Photocurable polyolefins and compositions

Abstract

The present invention aims to provide photocurable polyolefins, such as photocurable liquid polyolefins, and photocurable raw materials that can form molded articles having high photocurability and exhibiting minimal changes in appearance and mechanical properties over time after light irradiation. [Solution] Modified ethylene-α-olefin copolymer (A) that satisfies the following requirements (a1) to (a3) ​​and contains an average of 0.3 or more (meth)acryloyl groups per molecule: (a1) The content of constituent units derived from ethylene is in the range of 15 to 85 mol% when the sum of the content of constituent units derived from ethylene and the content of constituent units derived from α-olefins having 3 to 20 carbon atoms is taken as 100 mol%; (a2) The number average molecular weight (Mn) is in the range of 400 to 40,000; (a3) ​​The internal olefin content per 1,000 carbon atoms based on Mn is 2 or less on average.

Description

[Technical Field]

[0001] The present invention relates to a photocurable polyolefin and its composition, and more particularly to a photocurable modified ethylene-α-olefin copolymer containing a (meth)acryloyl group and its composition. [Background technology]

[0002] Photocurable resins, which form cross-linked structures through reactions between polymerizable oligomers and monomers such as vinyl groups, (meth)acryloyl groups, and epoxy groups, starting with radicals and cations generated by light irradiation, are attracting attention from the perspective of energy conservation and reduction of environmental impact. UV-curable resins, which utilize ultraviolet light as the light source, can be cured at room temperature in a short time, resulting in less damage to the substrate and enabling energy-efficient handling. Furthermore, since the resin is mainly composed of low molecular weight oligomers, viscosity reduction with thinner is unnecessary, thus reducing the environmental impact. In addition, it is possible to create three-dimensional images using UV-curable resins by irradiating with ultraviolet light simultaneously with coating, as in 3D printers. For this reason, the application of UV-curable resins in paints, inks, coating materials, adhesives, plate-making materials, resists, and encapsulants is being considered. The application of such photocurable resins to low-polarity substrates such as polyolefins is also being explored.

[0003] When applying photocurable resins to polyolefins, they are often used in the form of photocurable liquid polyolefins. However, photocurable resins must possess functional groups capable of generating radicals and / or cations upon irradiation with light, such as (meth)acryloyl groups. For this reason, photocurable resins have been considered difficult to use with low-polarity substrates such as polyolefins. Despite this, various attempts have been made to apply photocurable resins to low-polarity substrates such as polyolefins, and several reports have been published on these attempts.

[0004] Patent documents 1 and 2 propose polyisoprene as a conjugated diene polymer having a specific (meth)acryloyl group. It is characterized by small volume change before and after photocuring and high mechanical properties after photocuring, but the changes over time of the photocured product are not mentioned. Furthermore, patent document 3 proposes a method for producing polybutadiene having a specific molecular structure by introducing (meth)acrylic acid ester. Excellent photocurability is proposed by measuring viscosity change before and after photocuring, but the quality of the photocured product is not mentioned. In addition, patent document 4 proposes hydrogenated polybutadiene having a specific molecular structure by introducing (meth)acrylic acid ester. It is characterized by improved yellowing immediately after photocuring and after heat resistance testing compared to conventional modified polybutadiene due to hydrogenation. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2003-192745 [Patent Document 2] Japanese Patent Publication No. 2003-192750 [Patent Document 3] Patent No. 5265116 [Patent Document 4] Patent No. 6059356 [Overview of the project] [Problems that the invention aims to solve]

[0006] Conventional photocurable liquid polyolefins may contain unsaturated bonds within the molecule, particularly unsaturated bonds based on internal olefins derived from isoprene or butadiene, which has presented challenges in the long-term stability of the quality of the photocured product.

[0007] The present invention aims to provide photocurable polyolefins, such as photocurable liquid polyolefins, and photocurable raw materials that can form molded articles having high photocurability and exhibiting minimal changes in appearance and mechanical properties over time after light irradiation. [Means for solving the problem]

[0008] As a result of diligent research to solve the above problems, the present inventors have found that the above problems can be solved by using a modified ethylene-α-olefin copolymer that satisfies specific requirements as a photocurable polyolefin, such as a photocurable liquid polyolefin, and have completed the present invention.

