particle diameter in the range of 0.5 to 300 μm. Specifically, examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, (co)polymers produced mainly from vinylcyclohexane and styrene, and modified products thereof. ​​

[0153] The method of use and the order of addition of each component of the polymerization catalyst can be chosen arbitrarily. Furthermore, at least two of the components in the catalyst may be in contact with each other beforehand. The cross-linked metallocene compound (L) (hereinafter also referred to as "component (L)") is typically 10 per liter of reaction volume. -9 ~10 -1 moles, preferably 10 -8 ~10 -2 It is used in quantities that equal moles.

[0154] The organometallic compound (N-1) (hereinafter also referred to as "component (N-1)") is used in an amount such that the molar ratio [(N-1) / M] of component (N-1) to the transition metal atom (M) in component (L) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

[0155] The organoaluminum oxy compound (N-2) (hereinafter also referred to as "component (N-2)") is used in an amount such that the molar ratio [(N-2) / M] of aluminum atoms in component (N-2) to transition metal atoms (M) in component (L) is usually 10 to 5,000, preferably 20 to 2,000.

[0156] The ionic compound (N-3) (hereinafter also referred to as "component (N-3)") is used in an amount such that the molar ratio [(N-3) / M] of component (N-3) to the transition metal atom (M) in component (L) is usually 1 to 10,000, preferably 1 to 5,000.

[0157] The polymerization temperature is typically -50 to 300°C, preferably 30 to 250°C, more preferably 100 to 250°C, and even more preferably 130 to 200°C. In the polymerization temperature range described above, as the temperature increases, the viscosity of the solution during polymerization decreases, and the heat of polymerization is also easily removed. The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure (MPa-G) (i.e., above atmospheric pressure (atmospheric pressure + 10 MPa) or below), preferably atmospheric pressure to 8 MPa-G (i.e., above atmospheric pressure (atmospheric pressure + 8 MPa) or below).

[0158] Polymerization reactions can be carried out using batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out continuously in two or more polymerizers with different reaction conditions. The molecular weight of the resulting copolymer can be adjusted by changing the hydrogen concentration and polymerization temperature in the polymerization system. Furthermore, it can also be adjusted by the amount of the component (N) used. When hydrogen is added, an appropriate amount is approximately 0.001 to 5,000 NL per kilogram of the resulting copolymer.

[0159] The polymerization solvent used in liquid-phase polymerization is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon with a boiling point of 50°C to 200°C at atmospheric pressure. Specific examples of polymerization solvents include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Hexane, heptane, octane, decane, and cyclohexane are particularly preferred. The α-olefin itself, which is the target of polymerization, can also be used as the polymerization solvent. Aromatic hydrocarbons such as benzene, toluene, and xylene, as well as halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane, can also be used as polymerization solvents; however, their use is undesirable from the perspective of reducing environmental impact and minimizing impact on human health.

[0160] The kinematic viscosity of an olefin polymer at 100°C depends on the molecular weight of the polymer. That is, a high molecular weight results in high viscosity, and a low molecular weight results in low viscosity; therefore, the kinematic viscosity at 100°C is adjusted by adjusting the molecular weight as described above. In addition, 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 conventionally known methods such as vacuum distillation. Furthermore, the obtained polymer may be subjected to hydrogenation (hereinafter also referred to as hydrogenation) by conventionally known methods. If the double bonds of the polymer obtained by hydrogenation are reduced, the oxidation stability and heat resistance are improved.

[0161] The resulting ethylene-α-olefin copolymer (X) may be used alone, or two or more copolymers with different molecular weights or different monomer compositions may be combined.

[0162] The modified copolymer (A) may contain structural units derived from at least one biomass-derived monomer (e.g., ethylene, α-olefin, carboxylic acid compounds (S), reactive compounds (T)). The monomers used as raw materials for the modified copolymer (A) may consist solely of biomass-derived monomers, or they may consist of both biomass-derived monomers and fossil fuel-derived monomers. The biomass-derived monomers are obtained by known methods. It is preferable for the modified copolymer (A) to contain structural units derived from biomass-derived monomers from the viewpoint of reducing environmental impact. The aforementioned fossil fuels are petroleum, coal, natural gas, shale gas, or combinations thereof. Biomass refers to all renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, of plant or animal origin.

[0163] The modified copolymer (A) may contain structural units derived from at least one type of chemically recycled monomer (e.g., ethylene, α-olefin, carboxylic acid compounds (S), reactive compounds (T)). Furthermore, the monomers used as raw materials for the modified copolymer (A) may consist solely of chemically recycled monomers, or they may consist of both chemically recycled monomers and fossil fuel-derived monomers. The chemically recycled monomers can be obtained by known methods. It is preferable for the modified copolymer (A) to contain structural units derived from chemically recycled monomers from the viewpoint of reducing environmental impact (mainly waste reduction).

[0164] [Lubricant base oil (B)] The lubricating oil base oil (B), which is one of the components of this composition, is one or more base oils selected from the group consisting of mineral oils and synthetic oils. Mineral oil or synthetic oil may be used alone, or any mixture of two or more selected from mineral oils and synthetic oils may be used. Lubricating oil base oil (B) may be used alone or in combination of two or more types.

[0165] The lubricating oil base oil (B) satisfies the following requirements (b-1) and (b-2). (b-1) Kinematic viscosity at 100°C is 1-10 mm 2 It is / s. (b-2) The viscosity index is 90 or higher.

