Modified copolymer and method for producing modified copolymer

Abstract

To provide a modified copolymer with excellent compatibility with polar materials and a method for producing the copolymer. [Solution] Modified copolymer (A) comprising a main chain portion (P) derived from an ethylene-α-olefin copolymer (X) and a graft-modified portion (Q), satisfying requirements (a-1) to (a-5): (a-1) The content of structural units derived from ethylene in the main chain portion (P) is 10 to 90 mol% (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 100 mol%); (a-2) The Mw determined by GPC is 1,000 to 50,000; (a-3) The content of the graft-modified portion (Q) is 1 to 20 mass% (the sum of the main chain portion (P) and the graft-modified portion (Q) is 100 mass%); (a-4) The graft-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.

Description

[Technical Field]

[0001] This invention relates to a modified copolymer and a method for producing a modified copolymer. [Background technology]

[0002] Ethylene-α-olefin copolymers are used in a variety of applications, including rubber softeners, paint additives, lubricant additives, plasticizers, and metalworking fluids. However, due to the low polarity inherent in their structure, ethylene-α-olefin copolymers have limited compatibility with other materials and thus have restricted applications. Therefore, development is underway to create modified copolymers with added polar functional groups, such as modified maleic anhydride copolymers, which are commonly known as acid-modified copolymers.

[0003] For example, an imide group-containing low molecular weight ethylene copolymer has been proposed as a useful novel compound that, when added to industrial gear oil or the like, imparts excellent detergency and provides a composition with excellent shear stability (for example, Patent Document 1). Furthermore, modified polyolefin resins that offer an excellent balance of heat resistance and solution stability, making them suitable for use in primers, paints, inks, adhesives, and the like, have been proposed (for example, Patent Documents 2 and 3). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-59119 [Patent Document 2] Japanese Patent Publication No. 2019-210359 [Patent Document 3] Japanese Patent Publication No. 2020-37687 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, from the perspective of expanding the application range of ethylene-α-olefin copolymers, copolymers with polar functional groups are still in short supply, and there is a need for ethylene-α-olefin copolymers with more polar or more reactive functional groups.

[0006] The object of the present invention is to provide a modified copolymer with excellent compatibility with polar materials and a method for producing the copolymer. [Means for solving the problem]

[0007] 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.

[0008] [1] Modified copolymer (A) comprising a main chain portion (P) derived from an ethylene-α-olefin copolymer (X) and a graft-modified portion (Q), and satisfying the following requirements (a-1) to (a-5): (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.

[0009] [2] The modified copolymer (A) 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 their derivatives 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).

[0010] [3] The modified copolymer (A) 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%.

[0011] [4] The modified copolymer (A) according to [2] or [3], wherein the reactive compound (T) further has one or more amino groups as functional groups that can react with the carboxylic acid compound (S).

[0012] [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 modified copolymer (A) described in any of [2] to [4], which is a compound represented by -NH2 (where j is an integer from 1 to 5 and k is an integer from 0 to 3).

[0013] [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. A modified copolymer (A) 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%.

[0014] A method for producing a modified copolymer (A) 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 copolymer (A), and A method for producing a modified copolymer (A) containing the above.

[0015] [8] The ethylene-α-olefin copolymer (X) satisfies the following requirements (x-1) to (x-4): A method for producing the modified copolymer (A) according to [7], 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]

[0016] The modified copolymer of the present invention exhibits excellent compatibility with polar materials. Therefore, it can be suitably used as an additive for coating materials and lubricating oils. [Modes for carrying out the invention]

[0017] [Modified copolymer (A)] The modified copolymer (A) of the present invention is characterized by comprising a main chain portion (P) derived from an ethylene-α-olefin copolymer (X) and a graft-modified portion (Q).

[0018] 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.

[0019] ·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%. When the content of structural units derived from ethylene is within the aforementioned range, a non-crystalline amorphous copolymer is obtained, and a modified copolymer (A) with excellent fluidity and compatibility with polar materials can be easily obtained.