[0009] The present invention provides the following: [1] Modified ethylene-α-olefin copolymer (A) that satisfies the following requirements (a1) to (a3) ​​and contains an average of 0.3 or more (meth)acryloyl groups per molecule: (a1) The content of constituent units derived from ethylene is in the range of 15 to 85 mol%, when the sum of the content of constituent units derived from ethylene and the content of constituent units derived from α-olefins having 3 to 20 carbon atoms is taken as 100 mol%; (a2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent is in the range of 400 to 40,000; (a3) The internal olefin content per 1,000 carbon atoms is 2 or less on average, based on the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent. [2] The modified ethylene-α-olefin copolymer (A) described in [1] that satisfies the following requirement (a4): (a4) No peaks were observed in the number-average molecular weight (Mn) of 100,000 or higher, as measured by gel permeation chromatography (GPC) and converted to polystyrene equivalent. [3] A modified ethylene-α-olefin copolymer (A) according to [1] or [2], wherein the Brookfield viscosity at 45°C is 350 Pa·s or less. [4] A modified ethylene-α-olefin copolymer (A) according to any one of [1] to [3], wherein the α-olefin is propylene. [5] A modified ethylene-α-olefin copolymer (A) according to any one of [1] to [4], comprising a constituent unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters. [6] A step (S1) involves graft-modifying an ethylene-α-olefin copolymer (A') with one or more compounds (X) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, Following the above step (S1), a graft modification step (S2) is performed with one or more compounds (Y) selected from the group consisting of methacrylic acid derivatives and acrylic acid derivatives, in the presence of one or more compounds (Z) selected from the group consisting of quinone derivatives and phenol derivatives. A method for producing a modified ethylene-α-olefin copolymer (A) containing the above. [7] The method for producing a modified ethylene-α-olefin copolymer (A) according to [6], wherein step (S2) is a step (S2-1) in which a mixture of compound (Y) and compound (Z) is added to the modified ethylene-α-olefin copolymer (A'') obtained in step (S1). [8] A method for producing a modified ethylene-α-olefin copolymer (A) according to [6] or [7], wherein the compound (X) is maleic anhydride. [9] A method for producing a modified ethylene-α-olefin copolymer (A) according to any one of [6] to [8], wherein the compound (Y) is one or more compounds selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

[10] A composition comprising a (meth)acrylic monomer and the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5].

[11] A composition comprising a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups in the molecule and the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5].

[12] A molded article comprising the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5] or the composition described in

[10] or

[11] .

[13] A raw material for a molded article comprising the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5] or the composition described in

[10] or

[11] .

[14] An adhesive comprising the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5] or the composition described in

[10] or

[11] .

[15] A sealing material comprising the modified ethylene-α-olefin copolymer (A) described in any one of [1] to [5] or the composition described in

[10] or

[11] . [Effect of the Invention]

[0010] According to the present invention, it is possible to provide a photocurable polyolefin such as a photocurable liquid polyolefin that has sufficiently high photocurability and has little change over time in appearance and mechanical properties after light irradiation. [Embodiments for Carrying Out the Invention]

[0011] Hereinafter, the present invention will be specifically described. In this specification, "~" indicating a numerical range means "M or more and N or less" when expressed as, for example, "M~N" (M and N are numerical values satisfying M < N) unless otherwise specified.

[0012] In this specification, when M is an olefin constituting a polymer, the expression "constituent unit derived from M" is sometimes used. This refers to "the constituent unit corresponding to M," that is, a constituent unit having a pair of bonds formed when the π bond constituting the double bond of M opens.

[0013] In this specification, when M is the olefin constituting a polymer, the expression "M constituent unit content" is sometimes used. However, if the polymer is a modified polymer, this refers to the molar content of olefin M in the polymer before modification.

[0014] In this specification, the term "(meth)acrylic" is used as a concept encompassing acrylic, methacrylic, and both acrylic and methacrylic, and the term "(meth)acryloyl group" is used as a concept encompassing acryloyl group, methacryloyl group, and both acryloyl and methacryloyl groups.