[0166] ·Requirements (b-1) The kinematic viscosity of lubricating oil base oil (B) at 100°C (according to JIS K 2283) is 1 to 10 mm². 2 The interval is / s, preferably 1.5-9mm. 2 / s, more preferably 2.0~8mm 2 It is / s. When the kinematic viscosity of the lubricating oil base oil (B) at 100°C is within the aforementioned range, this composition exhibits an excellent balance between temperature viscosity characteristics and heat resistance stability.

[0167] ·Requirements (b-2) The viscosity index of the lubricating oil base oil (B) (according to JIS K 2283) is 90 or higher, preferably 95 or higher, more preferably 100 or higher, and even more preferably 110 or higher. There is no particular upper limit to the viscosity index, but for example, it is 160. When the viscosity index of the lubricating oil base oil (B) is within the aforementioned range, this composition exhibits excellent temperature viscosity characteristics.

[0168] Lubricating oil base oils differ in performance and quality, such as viscosity characteristics, heat resistance, and oxidation stability, depending on their manufacturing and refining methods. The American Petroleum Institute (API) classifies lubricating oil base oils into five groups: I, II, III, IV, and V. These API categories are defined in API 1509, Engine Oil Licensing and Certification System, 22nd Edition, October 2023, and are shown in Table 1.

[0169] [Table 1]

[0170] • Mineral oil Mineral oils belong to groups I to III in the API categories mentioned above. The quality of mineral oil is as described above, and depending on the refining method, mineral oil of each of the aforementioned qualities can be obtained. Examples of mineral oils include lubricating oil fractions obtained by vacuum distillation of atmospheric residue obtained by atmospheric distillation of crude oil, and then refined by one or more processes such as solvent delamination, solvent extraction, hydrocracking, solvent dewaxing, and hydrorefining, or lubricating oil base oils such as wax isomerized mineral oil.

[0171] Furthermore, gas-to-liquid (GTL) base oils obtained by the Fischer-Tropsch process are also suitable base oils for use as Group III mineral oils. Such GTL base oils are sometimes treated as Group III+ lubricating oil base oils, and are described, for example, in the patent documents European Patent No. 776959, European Patent No. 668342, International Publication No. 97 / 21788, International Publication No. 00 / 15736, International Publication No. 00 / 14188, International Publication No. 00 / 14187, International Publication No. 00 / 14183, International Publication No. 00 / 14179, International Publication No. 00 / 08115, International Publication No. 99 / 41332, European Patent No. 1029029, International Publication No. 01 / 18156, and International Publication No. 01 / 57166.

[0172] ·Synthetic oil Synthetic oils belong to Group IV or Group V in the API categories. The synthetic oils contained in this composition preferably include synthetic oils belonging to Group IV or Group V, and more preferably include esters and non-ester synthetic oils.

[0173] Poly-α-olefins belonging to Group IV can be obtained by oligomerizing higher α-olefins with an acid catalyst, as described in U.S. Patent No. 3,780,128, U.S. Patent No. 4,032,591, Japanese Patent Publication No. 1-163136, etc. Among these, low molecular weight oligomers of at least one olefin selected from olefins with 8 or more carbon atoms can be used as poly-α-olefins. When poly-α-olefins are used as the lubricating oil base oil, a lubricating oil composition with extremely excellent temperature viscosity characteristics, low-temperature viscosity characteristics, and heat resistance can be obtained.

[0174] Poly-α-olefins are industrially available and have a kinematic viscosity of 1.7 mm at 100°C. 2 / s~10mm 2 Products with a saturation factor of / s are commercially available. Examples include Spectrasyn from ExxonMobil Chemical, Durasyn from Ineos Oligmers, and Synfluid from Chevron Phillips Chemical.

[0175] Examples of synthetic oils belonging to Group V include alkylbenzenes, alkylnaphthalenes, isobutene oligomers or their hydrides, paraffins, polyoxyalkylene glycols, dialkyldiphenyl ethers, polyphenyl ethers, and esters.

[0176] Most alkylbenzenes and alkylnaphthalenes are typically dialkylbenzenes or dialkylnaphthalenes with alkyl chain lengths of 6 to 14 carbon atoms, and such alkylbenzenes or alkylnaphthalenes are produced by the Friedel-Kraft alkylation reaction of benzene or naphthalene with an olefin. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be linear or branched olefins or combinations thereof. Methods for producing these are described, for example, in U.S. Patent No. 3,909,432.

[0177] Furthermore, fatty acid esters are preferred as esters from the viewpoint of compatibility with the modified copolymer (A). Fatty acid esters are not particularly limited, but examples include fatty acid esters consisting only of carbon, oxygen, and hydrogen, such as monoesters produced from a monobasic acid and an alcohol; diesters produced from a dibasic acid and an alcohol, or from a diol and a monobasic acid or an acid mixture; and polyol esters produced by reacting diols, triols (e.g., trimethylolpropane), tetraols (e.g., pentaerythritol), hexaols (e.g., dipentaerythritol), etc., with a monobasic acid or an acid mixture. Examples of these esters include ditridecyl glutarate, di-2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, tridecyl pelargonate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, trimethylolpropane caprylate, trimethylolpropane pelargonate, trimethylolpropane triheptanoate, pentaerythritol-2-ethylhexanoate, pentaerythritol pelargonate, and pentaerythritol tetraheptanoate.

[0178] From the viewpoint of compatibility with the modified copolymer (A), the alcohol moiety constituting the ester is preferably an alcohol with two or more hydroxyl groups, and the fatty acid moiety is preferably a fatty acid with eight or more carbon atoms. However, in terms of manufacturing cost, fatty acids with 20 or fewer carbon atoms, which are readily available industrially, are preferred. The ester may consist of only one type of fatty acid, and the effects of the present invention can also be fully demonstrated by using a fatty acid ester produced using a mixture of two or more acids.