[0020] In this specification, "structural unit derived from ethylene" means the structural unit corresponding to ethylene, i.e., the structural unit represented by -CH2-CH2-. Similarly, "structural unit derived from α-olefin" means the structural unit corresponding to α-olefin, i.e., the structural unit represented by -CH2-CRR'- (where R and R' are independently a hydrogen atom or an alkyl group).

[0021] The content of ethylene-derived structural units in the modified copolymer (A) and the ethylene-α-olefin copolymer (X) described later is: 13 It can be measured by 13C-NMR, and peak identification and quantification can be performed, for example, according to the method described later and the method described in "Polymer Analysis Handbook" (published by Asakura Shoten, pp. 163-170). Specifically, the content of structural units derived from ethylene is measured by the method described in the examples below.

[0022] ·Requirements (a-2) The weight-average molecular weight (Mw) of the modified copolymer (A), determined by gel permeation chromatography (GPC), is 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 2,500 to 30,000, even more preferably 3,000 to 20,000, and particularly preferably 5,000 to 15,000. When the weight-average molecular weight (Mw) is within the aforementioned range, a modified copolymer (A) with excellent fluidity and compatibility with polar materials can be easily obtained.

[0023] 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.

[0024] ·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.

[0025] 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.

[0026] ·Requirements (a-4) The graft-modified portion (Q) of the modified copolymer (A) contains one or more primary hydroxy groups, and preferably contains one or more primary hydroxy groups and one or more amide groups or imide groups. When the graft-modified portion (Q) contains one or more of the aforementioned functional groups, the compatibility with polar materials is excellent. Examples of the primary hydroxy group include -C j H 2j O k j(CH2CH2O)k-CH2-OH (where j is an integer of 1 to 5, and k is an integer of 0 to 3).

[0027] · Requirement (a-5) In differential scanning calorimetry (DSC) of the modified copolymer (A), substantially no heat of fusion (ΔH) is observed within the range of 0 to 300°C. Here, the phrase "substantially no heat of fusion (ΔH) is observed" means that no melting peak is observed, or the measured heat of fusion (ΔH) is 1 J / g or less. When substantially no heat of fusion (ΔH) is observed within the range of 0 to 300°C, it means that the modified copolymer (A) is an amorphous copolymer having no crystallinity, which is excellent in fluidity and excellent in compatibility with polar materials. Specifically, the heat of fusion (ΔH) of the modified copolymer (A), the ethylene·α-olefin copolymer (X) described below, and the acid-modified copolymer (Y) described below is measured by the method described in the Examples mentioned later.

[0028] <Main chain portion (P)> The modified copolymer (A) comprises a main chain portion (P) derived from an ethylene·α-olefin copolymer (X). Examples of the α-olefin constituting the ethylene·α-olefin copolymer (X) include α-olefins having 3 or more carbon atoms other than ethylene, preferably α-olefins having 3 to 20 carbon atoms, more preferably α-olefins having 3 to 10 carbon atoms.

[0029] 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.

[0030] 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.

[0031] ·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.

[0032] ·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.

[0033] 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.

[0034] ·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.

[0035] ·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.

[0036] <Graft degeneration area (Q)> The modified copolymer (A) contains a graft-modified region (Q). Preferably, the graft-modified portion (Q) 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.

[0037] 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%.

[0038] 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.

[0039] 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).

[0040] 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.

[0041] 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.

[0042] 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).

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] [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 that includes 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)").

[0048] <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).

[0049] 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).

[0050] 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).

[0051] 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).

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] • 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] <Process (S2)> In step (S2), 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) 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).

[0064] 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).

[0065] 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.

[0066] 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.