[0015] [Modified ethylene-α-olefin copolymer (A)] The modified ethylene-α-olefin copolymer (A) according to the present invention [hereinafter sometimes abbreviated as "copolymer (A)"] satisfies the following requirements (a1) to (a3) ​​and contains 0.3 or more (meth)acryloyl groups on average per molecule.

[0016] <(meth)acryloyl group> The (meth)acryloyl groups contained in the modified ethylene-α-olefin copolymer (A) function as functional groups capable of generating radicals and / or cations upon irradiation with light. The presence of these (meth)acryloyl groups allows the modified ethylene-α-olefin copolymer (A) to function as a photocurable polyolefin. Here, the modified ethylene-α-olefin copolymer (A) contains an average of 0.3 or more (meth)acryloyl groups per molecule, preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.8 or more (meth)acryloyl groups, to ensure sufficient curing by light irradiation. Regarding the provision in this invention that the number of (meth)acryloyl groups contained in the modified ethylene-α-olefin copolymer (A) may be less than 1 on average per molecule, the inventors believe that some molecules constituting the modified ethylene-α-olefin copolymer (A) contain 2 or more (meth)acryloyl groups per molecule, and that curing by light irradiation is possible. On the other hand, there is no particular upper limit to the number of (meth)acryloyl groups contained in the modified ethylene-α-olefin copolymer (A), but it is preferably 30 or less on average per molecule, and more preferably 10 or less. That is, the number of (meth)acryloyl groups contained in the modified ethylene-α-olefin copolymer (A) is 0.3 or more on average per molecule, preferably 0.4 to 30. The number may be 0.5 to 30. In addition, in a preferred and exemplary embodiment of the present invention, the number is 0.8 to 10.

[0017] Here, in one of the typical aspects of the present invention, the (meth)acryloyl group is included as part of a structural unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters in the modified ethylene-α-olefin copolymer (A). In other words, in one of the typical aspects of the present invention, the modified ethylene-α-olefin copolymer (A) contains a structural unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters.

[0018] The structural unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters usually has one or more bonds in the alcohol moiety constituting the methacrylic acid ester or acrylic acid ester. For example, -(R AL -O) x -C(=O)-CH(-R AC )=CH2···[E1] Or -O-(R AL -O) x -C(=O)-CH(-R AC )=CH2···[E2] Has a structure represented by. Here, the R AC Is a hydrogen atom or a methyl group, the R AL Is a divalent or higher hydrocarbon group, and x is an integer of 1 or more, for example, 1 or 2. Here, the R AL May have one or more alcoholic hydroxy groups, may have one or more aryloxy groups, one or more -(R AL ’-O) y -C(=O)-CH(-R AC ’)=CH2···[Ea1] Or -O-(R AL ’-O) y -C(=O)-CH(-R AC ’)=CH2···[Ea2] May have a group represented by. Here, the R AC' is a hydrogen atom or a methyl group, and the R AL ' is a hydrocarbon group with two or more valent values, and y is an integer of 0 or 1 or more, for example, 0 or 1. The R AL ' may have one or more alcoholic hydroxyl groups, one or more aryloxy groups, or one or more groups represented by the above formula [Ea1] or [Ea2].

[0019] Furthermore, the R AC and R AC ' may be the same, or may be different from each other. The R AL and R AL ' may be the same, or may be different from each other. The R AL If there are 2 or more of these R AL These may be the same, or they may be different from each other. Similarly, the R AL If there are 2 or more of these R AL ' may be the same, or may be different from each other, and the R AC If there are 2 or more of these R AC ' may be the same, or they may be different from each other.

[0020] In exemplary and preferred embodiments of the present invention, the R AL x is an alkanediyl group, particularly preferably an ethane-1,2-diyl group, and x is 1.

[0021] In the modified ethylene-α-olefin copolymer (A), the constituent units corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters may be directly bonded to the ethylene-α-olefin copolymer portion constituting the main chain, or they may be indirectly bonded via other constituent units. For example, the ethylene-α-olefin copolymer portion constituting the main chain may be directly bonded to other constituent units, and the other constituent units may be directly bonded to the "constituent units corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters." In an exemplary embodiment of the present invention, the other constituent units are constituent units corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. In many cases, these "constituent units corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives" have a bond at a site corresponding to the ethylenic double bond of the corresponding unsaturated carboxylic acid or unsaturated carboxylic acid derivative, and a bond on a carbon atom constituting the carbonyl group.