[0179] More specifically, examples of fatty acid esters include trimethylolpropane, lauric acid, and stearic acid mixed triesters and diisodecyl adipates. These are preferred in terms of compatibility with saturated hydrocarbon components such as modified copolymers (A) and with antioxidants, corrosion inhibitors, wear inhibitors, friction modifiers, pour point depressants, rust inhibitors, and defoamers having polar groups, as described later.

[0180] <Other ingredients> This composition may optionally contain additives such as extreme pressure agents, detergent dispersants, viscosity index improvers, antioxidants, corrosion inhibitors, wear inhibitors, friction modifiers, pour point depressants, rust inhibitors, and defoamers, as long as they do not impair the objectives of the present invention. Each additive may be used alone or in combination of two or more.

[0181] <Extreme pressure agents> Extreme pressure additives are a general term for substances that have an anti-seize effect when metal-to-metal contact, such as gears, is exposed to high load conditions. They are not particularly limited, but examples include sulfur-based extreme pressure additives such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, sulfurized oils and fats, and sulfurized olefins; phosphoric acids such as phosphate esters, phosphite esters, phosphate ester amine salts, and phosphite ester amines; and halogen compounds such as chlorinated hydrocarbons. Two or more of these compounds may also be used in combination.

[0182] Furthermore, before extreme pressure lubrication conditions are reached, hydrocarbons or other organic components constituting the lubricating oil composition may carbonize due to heating and shearing, potentially forming a carbide film on the metal surface. Therefore, when using extreme pressure additives alone, the carbide film may hinder contact between the additive and the metal surface, potentially preventing the additive from achieving its full effect.

[0183] Extreme pressure additives may be added alone, but since this composition mainly consists of saturated hydrocarbons such as modified copolymer (A), it is preferable from the viewpoint of dispersibility to add them after dissolving them in a lubricating oil base such as mineral oil or synthetic hydrocarbon oil, along with other additives used beforehand. Specifically, it is more preferable to select a so-called additive package, in which various components such as extreme pressure additive components are pre-blended and then dissolved in a lubricating oil base such as mineral oil or synthetic hydrocarbon oil, and add it to the lubricating oil composition.

[0184] Preferred additive packages include Anglamol-98A, Anglamol-6043, Angramol 6085U, and LUBRIZOL 1047U from LUBRIZOL, HITEC1532, HITEC307, and HITEC3339 from AFTON CHEMICAL, and Additin RC 9410 from RHEIN CHEMIE.

[0185] Extreme pressure additives are used as needed in an amount ranging from 0% to 10% by mass relative to 100% by mass of the lubricating oil composition.

[0186] <Cleansing Dispersant> Examples of cleaning and dispersing agents include metal sulfonates, metal phenates, metal phosphanates, and succinimides. Alkali metal and alkaline earth metal salicylates, phenates, and sulfonates are preferred in the lubricating oil composition of the present invention. Specifically, examples include calcium or magnesium sulfonates; phenates; salicylates; succinimides; and benzylamines. Detergent dispersants are used as needed in an amount ranging from 0 to 15% by mass relative to 100% by mass of the lubricating oil composition.

[0187] <Viscosity index improver> In addition to ethylene-α-olefin copolymers (excluding modified ethylene-α-olefin copolymer (A)), other known viscosity index improvers such as olefin copolymers, methacrylate copolymers, and liquid polybutenes with molecular weights exceeding 50,000 can be used in combination as viscosity index improvers. Viscosity index improvers are used as needed in an amount ranging from 0 to 50% by mass relative to 100% by mass of the lubricating oil composition.

[0188] <Antioxidant> Examples of antioxidants include phenolic and amine compounds such as 2,6-di-tert-butyl-4-methylphenol. Antioxidants are used as needed in an amount ranging from 0% to 3% by mass relative to 100% by mass of the lubricating oil composition.

[0189] <Corrosion inhibitor> Examples of corrosion inhibitors include compounds such as benzotriazole, benzimidazole, and thiadiazole. Corrosion inhibitors are used as needed in an amount ranging from 0% to 3% by mass relative to 100% by mass of the lubricating oil composition.

[0190] <Abrasion-resistant agent> Examples of wear-resistant agents include inorganic or organic molybdenum compounds such as molybdenum disulfide, graphite, antimony sulfide, and polytetrafluoroethylene. The anti-wear agent is used as needed in an amount of 0 to 3% by mass relative to 100% by mass of the lubricating oil composition.

[0191] <Friction modifier> Examples of friction modifiers include amine compounds, imide compounds, fatty acid esters, fatty acid amides, and fatty acid metal salts, which have at least one C6-C30 alkyl or alkenyl group, particularly a linear alkyl or linear alkenyl group, in their molecules.

[0192] Examples of amine compounds include linear or branched aliphatic monoamines having 6 to 30 carbon atoms, preferably linear; linear or branched aliphatic polyamines, preferably linear; or alkylene oxide adducts of these aliphatic amines. Examples of imide compounds include succinimides having linear or branched alkyl or alkenyl groups with 6 to 30 carbon atoms, and / or modified compounds thereof with carboxylic acids, boric acid, phosphoric acid, sulfuric acid, etc.

[0193] Examples of fatty acid esters include esters of linear or branched fatty acids having 7 to 31 carbon atoms, preferably linear fatty acids, with aliphatic monohydric alcohols or aliphatic polyhydric alcohols. Examples of fatty acid amides include amides of linear or branched fatty acids having 7 to 31 carbon atoms, preferably linear fatty acids, and aliphatic monoamines or aliphatic polyamines. Examples of fatty acid metal salts include alkaline earth metal salts (magnesium salts, calcium salts, etc.) and zinc salts of linear or branched fatty acids having 7 to 31 carbon atoms, preferably linear fatty acids. Friction modifiers are used as needed in an amount ranging from 0 to 5.0% by mass relative to 100% by mass of the lubricating oil composition.