[0067] The reaction temperature is typically 100 to 200°C, preferably 110 to 190°C, and more preferably 120 to 180°C. The reaction time is typically 1 minute to 20 hours, preferably 1.5 minutes to 10 hours, and more preferably 2.0 minutes to 5 hours. The reaction atmosphere is preferably an inert gas atmosphere under normal pressure or reduced pressure.

[0068] <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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] • 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].

[0073] [ka]

[0074] (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.

[0075] 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] j is an integer between 1 and 4, preferably 2. n is an integer between 1 and 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] 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].

[0097] [ka] In equation [II], Y, M, R 1 ~R 14 Q and j have the same signs as in the above formula [1].

[0098] 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).

[0099] 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.

[0100] 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.

[0101] 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.

[0102] ·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).

[0103] (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, each 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-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum; tri-branched alkylaluminums such as triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tri(4-methylphenyl)aluminum; dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride; those represented by the general formula (i-C4H9) x Al y (C5H 10 ) z (wherein x, y and z are positive numbers, and z≦2x) alkenylaluminums such as isoprenylaluminum; alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; those represented by 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.

[0104] (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, M 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.

[0105] (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 the organoaluminum oxy compound (N-2). Specifically, examples include compounds represented by the following general formula [III] and compounds represented by the following general formula [IV].

[0106] [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.

[0107] 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.

[0108] 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 refer to 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 is insoluble or sparingly soluble in benzene.

[0109] Furthermore, examples of organoaluminum oxy compounds (N-2) include modified methylaluminoxanes represented by the following general formula [V].

[0110] [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.

[0111] 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. For this reason, 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 in which Rx is 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)).

[0112] Furthermore, as organoaluminum oxy compounds (N-2), organoaluminum oxy compounds containing boron represented by the following general formula [VI] can also be mentioned.

[0113] [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.

[0114] Compounds (N-3) that react with a crosslinked 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 Patent Publication No. 1-501950, Japanese Patent Publication No. 1-502036, Japanese Patent Application Publication No. 3-179005, Japanese Patent Application Publication No. 3-179006, Japanese Patent Application Publication No. 3-207703, Japanese Patent Application Publication No. 3-207704, and U.S. Patent No. 5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

[0115] The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].

[0116] [ka]

[0117] In formula [VII], R e+ H + Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations containing transition metals. f ~R i These substituents may be the same or different from each other, and are selected from the group consisting of hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups, nitrogen-containing groups, oxygen-containing groups, halogen atoms, and halogen-containing groups, and are preferably substituted aryl groups.

[0118] Specific examples of the above-mentioned carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(4-methylphenyl)carbenium cation, and tris(3,5-dimethylphenyl)carbenium cation.

[0119] Specifically, examples of the above-mentioned ammonium cations 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.

[0120] Examples of the phosphonium cations mentioned above include triarylphosphonium cations such as triphenylphosphonium cation, tris(4-methylphenyl)phosphonium cation, and tris(3,5-dimethylphenyl)phosphonium cation.

[0121] R e+ Among the above specific examples, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

[0122] Examples of ionized compounds that are preferably used include triphenylcarbenium tetraphenyl borate, 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.

[0123] 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.

[0124] 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.

[0125] Examples of ionized compounds that are preferably used include di-n-propylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate, which contain dialkylammonium cations.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] 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.

[0135] The ion-exchange layered compound may be a layered compound with expanded interlayers obtained by utilizing ion exchange properties to exchange exchangeable ions between layers with another large bulky ion. Such bulky ions play a role of supporting pillars for the layered structure, and are usually called pillars. In addition, 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 (R is a hydrocarbon group, etc.), [Al 13 O4(OH) 24 7+ , [Zr4(OH) 14 2+ , [Fe3O(OCOCH3)6] + and metal hydroxide ions such as the above. These compounds may be used singly or in combination of two or more kinds.

[0136] When intercalating these compounds, polymers obtained by hydrolytic polycondensation of metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (R is a hydrocarbon group, etc.), colloidal inorganic compounds such as SiO2, and the like can also be allowed to coexist. Examples of pillars include oxides formed by intercalating the above metal hydroxide ions between layers followed by heating and dehydration.