[0022] If the other constituent unit corresponds to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, then the "constituent unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters" often has a structure represented by formula [E2].

[0023] For example, a modified ethylene-α-olefin copolymer (A) having "constituent units corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters" and "constituent units corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives" can be obtained by graft polymerizing one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives onto an ethylene-α-olefin copolymer, as described later, and then further reacting with one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. In this embodiment of the modified ethylene-α-olefin copolymer (A), it is presumed that the ethylene-α-olefin copolymer portion constituting the main chain is directly bonded to "constituent units corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives," and that "constituent units corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives" are directly bonded to "constituent units corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters." Here, the "constituent unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters" is often considered to bond with a carbol group contained in the "constituent unit corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives." In one preferred embodiment of the present invention, the "constituent unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters" in such a modified ethylene-α-olefin copolymer (A) has a structure represented by the formula [E2]. An example of a modified ethylene-α-olefin copolymer (A) in this embodiment is one in which the "constituent unit corresponding to one or more compounds selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives" has a constituent unit corresponding to maleic anhydride, and such a modified ethylene-α-olefin copolymer (A) is, for example, -CH(-C(=O)-OH)-CH2-C(=O)-O-(R AL -O)x -C(=O)-CH(-R AC )=CH2···[E2-1a] or -CH(-CH2-C(=O)-OH)-C(=O)-O-(R AL -O) x -C(=O)-CH(-R AC )=CH2···[E2-1b] (R AC , the R AL And x is R in the above formula [E2] AC , R AL It has a structure that is the same as x and x respectively.

[0024] The number of (meth)acryloyl groups contained in the modified ethylene-α-olefin copolymer (A) is: 1 This can be confirmed by calculating the ratio of vinyl hydrogen of the (meth)acryloyl group to the total hydrogen of the modified ethylene-α-olefin copolymer using 1H NMR.

[0025] <Requirements that modified ethylene-α-olefin copolymer (A) must satisfy> The modified ethylene-α-olefin copolymer (A) according to the present invention satisfies the following requirements (a1) to (a3).

[0026] Requirements (a1) The content of constituent units derived from ethylene (sometimes abbreviated as "ethylene content") is between 15 and 85 mol%, when the sum of the content of constituent units derived from ethylene and the content of constituent units derived from α-olefins is taken as 100 mol%.

[0027] Requirement (a1) specifies that the modified ethylene-α-olefin copolymer (A) contains constituent units derived from ethylene and constituent units derived from α-olefin, and specifies the ratio of the content of constituent units derived from ethylene to the total content of constituent units derived from ethylene and constituent units derived from α-olefin.

[0028] Here, "constituent units derived from ethylene" refers to the constituent units corresponding to ethylene, i.e., the constituent units represented as -CH2-CH2-. Similarly, "constituent units derived from α-olefins" refers to the constituent units corresponding to α-olefins, i.e., the constituent units represented as -CH2-CRR'- (where R and R' are independently hydrogen atoms or alkyl groups).

[0029] The ethylene content is 15 to 85 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and even more preferably 40 to 60 mol%. If the ethylene content is too high or too low, the crystallinity will increase, which may cause turbidity due to crystallization, or the photocurability may deteriorate due to the turbidity.

[0030] The ethylene content of the modified ethylene-α-olefin copolymer (A) is: 13 The peaks can be measured using 13C-NMR, and for example, the peaks can be identified and quantified according to the method described later and the method described in the "Handbook of Polymer Analysis" (published by Asakura Shoten, pp. 163-170).

[0031] Examples of α-olefins constituting the modified ethylene-α-olefin copolymer (A) according to the present invention include α-olefins other than ethylene that have 3 or more carbon atoms. Typical examples include α-olefins with 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, and 1-eicosene. These α-olefins may be used individually or in combination of two or more.