[0194] <Pour point depressant> Various known pour point depressants can be used as pour point depressants. Specifically, polymer compounds containing organic acid ester groups are used, and vinyl polymers containing organic acid ester groups are particularly preferred. Examples of vinyl polymers containing organic acid ester groups include (co)polymers of alkyl methacrylate, (co)polymers of alkyl acrylate, (co)polymers of alkyl fumarate, (co)polymers of alkyl maleate, and alkylated naphthalene.

[0195] Such pour point depressants typically have a melting point of -13°C or lower, preferably -15°C, and more preferably -17°C or lower. The melting point of the pour point depressant is measured using a differential scanning calorimeter (DSC). Specifically, the melting point is determined from the endothermic curve obtained when approximately 5 mg of the sample is placed in an aluminum pan, heated to 200°C, held at 200°C for 5 minutes, cooled to -40°C at a rate of 10°C / min, held at -40°C for 5 minutes, and then heated again at a rate of 10°C / min.

[0196] The pour point depressant further has a polystyrene-based weight-average molecular weight (Mw) obtained by gel permeation chromatography (GPC) in the range of 20,000 to 400,000, preferably 30,000 to 300,000, and more preferably 40,000 to 200,000. The pour point depressant is used as needed, typically in an amount of 0 to 2% by mass, preferably 0.1 to 1.5% by mass, and more preferably 0.2 to 1.0% by mass, based on 100% by mass of the lubricating oil composition.

[0197] <Rust Inhibitor> Examples of rust inhibitors include various amine compounds, metal carboxylate salts, polyhydric alcohol esters, phosphorus compounds, and sulfonates. Rust inhibitors are used as needed in an amount ranging from 0% to 3% by mass relative to 100% by mass of the lubricating oil composition.

[0198] <Antifoaming agent> Examples of antifoaming agents include silicone-based compounds such as dimethylsiloxane and silica gel dispersions, as well as alcohol-based or ester-based compounds. The defoaming agent is used as needed in an amount of 0 to 0.2% by mass relative to 100% by mass of the lubricating oil composition.

[0199] In addition to the aforementioned additives, anti-emulsifiers, colorants, oiliness enhancers, and other substances may be used as needed. For low-viscosity lubricating oils, so-called DI packages are industrially supplied, which are formulated with various necessary additives for this application and concentrated and dissolved in lubricating oils such as mineral oil or synthetic oil. Such DI packages can also be applied to this composition.

[0200] [Method for producing this composition] This composition can be prepared by mixing, for example, a modified copolymer (A) or a modified copolymer (A)-containing concentrate (AC) produced by the method described in "Method for Producing Modified Copolymer (A)" above, a lubricating oil base oil (B), and other components as needed, at a desired temperature using a stirrer.

[0201] As one embodiment, when using a modified copolymer (A) produced by the method described in the "Method for Producing Modified Copolymer (A)" (for example, methods (S1) and (S2-1)), the method may further include the step of stirring the lubricating oil base oil (B) and the modified ethylene-α-olefin copolymer (A) to obtain a concentrate (AC) containing the modified ethylene-α-olefin copolymer (A).

[0202] In another embodiment, the acid-modified copolymer (Y) obtained by the method (S1) described in the "Method for Producing Modified Copolymer (A)" may be reacted with a reactive compound (T) in the lubricating oil base oil (B), and further stirred to obtain a concentrate (AC) containing modified ethylene-α-olefin copolymer (A).

[0203] In the process of obtaining a modified copolymer (A)-containing concentrate (AC), the reaction temperature is typically 100 to 200°C, and the reaction time is typically 10 minutes to 20 hours. The reaction atmosphere may be an atmospheric atmosphere, an inert gas atmosphere, or an atmosphere with a small amount of inert gas flowing through it. The reaction pressure is preferably a reduced pressure of typically 50 to 200 mmHg.

[0204] [Uses of this composition] This composition can be suitably used in lubricating oil compositions such as automobile engine oil, automobile gear oil, automobile transmission oil, industrial lubricating oil, and hydraulic oil. By using a modified copolymer (A) that exhibits a good balance between viscosity adjustment ability and water solubility improvement ability, it is possible to achieve both viscosity adjustment to the desired level and water solubility with a lower additive amount, thereby providing a lubricating oil composition with the desired viscosity and excellent water solubility at a lower cost. [Examples]

[0205] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" refers to "parts by mass".

[0206] [Methods for measuring the structure, molecular weight, etc. of raw materials] The structure and molecular weight of each copolymer were measured by the following method. <Ethylene content (mol%)> 13 The ethylene content (mol%) in each copolymer was measured using 1C-NMR spectroscopy under the following conditions and equipment: A JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer was used; solvent: orthodichlorobenzene / deuterated benzene (80% / 20% vol) mixed solvent; sample concentration: 55 mg / 0.6 mL; measurement temperature: 120°C; observed nucleus: 13 Measurements were performed under the following conditions: C (125MHz), sequence: single-pulse proton decoupling, pulse width: 4.7μs (45° pulse), repetition time: 5.5 seconds, number of integrations: 10,000 or more, and chemical shift reference value: 27.50ppm. 13 Based on the reports of G.J. Ray (Macromolecules, 10,773 (1977)), J.C. Sandall (Macromolecules, 15,353 (1982)), and K. Kimura (Polymer, 25,4418 (1984)), the ethylene content was determined from the 1C-NMR spectrum.