[0137] 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 support (R) include granular or fine-particle solids having 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. ​​

[0138] The method of use and order of addition of each component of the polymerization catalyst may be arbitrarily selected. Further, at least two or more of each component in the catalyst may be brought into contact in advance. The crosslinked metallocene compound (L) (hereinafter also referred to as "component (L)") is usually used in an amount of 10 -9 ~10 -1 mol per liter of reaction volume, preferably 10 -8 ~10 -2 mol per liter of reaction volume.

[0139] The organometallic compound (N-1) (hereinafter also referred to as "component (N-1)") is used in such an amount 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.

[0140] The organoaluminum oxy compound (N-2) (hereinafter also referred to as "component (N-2)") is used in such an amount that the molar ratio [(N-2) / M] of the aluminum atom in component (N-2) to the transition metal atom (M) in component (L) is usually 10 to 5,000, preferably 20 to 2,000.

[0141] The ionic compound (N-3) (hereinafter also referred to as "component (N-3)") is used in such an amount 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.

[0142] The polymerization temperature is usually -50 to 300°C, preferably 30 to 250°C, more preferably 100 to 250°C, still more preferably 130 to 200°C. In the polymerization temperature range within the above range, as the temperature increases, the viscosity of the solution during polymerization decreases, and removal of heat of polymerization also becomes easier. The polymerization pressure is usually normal pressure to 10 MPa gauge pressure (MPa-G) (that is, not lower than normal pressure and not higher than (normal pressure + 10 MPa)), preferably normal pressure to 8 MPa-G (that is, not lower than normal pressure and not higher than (normal pressure + 8 MPa)).

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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).

[0149] [Applications of Modified Copolymer (A)] Modified copolymer (A) is more polar than conventional modified ethylene-α-olefin copolymers and exhibits excellent compatibility with polar materials. In particular, since modified copolymer (A) has one or more primary hydroxyl groups in the graft-modified portion (Q), it exhibits excellent compatibility with materials containing hydroxyl groups. For this reason, it can be suitably used as an additive in coating materials such as inks, paints, and heat sealants; and as an additive in lubricants such as automotive engine oil, automotive gear oil, automotive transmission oil, industrial lubricants, hydraulic oil, metalworking oil, and cutting oil.

[0150] 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; and polar resins such as polyamides, polyacetals, polyesters, polycarbonates, and polyketones.

[0151] When used as an additive in lubricating oils, its higher polarity compared to conventional modified ethylene-α-olefin copolymers results in excellent compatibility with various polar additives such as detergents, dispersants, friction modifiers, lubricity agents, antioxidants, and rust inhibitors, thus expanding the range of formulation designs. Furthermore, by having one or more primary hydroxyl groups in the graft-modified portion (Q), it is expected to suppress the formation of water droplets from moisture mixed in the oil, thereby preventing lubrication failures.

[0152] Furthermore, since the graft-modified portion (Q) of the modified copolymer (A) has primary hydroxyl groups, improved reactivity with reactive groups such as isocyanates and epoxides can be expected. For this reason, it is considered useful as a reactive plasticizer for urethanes, acrylics, and epoxys. [Examples]

[0153] 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".

[0154] [Methods for measuring the structure, molecular weight, etc. of raw materials] The structure, molecular weight and other properties of each copolymer were measured by the following methods. <Ethylene Content (mol%)> 13 The ethylene content (mol%) in each copolymer was measured by 13C-NMR using the following apparatus and conditions. Using an ECP500 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., measurement was performed under the following conditions: solvent: mixed solvent of orthodichlorobenzene / deuterated benzene (80 vol% / 20 vol%), sample concentration: 55 mg / 0.6 mL, measurement temperature: 120°C, observed nucleus: 13 13C (125 MHz), sequence: single pulse proton decoupling, pulse width: 4.7 µsec (45° pulse), repetition time: 5.5 sec, number of integrations: 10,000 times or more, reference value for chemical shift: 27.50 ppm. From the 13C-NMR spectrum measured as described above, 13 the ethylene content was determined based on the reports of G. J. Ray (Macromolecules, 10, 773 (1977)), J. C. Randall (Macromolecules, 15, 353 (1982)), K. Kimura (Polymer, 25, 4418 (1984)) et al.