[0032] Of these α-olefins, α-olefins having 3 to 10 carbon atoms are preferred, propylene and 1-butene are more preferred, and propylene is even more preferred, from the viewpoint that crystallinity can be effectively reduced, a liquid copolymer can be obtained, and a composition and molded article that exhibit the desired effects can be easily obtained. The ethylene content can be adjusted by changing the amount of ethylene charged when producing the modified ethylene-α-olefin copolymer (A).

[0033] Thus, the modified ethylene-α-olefin copolymer (A) contains a structural unit derived from ethylene, a structural unit derived from α-olefin, and a (meth)acryloyl group. In one typical embodiment of the present invention, the modified ethylene-α-olefin copolymer (A) contains a main chain consisting of structural units derived from ethylene and structural units derived from α-olefin, and a (meth)acryloyl group bonded to the main chain. However, in addition to the structural units derived from ethylene and structural units derived from α-olefin, the modified ethylene-α-olefin copolymer (A) may further have structural units derived from cyclic olefins as structural units derived from other monomers. Here, "structural units derived from cyclic olefins" refers to structural units corresponding to cyclic olefins, i.e., structural units represented as -CRR'-CR''R'''- (where R, R', R'' and R''' are each independently hydrogen atoms or alkyl groups, and at least one of R and R' and one of R'' and R'''' are bonded to each other to form a ring).

[0034] Examples of cyclic olefins include cyclic olefins having 3 to 30 carbon atoms, preferably 3 to 20, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and tetracyclododecene. When the modified ethylene-α-olefin copolymer (A) contains structural units derived from cyclic olefins, the content of structural units derived from cyclic olefins can be, for example, 20 parts by mass or less, preferably 10 parts by mass or less, based on 100 parts by mass of the total content of structural units derived from ethylene and structural units derived from α-olefins.

[0035] The ethylene and α-olefin monomers constituting the modified ethylene-α-olefin copolymer (A) may be, for example, monomers derived from fossil fuels or monomers derived from biomass, and these monomers may be used individually or in combination of two or more. In other words, the modified ethylene-α-olefin copolymer (A) may consist only of monomers derived from fossil fuels, or only of monomers derived from biomass, or a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0036] Fossil fuels include 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.

[0037] Requirement (a2) The number-average molecular weight (Mn), measured by gel permeation chromatography (GPC) and calculated on a polystyrene basis, is in the range of 400 to 40,000.

[0038] Requirement (a2) specifies that the molecular weight of the modified ethylene-α-olefin copolymer (A) is within a certain range. In this specification, the number-average molecular weight (Mn) of the modified ethylene-α-olefin copolymer (A) is the value obtained by measuring by gel permeation chromatography (GPC) and converting it to polystyrene equivalent.

[0039] From the viewpoint of ensuring good photocurability, the Mn content of the modified ethylene-α-olefin copolymer (A) is 400 to 40,000, preferably 600 to 20,000, more preferably 800 to 12,000, and even more preferably 1,000 to 8,000.

[0040] If the number-average molecular weight (Mw) is too high, the viscosity will increase, which may worsen handling properties, or the mobility will decrease, which may worsen photocurability. Conversely, if the number-average molecular weight (Mn) is too low, there may be unmodified copolymers that do not contain (meth)acryloyl groups, which may also worsen photocurability. The aforementioned number-average molecular weight (Mn) can be appropriately adjusted by adjusting the ratio of ethylene supply to hydrogen supply when polymerizing the ethylene-α-olefin copolymer.

[0041] Requirement (a3) The internal olefin content per 1,000 carbon atoms is measured by gel permeation chromatography (GPC) and, based on the number-average molecular weight (Mn) obtained in polystyrene equivalent, is 2 or less on average.

[0042] Requirement (a3) ​​is that the modified ethylene-α-olefin copolymer (A) contains an amount of The partial olefin content must be below a certain level. Here, in this specification, "internal olefin" refers to an olefin that has double bonds in parts other than the ends of its molecular chain, and is usually, R A -CH=CH-R B , RA -CR C =CH-R B ,or, R A -CR C =CR D -R B (R A ,R B ,R C and R D Each of these is an alkyl group having 1 or more carbon atoms, and two or more of these may be bonded to each other to form a ring. The structure is represented by ( ).