[0207] <Kinematic viscosity at 100°C> The kinematic viscosity at 100°C (100°C kinematic viscosity) was measured and calculated according to the method described in JIS K 2283:2000.

[0208] <Number-average molecular weight, weight-average molecular weight, and molecular weight distribution> Using gel permeation chromatography (GPC), the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were calculated in terms of polystyrene molecular weight, following a general calibration procedure. From these values, the molecular weight distribution (Mw / Mn) was calculated. High-speed GPC measurement device: HLC-8320GPC (manufactured by Tosoh Corporation) Separation column: TSKgel Super MultiporeHZ-M Four units (manufactured by Tosoh Corporation) connected in series. Column temperature: 40℃ Mobile phase: Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) Mobile phase flow rate: 0.35mL / min Sample concentration: 5.5 g / L Sample injection volume: 20 μL Detector: Differential refractometer Standard polystyrene: PStQuick MP-M (manufactured by Tosoh Corporation)

[0209] <Content ratio of structural units derived from carboxylic acid compounds (S) in acid-modified copolymer (Y)> 1 The content percentage (mass%) of structural units (modification sites) derived from carboxylic acid compounds (S) in the acid-modified copolymer (Y) was measured using the following apparatus and conditions via 1H-NMR. A Bruker BioSpin AVANCE III-cryo-500 nuclear magnetic resonance spectrometer (500 MHz) was used, with the following conditions: solvent: 1,1,2,2-tetrachloroethane-d2, measurement temperature: 120°C, spectral width: 20 ppm, pulse repetition time: 30 seconds, pulse width: 5.00 μs. The measurements were performed as described above. 1 The above content ratio was determined by calculating the area ratio of peaks characteristic of carboxylic acid compounds (S) (such as hydrogen atoms bonded to the α-carbon of the carbonyl group) from the 1H-NMR spectrum.

[0210] <Acid value> The acid value was measured according to the method compliant with JIS K 2501:2003.

[0211] <Heat of fusion (ΔH)> Using a differential scanning calorimeter (DSC220, Seiko Instruments Inc.), approximately 5.0 mg of the sample was heated from 30°C to 200°C at a heating rate of 10°C / min under a nitrogen atmosphere and held at that temperature for 10 minutes. It was then cooled to -100°C at a cooling rate of 10°C / min and held at that temperature for 5 minutes, before being heated again to 200°C at a heating rate of 10°C / min to obtain a DSC curve. The obtained DSC curve was analyzed in accordance with JIS K 7121:2012 to calculate the heat of fusion (ΔH). The heat of fusion (ΔH) of the modified copolymer (A) in concentrate form dissolved in the lubricating oil base (B) was determined by subtracting the value obtained by multiplying the heat of fusion (ΔH) of the lubricating oil base (B) by the mass ratio of the mineral oil from the heat of fusion (ΔH) of the concentrate.

[0212] <Percentage of graft-degenerated area (Q) content> In the modified copolymers (A1) and (A2) described in the following examples, the content of the graft-modified portion (Qs) was 50 mol%, meaning that the structural units derived from the carboxylic acid compound (S) and the reactive compound (T) were in equimolar ratios, and the reaction rate of the structural units derived from the carboxylic acid compound (S) was >99%. Therefore, the content of the graft-modified portion (Q) was calculated from the content of structural units derived from the carboxylic acid compound in the raw material acid-modified copolymers (Y1) and (Y2) and the mass ratio of the reactive compound (T) added to synthesize the modified copolymers (A1) and (A2). For example, in Example 1, 10.7 g of 2-(2-aminoethoxy)ethanol was added as the reactive compound (T) to 199 g of acid-modified copolymer (Y1) having a structural unit content of 5.0% by mass derived from carboxylic acid compounds, so the calculation can be made as follows. (Percentage of graft-modified region (Q) [mass%]) =(199 × 5.0 ÷ 100 + 10.7) ÷ (199 + 10.7) =0.0984≒9.8[mass%]

[0213] [Manufacturing Example 1] Production of ethylene-propylene copolymer (X1) In a 2 L continuous polymerization reactor with a stirring blade and sufficient nitrogen purging, 1 L of dehydrated and purified hexane is charged, and ethyl aluminum sesquichloride (Al(C2H5)) is adjusted to 96 mmol / L. 1.5 ·Cl 1.5 A hexane solution of VO(OC2H5)Cl2 was continuously supplied at a rate of 500 mL / h for 1 hour. Then, a hexane solution of VO(OC2H5)Cl2 adjusted to 16 mmol / L was continuously supplied at a rate of 500 mL / h, along with hexane at a rate of 500 mL / h. Meanwhile, the polymerization liquid was continuously withdrawn from the top of the polymerization reactor to maintain a constant level of 1 L in the polymerization liquid chamber. Next, ethylene gas was supplied at a rate of 45 L / h, propylene gas at a rate of 45 L / h, and hydrogen gas at a rate of 80 L / h using a bubbling tube. The copolymerization reaction was carried out at 35°C by circulating a refrigerant through a jacket attached to the outside of the polymerization reactor.

[0214] The reaction was carried out under the above conditions to obtain a polymerization solution containing ethylene-propylene copolymer. The obtained polymerization solution was demineralized with hydrochloric acid, then added to a large amount of methanol to precipitate the polymer, and then dried under reduced pressure at 130°C for 24 hours to obtain ethylene-propylene copolymer (X1). The ethylene content of ethylene-propylene copolymer (X1) was 54 mol%, and the kinematic viscosity at 100°C was 155 mmHg. 2 The values ​​were / s, Mw was 5,200, Mw / Mn was 1.7, and the heat of fusion (ΔH) was virtually undetectable in the range of 0 to 300°C.