[0155] <Kinematic Viscosity at 100°C> Kinematic viscosity at 100°C (100°C kinematic viscosity) was measured and calculated by the method described in JIS K 2283:2000.

[0156] <Number Average Molecular Weight, Weight Average Molecular Weight and Molecular Weight Distribution> By gel permeation chromatography (GPC), weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene molecular weight were calculated according to the general calibration procedure, and molecular weight distribution (Mw / Mn) was calculated from these values. High-speed GPC measurement device: HLC-8320GPC (manufactured by Tosoh Corporation) Separation column: TSKgel Super MultiporeHZ-M (manufactured by Tosoh Corporation) four columns connected in series Column temperature: 40°C Mobile phase: tetrahydrofuran (manufactured by Wako Pure Chemical Corporation) 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)

[0157] <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.

[0158] <Acid value> The acid value was measured according to the method compliant with JIS K 2501:2003.

[0159] <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).

[0160] <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%]

[0161] [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.

[0162] 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.

[0163] [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-tert-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.

[0164] 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.

[0165] [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.

[0166] [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.

[0167] [Example 1] 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.

[0168] [Example 2] Production of modified ethylene-propylene copolymer (A2) The procedure was carried out in the same manner as in Example 1, except that the acid-modified copolymer (Y1) was changed to an 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 the carboxylic acid compound (S) of the 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 the carboxylic acid compound (S) (Qs) was 50 mol%, and the heat of fusion (ΔH) was substantially not measured in the range of 0 to 300°C.

[0169] [Comparative Examples 1 and 2] For Comparative Examples 1 and 2, the acid-modified copolymer (Y1) obtained in Production Example 3 and the acid-modified copolymer (Y2) obtained in Production Example 4 were used as comparative modified copolymers, respectively.

[0170] <Solvent solubility test> In a glass vial with a lid, the modified copolymer (A1), modified copolymer (A2), acid-modified copolymer (Y1), or acid-modified copolymer (Y2) obtained in the above manufacturing example and example, along with the solvent listed in Table 1, were placed so that the concentration of each copolymer was 10% by mass. After sealing the glass vial, it was shaken by hand for 1 minute. Next, it was treated with ultrasound for 60 minutes, then allowed to stand for 24 hours, and its appearance was evaluated according to the following criteria. The evaluation results are shown in Table 1. 2: An emulsion was obtained in which the copolymer was dispersed in the solution. 1: The copolymer and the solvent were completely separated. [Table 1]

Claims

1. A modified copolymer (A) comprising a main chain portion (P) derived from an ethylene-α-olefin copolymer (X) and a graft-modified portion (Q), satisfying the following requirements (a-1) to (a-5): (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) Substance scanning calorimetry (DSC) shows that virtually no heat of fusion (ΔH) is observed in the range of 0 to 300°C.

2. 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 compounds (S), The modified copolymer (A) according to claim 1, having one or more primary hydroxyl groups as functional groups that can react with the carboxylic acid compound (S).

3. The modified copolymer (A) 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 modified copolymer (A) 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 modified copolymer (A) according to claim 2, which is a compound 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 modified copolymer (A) 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 a modified copolymer (A) according to any one of claims 2 to 6, 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 copolymer (A), and A method for producing a modified copolymer (A) containing

8. The ethylene-α-olefin copolymer (X) satisfies the following requirements (x-1) to (x-4), A method for producing the modified copolymer (A) according to claim 7, 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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