[0043] On the other hand, "terminal olefins" refer to olefins that have a double bond at the terminal end of their molecular chain, and are usually, CH2=CH-R E ,or, CH2=CR F -R E (R E and R F Each of these is an alkyl group having 1 or more carbon atoms, and they may be bonded to each other to form a ring. The structure is represented by ( ).

[0044] In modified ethylene-α-olefin copolymer (A), the "internal olefin content" essentially refers to the content of double bonds in modified ethylene-α-olefin copolymer (A) that can be present in parts other than the terminals of the molecular chains constituting the modified ethylene-α-olefin copolymer (A), i.e., C A -CH=CH-C B , C A -CC C =CH-C B ,or, C A -CC C =CC D -C B (C A ,C B ,C C and C DThis refers to the content of the structure represented by ), which is a carbon atom adjacent to the carbon atom that forms the double bond. This "internal olefin content" is the content of double bonds that can be present in the terminal parts of the molecular chains constituting the modified ethylene-α-olefin copolymer (A), calculated from the total content of double bonds contained in the modified ethylene-α-olefin copolymer (A) (i.e., CH2= CH-C E ,or, CH2=CC F -C E (C E and C F This refers to a carbon atom adjacent to a carbon atom that forms a double bond. It can also be seen as subtracting the content of the structure represented by ). The inventors believe that if the internal olefin content contained in the molecule of the modified ethylene-α-olefin copolymer (A) is below a certain level, that is, if the number of double bonds that can exist in the modified ethylene-α-olefin copolymer (A) other than the ends of the molecular chain is small, then the molded article obtained by irradiating the modified ethylene-α-olefin copolymer (A) with light will show little change in appearance and mechanical properties over time. Such a modified ethylene-α-olefin copolymer (A) can be obtained, for example, by the method described in the "Method for Producing Modified Ethylene-α-Olefin Copolymer (A)" below.

[0045] The internal olefin content of the modified ethylene-α-olefin copolymer (A) is, on average, 2 or less, preferably 1 or less, more preferably 0.5 or less, and even more preferably 0.2 or less. If the internal olefin content of the modified ethylene-α-olefin copolymer (A) is too high, the internal olefin may react with oxygen in the air due to light or heat, which may cause yellowing of the appearance or a decrease in mechanical properties due to decomposition reactions.

[0046] The internal olefin content of the modified ethylene-α-olefin copolymer (A) is: 1It can be measured by 1H-NMR, and specifically can be determined by the method described in the examples below. Here, theoretically, as an internal olefin that may be contained in the modified ethylene-α-olefin copolymer (A), an olefin having a structure represented by RR'C=CR''R''' (R, R', R'', R''' are alkyl groups) can also be assumed, and to confirm the presence of such an olefin... 13 It is also thought that measurement by 13C-NMR method is necessary. However, the inventors have found that the possibility of internal olefins having such a structure appearing is extremely low. Therefore, when determining the internal olefin content of modified ethylene-α-olefin copolymer (A), in many cases, 13 We believe it is not necessary to use 1C-NMR measurement in conjunction with this method.

[0047] <Requirements that modified ethylene-α-olefin copolymer (A) should preferably satisfy> In addition to the above requirements (a1) to (a3), the modified ethylene-α-olefin copolymer (A) according to the present invention is preferably also satisfied with the following requirement (a4).

[0048] Requirement (a4) No peaks were observed in the number-average molecular weight (Mn) above 100,000, as measured by gel permeation chromatography (GPC) and converted to polystyrene equivalent.

[0049] Requirement (a4) stipulates that the modified ethylene-α-olefin copolymer (A) substantially does not contain any components with very large molecular weights. Here, components with very large molecular weights that may be included in the modified ethylene-α-olefin copolymer (A) include homopolymers that may be produced as by-products during the manufacturing process of the modified ethylene-α-olefin copolymer (A), such as homopolymers of methacrylic acid derivatives and homopolymers of acrylic acid derivatives. If the modified ethylene-α-olefin copolymer (A) does not contain polymer components with a number average molecular weight (Mn) of 100,000 or more (for example, homopolymers of methacrylic acid derivatives and homopolymers of acrylic acid derivatives), it tends to exhibit excellent curability, such as rapid photocuring. Here, "no peak detected" means that there are no peaks above the detection limit.