[0215] [Manufacturing Example 2] Manufacturing of ethylene-propylene copolymer (X2) A 2 L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 710 mL of heptane and 145 g of propylene. After raising the temperature of the system to 150 °C, the total pressure was increased to 3 MPaG by supplying 0.40 MPa of hydrogen and 0.27 MPa of ethylene. Next, 0.4 mmol of triisobutylaluminum, [methylphenylmethylene (η) 5 -cyclopentadienyl)(η 5 Polymerization was initiated by introducing 0.0001 mmol of -2,7-di-t-butylfluorenyl)zirconium dichloride and 0.001 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate under pressure with nitrogen and stirring at 400 rpm. Subsequently, the total pressure was maintained at 3 MPaG by continuously supplying only ethylene, and polymerization was carried out at 150°C for 5 minutes. Polymerization was stopped by adding a small amount of ethanol to the system, and unreacted ethylene, propylene, and hydrogen were purged. The resulting polymerization solution was washed three times with 1000 mL of 0.2 mol / L hydrochloric acid, followed by three washes with 1000 mL of distilled water, dried with magnesium sulfate, and the solvent was removed under reduced pressure to obtain crude ethylene-propylene copolymer.

[0216] In a 1 L stainless steel autoclave, 100 mL of a hexane solution of 0.5% by mass Pd / alumina catalyst (hydrogenation catalyst) and 500 mL of a 30% by mass hexane solution of the obtained crude ethylene-propylene copolymer were added. After sealing the autoclave, nitrogen purging was performed. Next, the temperature was raised to 140°C while stirring, the system was purged with hydrogen, and the pressure was increased to 1.5 MPa with hydrogen for a hydrogenation reaction to be carried out for 15 minutes. After filtering off the hydrogenation catalyst from the reaction solution, the solvent was removed by distillation under reduced pressure, and the ethylene-propylene copolymer (X2) was obtained by drying under reduced pressure at 80°C for 24 hours. The ethylene content of the ethylene-propylene copolymer (X2) was 53 mol%, and the kinematic viscosity at 100°C was 608 mmHg. 2 The values ​​were / s, Mw was 8,600, Mw / Mn was 1.8, and virtually no heat of fusion (ΔH) was observed in the range of 0 to 300°C.

[0217] [Manufacturing Example 3] Production of acid-modified ethylene-propylene copolymer (Y1) 100 g of ethylene-propylene copolymer (X1) was charged into a 200 mL glass reactor with a stirrer, equipped with a nitrogen inlet tube, water-cooled condenser, thermometer, and two dropping funnels. After raising the temperature, nitrogen bubbling was started at 120°C and the system was maintained at 160°C. Then, 6.6 g of maleic anhydride (heated to around 70°C to make it liquid) and 1.3 g of di-tert-butyl peroxide, which had been pre-loaded into two dropping funnels, were supplied over 5 hours, and the mixture was allowed to react for 1 hour after the supply was complete. Next, the temperature was further raised to 175°C, and after depressurizing the system, impurities (unreacted maleic anhydride and decomposition products of di-tert-butyl peroxide) were removed by gradually reducing the pressure with a vacuum pump for 1 hour while aeration with nitrogen. Through these operations, maleic anhydride-modified ethylene-propylene copolymer (Y1) (hereinafter also referred to as "acid-modified copolymer (Y1)") was obtained. The acid-modified copolymer (Y1) had a structural unit content of carboxylic acid compounds of 5.0% by mass, a Mw of 5,500, a Mw / Mn ratio of 1.9, and an acid value of 52 mgKOH / g. The heat of fusion (ΔH) was virtually undetectable in the range of 0 to 300°C.

[0218] [Manufacturing Example 4] Production of acid-modified ethylene-propylene copolymer (Y2) Except for changing ethylene-propylene copolymer (X1) to ethylene-propylene copolymer (X2), changing the supply amount of maleic anhydride to 2.8 g, changing the supply amount of di-tert-butyl peroxide to 0.6 g, and changing the supply time of maleic anhydride and di-tert-butyl peroxide to 2 hours, the same procedure as in Production Example 3 was followed to obtain maleic anhydride-modified ethylene-propylene copolymer (Y2) (hereinafter also referred to as "acid-modified copolymer (Y2)"). The content of structural units derived from carboxylic acid compounds in acid-modified copolymer (Y2) was 2.0% by mass, Mw was 9,200, Mw / Mn was 2.0, and the acid value was 23 mgKOH / g. The heat of fusion (ΔH) was not substantially measured in the range of 0 to 300°C.

[0219] [Manufacturing Example 5] Production of Modified Ethylene-Propylene Copolymer (A1) In a 300 mL glass reactor equipped with a stirrer, nitrogen inlet tube, water-cooled condenser, and thermometer, 199 g of acid-modified copolymer (Y1) and 10.7 g of 2-(2-aminoethoxy)ethanol were charged and reacted in an oil bath at 150°C for 3 minutes to obtain modified ethylene-propylene copolymer (A1) (hereinafter also referred to as "modified copolymer (A1)"). The reaction rate of structural units derived from carboxylic acid compounds (S) in modified copolymer (A1) was >99%, the ethylene content was 54 mol%, the graft-modified portion (Q) content was 9.8 mass%, Mw was 6,800, Mw / Mn was 2.3, and the content of sites derived from carboxylic acid compounds (S) (Qs) was 50 mol%. The heat of fusion (ΔH) was not substantially measured in the range of 0 to 300°C.

[0220] [Manufacturing Example 6] Production of Modified Ethylene-Propylene Copolymer (A2) The process was carried out in the same manner as in Production Example 5, except that acid-modified copolymer (Y1) was changed to acid-modified copolymer (Y2) and the amount of 2-(2-aminoethoxy)ethanol added was changed to 4.2 g, to obtain a modified ethylene-propylene copolymer (A2) (hereinafter also referred to as "modified copolymer (A2)"). The reaction rate of structural units derived from carboxylic acid compounds (S) in modified copolymer (A2) was >99%, the ethylene content was 53 mol%, the graft modification content was 4.0 mass%, Mw was 10,100, Mw / Mn was 2.3, and the content of sites derived from carboxylic acid compounds (S) (Qs) was 50 mol%, and the heat of fusion (ΔH) was substantially not measured in the range of 0 to 300°C.

[0221] [Manufacturing Example 7] Manufacturing of Concentrate (AC1) In a 300 mL glass reactor equipped with a stirrer, a nitrogen inlet tube, and a thermometer, 69.6 g of modified copolymer (A1) and Yubase-4 (manufactured by SK Lubricants, kinematic viscosity at 100°C = 4.25 mm) were added as lubricating oil base oil (B). 2 / s, 40℃ kinematic viscosity=19.80mm 269.8g of lubricating oil (B1), with a viscosity index of 121, was charged and heated to 100°C. The mixture was stirred for 2 hours under reduced pressure of 70-100 mmHg while a small amount of nitrogen was flowed through it to obtain a concentrate (AC1) containing 49.9% by mass of modified copolymer (A1'). In the concentrate (AC1), the reaction rate of the carboxylic acid compound (S)-derived portion of the modified copolymer (A1') was >99%, the ethylene content was 54 mol%, the graft modification portion (Q) content was 9.8% by mass, Mw was 6,700, and the carboxylic acid compound (S)-derived portion (Qs) content was 50 mol%. The heat of fusion (ΔH) was not substantially measured in the range of 0-300°C.

[0222] [Manufacturing Example 8] Manufacturing of Concentrate (AC2) In a 300 mL glass reactor equipped with a stirrer, nitrogen inlet tube, and thermometer, 60.0 g of modified copolymer (A2) and 61.1 g of lubricating oil base oil (B1) were charged. The mixture was heated to 100°C and stirred under reduced pressure of 70-100 mmHg for 2 hours while a small amount of nitrogen was flowed through it to obtain a concentrate (AC2) containing 49.5% by mass of modified copolymer (A2'). In the concentrate (AC2), the reaction rate of the carboxylic acid compound (S)-derived moieties of the modified copolymer (A2') was >99%, the ethylene content was 54 mol%, the graft modification moieties (Q) content was 7.5% by mass, the Mw was 16,800, and the carboxylic acid compound (S)-derived moieties (Qs) content was 65 mol%. The heat of fusion (ΔH) was virtually undetectable in the range of 0-300°C.

[0223] [Manufacturing Example 9] Manufacturing of Concentrate (AC3) In a 300 mL glass reactor equipped with a stirrer, nitrogen inlet tube, and thermometer, 125 g of acid-modified copolymer (Y1) and 88.1 g of lubricating oil base oil (B1) were charged and the mixture was heated to 45°C and stirred to obtain a homogeneous solution. 6.7 g of 2-(2-aminoethoxy)ethanol was added and the mixture was stirred for 30 minutes to allow the reaction to proceed. Next, the mixture was heated to 120°C and stirred under reduced pressure of 70-100 mmHg while a small amount of nitrogen was flowed through it for 2 hours to obtain a concentrate (AC3) containing 59.8% by mass of modified copolymer (A3). In the concentrate (AC3), the reaction rate of the carboxylic acid compound (S)-derived moiety of the modified copolymer (A3) was >99%, the ethylene content was 54 mol%, the graft modification moiety (Q) content was 9.8 mass%, Mw was 7,900, and the carboxylic acid compound (S)-derived moiety (Qs) content was 50 mol%. The heat of fusion (ΔH) was virtually undetectable in the range of 0 to 300°C.

[0224] [Manufacturing Example 10] Manufacturing of Concentrate (AC4) In a 300 mL glass reactor equipped with a stirrer, nitrogen inlet tube, and thermometer, 112 g of acid-modified copolymer (Y2) and 115 g of lubricating oil base oil (B1) were charged. The mixture was heated to 50°C and stirred to obtain a homogeneous solution. 2.4 g of 2-(2-aminoethoxy)ethanol was added, and the mixture was stirred for 30 minutes. Next, the mixture was heated to 120°C and stirred under reduced pressure of 70-100 mmHg for 1 hour while a small amount of nitrogen was flowed through it, to obtain a concentrate (AC4) containing 50.0% by mass of modified copolymer (A4). In the concentrate (AC4), the reaction rate of the carboxylic acid compound (S)-derived sites of the modified copolymer (A4) was >99%, the ethylene content was 53 mol%, the graft modification site (Q) content was 4.0 mass%, Mw was 11,100, and the carboxylic acid compound (S)-derived site (Qs) content was 50 mol%. The heat of fusion (ΔH) was virtually undetectable in the range of 0 to 300°C.

[0225] [Examples 1-5, Comparative Examples 1-3] A lubricating oil composition was prepared by mixing modified copolymer (A), concentrates (AC1) to (AC4), copolymers (X1) and (X2), acid-modified copolymer (Y1), lubricating oil base oil (B1), and a pour point depressant (BASF Irgaflo 720P) in the amounts shown in the "Formulation" column of Table 2. The kinematic viscosity of the obtained lubricating oil composition at 100°C was measured according to the method described above. The evaluation results are shown in Table 2.