[0050] <Other requirements for modified ethylene-α-olefin copolymer (A)> The modified ethylene-α-olefin copolymer (A) according to the present invention preferably satisfies the following requirement (a5) in addition to the above requirements (a1) to (a3) ​​and the optional requirement (a4).

[0051] Requirement (a5) The Brookfield viscosity (BF viscosity) at 45°C is 350 mPa·s or less. The BF viscosity of the modified ethylene-α-olefin copolymer (A) at 45°C is preferably 330 mPa·s or less, and more preferably 1.0 to 300 mPa·s.

[0052] When the BF viscosity is below a certain value, the number of bubbles tends to decrease when the modified ethylene-α-olefin copolymer (A) is cured, resulting in a better product appearance. On the other hand, if the BF viscosity is too high, the viscosity increases, which can worsen handling properties and reduce mobility, potentially leading to poor photocurability. Also, if the BF viscosity is too low, there may be unmodified copolymers that do not contain (meth)acryloyl groups, which can also lead to poor photocurability.

[0053] The aforementioned BF viscosity can be measured using a Brookfield viscometer in accordance with ASTM D2983. The BF viscosity can be adjusted by adjusting the ratio of ethylene supply to hydrogen supply when polymerizing the ethylene-α-olefin copolymer.

[0054] [Method for producing modified ethylene-α-olefin copolymer (A)] The modified ethylene-α-olefin copolymer (A) according to the present invention satisfies the above requirements (a1) to (a3), preferably requirements (a1) to (a4), and contains an average of 0.3 or more (meth)acryloyl groups per molecule. The method for producing such a modified ethylene-α-olefin 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. However, the modified ethylene-α-olefin copolymer (A) is, for example, A step (S1) involves graft-modifying an ethylene-α-olefin copolymer (A') with one or more compounds (X) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, Following the above step (S1), a step (S2) is performed in which the graft is modified with one or more compounds (Y) selected from the group consisting of methacrylic acid derivatives and acrylic acid derivatives, in the presence of one or more compounds (Z) selected from the group consisting of quinone derivatives and phenol derivatives. It can be obtained by a manufacturing method that includes [the specified component]. According to this manufacturing method, a modified ethylene-α-olefin copolymer (A) can be obtained that satisfies the above requirements (a1) to (a3) ​​as well as requirement (a4). In this step (S1), a modified ethylene-α-olefin copolymer (A'') is obtained, which is obtained by graft-modifying the ethylene-α-olefin copolymer (A') with compound (X). Step (S2) is typically carried out as a step of graft-modifying the modified ethylene-α-olefin copolymer (A'') with compound (Y) in the presence of compound (Z). By carrying out step (S2) in the presence of compound (Z), the formation of components with very large molecular weights (for example, homopolymers of compound (Y)) can be suppressed, and a modified ethylene-α-olefin copolymer (A) that satisfies the above requirement (a4) can be obtained. Details of compound (Z) will be described later in the section "Compound (Z) and other polymerization inhibitors" below. Here, the aforementioned step (S2) specifically refers to: Step (S2-1): Adding a mixture of compound (Y) and compound (Z) to the modified ethylene-α-olefin copolymer (A'') obtained in step (S1). It is preferable to include it.

[0055] <Compound (X)> The compound (X) is one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives. That is, the compound (X) may be an unsaturated carboxylic acid, or an unsaturated carboxylic acid derivative, or a combination of an unsaturated carboxylic acid and an unsaturated carboxylic acid derivative.

[0056] Examples of unsaturated carboxylic acids include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (endosis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid).

[0057] Examples of derivatives of unsaturated carboxylic acids include acid anhydrides of the aforementioned unsaturated carboxylic acids. Among unsaturated carboxylic acids and their derivatives, unsaturated dicarboxylic acids and their derivatives are more preferred, and maleic acid and maleic anhydride are particularly preferred, especially in the reaction to produce modified ethylene-α-olefin copolymer (A'') because they do not easily produce by-products such as homopolymers.