[0226] <Water solubility test> 50 g of the lubricating oil composition obtained in the examples and comparative examples was mixed with 10 μL of distilled water and stirred for 1 minute. After stopping the stirring, the presence or absence of undissolved water was checked. If there was no undissolved water, the addition of 10 μL increments was repeated until undissolved water appeared. If undissolved water was present, the total amount of water added up to that point was recorded and used as the water solubility value. The evaluation results are shown in Table 2.

[0227] [Table 2]

Claims

1. A lubricating oil composition comprising 1 to 80% by mass of a modified ethylene-α-olefin copolymer (A) that satisfies the following requirements (a-1) to (a-5), and 10 to 99% by mass of a lubricating oil base oil (B) that satisfies the following requirements (b-1) and (b-2), The modified ethylene-α-olefin copolymer (A) comprises a main chain portion (P) derived from the ethylene-α-olefin copolymer (X) and a graft-modified portion (Q). A lubricating oil composition in which the lubricating oil base oil (B) is one or more base oils selected from the group consisting of mineral oils and synthetic oils: (a-1) The content of structural units derived from ethylene in the main chain portion (P) is 10 to 90 mol% (provided that the sum of the content of structural units derived from ethylene and structural units derived from α-olefins in the main chain portion (P) is 100 mol%); (a-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (a-3) The content of the graft-modified portion (Q) is 1 to 20% by mass (provided that the total amount of the main chain portion (P) and the graft-modified portion (Q) is 100% by mass); (a-4) The graft-modified region (Q) contains one or more primary hydroxyl groups; (a-5) Substantially no heat of fusion (ΔH) is observed in the range of 0 to 300°C in differential scanning calorimetry (DSC); (b-1) Kinematic viscosity at 100°C is 1 to 10 mm ２ / s is; (b-2) The viscosity index is 90 or higher.

2. The lubricating oil composition according to claim 1, wherein the graft-modified portion (Q) comprises a structural unit (Qs) derived from one or more carboxylic acid compounds (S) selected from the group consisting of unsaturated carboxylic acids containing one or more carbon-carbon unsaturated bonds and their derivatives, and a structural unit (Qt) derived from a reactive compound (T) having two or more functional groups in its molecule that can react with the carboxylic acid compound (S), and having one or more primary hydroxyl groups as functional groups that can react with the carboxylic acid compound (S).

3. The lubricating oil composition according to claim 2, wherein the content of structural units (Qs) derived from the carboxylic acid compound (S) is 30 to 80 mol% (provided that the total of structural units (Qs) derived from the carboxylic acid compound (S) and structural units (Qt) derived from the reactive compound (T) is 100 mol%).

4. The lubricating oil composition according to claim 2, wherein the reactive compound (T) further has one or more amino groups as functional groups that can react with the carboxylic acid compound (S).

5. The carboxylic acid compound (S) is one or more compounds selected from the group consisting of maleic acid and maleic anhydride, and the reactive compound (T) is HO-CH ２ -C ｊ H ２ｊ O ｋ -NH ２ The lubricating oil composition according to claim 2, wherein the compound is represented by (where j is an integer from 1 to 5, and k is an integer from 0 to 3).

6. The content of structural units derived from ethylene in the main chain portion (P) is 30 to 70 mol%, The weight-average molecular weight (Mw) is 2,500 to 30,000. The content of the graft-modified portion (Q) is 2.0 to 12% by mass. The lubricating oil composition according to claim 2, wherein the content of structural units (Qs) derived from the carboxylic acid compound (S) is 35 to 70 mol%.

7. A method for producing the lubricating oil composition described in claim 2, The process involves graft-modifying the ethylene-α-olefin copolymer (X) with the carboxylic acid compound (S) to obtain an acid-modified copolymer (Y), The process involves reacting the acid-modified copolymer (Y) with the reactive compound (T) to obtain the modified ethylene-α-olefin copolymer (A). A method for producing a lubricating oil composition, including the following:

8. The method for producing a lubricating oil composition according to claim 7, further comprising the step of stirring the lubricating oil base oil (B) and the modified ethylene-α-olefin copolymer (A) to obtain a modified ethylene-α-olefin copolymer (A)-containing concentrate (AC).

9. A method for producing the lubricating oil composition described in claim 2, The process involves graft-modifying the ethylene-α-olefin copolymer (X) with the carboxylic acid compound (S) to obtain an acid-modified copolymer (Y), A method for producing a lubricating oil composition, comprising the steps of reacting the acid-modified copolymer (Y) with the reactive compound (T) in the lubricating oil base oil (B), and further stirring to obtain a concentrate (AC) containing a modified ethylene-α-olefin copolymer (A).

10. The ethylene-α-olefin copolymer (X) satisfies the following requirements (x-1) to (x-4), A method for producing the lubricating oil composition according to any one of claims 7 to 9, wherein the acid-modified copolymer (Y) satisfies the following requirements (y-1) to (y-3): (x-1) The content of structural units derived from ethylene is 10 to 90 mol% (where the sum of the content of structural units derived from ethylene and structural units derived from α-olefins is 100 mol%); (x-2) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (x-3) Kinematic viscosity at 100°C is 20 to 50,000 mm² ２ / s is; (x-4) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C; (y-1) The weight-average molecular weight (Mw) determined by gel permeation chromatography (GPC) is between 1,000 and 50,000; (y-2) The content of structural units derived from the carboxylic acid compound (S) is 0.1 to 20% by mass (provided that the sum of structural units derived from the carboxylic acid compound (S) and the main chain portion (P) is 100% by mass); (y-3) Substance scanning calorimetry (DSC) shows virtually no heat of fusion (ΔH) in the range of 0 to 300°C.

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