[0058] When the modified ethylene-α-olefin copolymer (A'') is produced using an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative, the content of the unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative in the modified ethylene-α-olefin copolymer (A'') is 1 to 20% by mass, preferably 2 to 15% by mass, and more preferably 3 to 10% by mass.

[0059] Among the aforementioned unsaturated carboxylic acids and their derivatives, some can be produced from biomass-derived raw materials, such as maleic acid and maleic anhydride. One or more compounds (X) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, which constitute the monomers of the modified ethylene-α-olefin copolymer (A''), may be, for example, monomers derived from fossil fuels or monomers derived from biomass, and these monomers may be used individually or in combination of two or more. In other words, the modified ethylene-α-olefin copolymer (A) may consist only of monomers derived from fossil fuels, or only of monomers derived from biomass, or a combination of monomers derived from fossil fuels and monomers derived from biomass.

[0060] When maleic acid and maleic anhydride are used, the acid value of maleic acid and maleic anhydride in the modified ethylene-propylene copolymer (A'') (measured in accordance with JIS K5902) is 10 to 220 mg KOH / g, preferably 20 to 160 mg KOH / g, and more preferably 30 to 110 mg KOH / g.

[0061] <Compound (Y)> The compound (Y) is one or more selected from the group consisting of derivatives of methacrylic acid and derivatives of acrylic acid. That is, the compound (Y) may be a derivative of methacrylic acid, an acrylic acid derivative, or a combination of two or more of these. Preferred examples of derivatives of methacrylic acid and acrylic acid include methacrylic acid esters having an alcoholic hydroxyl group and acrylic acid esters having an alcoholic hydroxyl group.

[0062] The alcoholic hydroxyl group can bond with the unsaturated carboxylic acid moiety or unsaturated carboxylic acid derivative moiety of the modified ethylene-α-olefin copolymer (A''), thereby forming an ester bond with the unsaturated carboxylic acid moiety or unsaturated carboxylic acid derivative moiety. As a result, the constituent unit corresponding to the methacrylic acid ester having an alcoholic hydroxyl group, or the constituent unit corresponding to the acrylic acid ester having an alcoholic hydroxyl group, is fixed with sufficient strength to the moiety corresponding to the ethylene-α-olefin copolymer (A') via the unsaturated carboxylic acid moiety or unsaturated carboxylic acid derivative moiety.

[0063] Examples of methacrylic acid esters having an alcoholic hydroxyl group and acrylic acid esters having an alcoholic hydroxyl group include, HO-(R AL -O) x -C(=O)-CH(-R AC )=CH2···[E2'] Examples include those having a structure represented by R. AC is a hydrogen atom or a methyl group, and the R AL R is a divalent hydrocarbon group, HO- is an alcoholic hydroxyl group, and x is an integer of 1 or more, for example, 1 or 2. Here, R AL It may have one or more alcoholic hydroxyl groups, and may have one or more aryloxy groups, and one or more -(R AL '-O) x-C(=O)-CH(-R AC ’)=CH2···[Ea1] or -O-(R AL ’-O) y -C(=O)-CH(-R AC ’)=CH2···[Ea2] It may have a group represented by. Here, the said R AC ’ is a hydrogen atom or a methyl group, and the said R AL ’ is a hydrocarbon group with a valence of 2 or more, and y is 0 or an integer of 1 or more, for example, 0 or 1. The said R AL ’ may have one or more alcoholic hydroxy groups, may have one or more aryloxy groups, and may have one or more groups represented by the above formula [Ea1] or the above formula [Ea2].

[0064] Also, the said R AC and the said R AC ’ may be the same, or may be different from each other. The said R AL and the said R AL ’ may be the same, or may be different from each other. When there are two or more of the said R AL , these R AL may be the same, or may be different from each other. Similarly, when there are two or more of the said R AL ’, these R AL ’ may be the same, or may be different from each other. When there are two or more of the said R AC ’, these R AC ’ may be the same, or may be different from each other.

[0065] Examples of the methacrylic acid ester having an alcoholic hydroxy group and the acrylic acid ester having an alcoholic hydroxy group include esters of a polyol having two or more hydroxy groups and methacrylic acid or acrylic acid with a smaller number of molecules than the number of hydroxy groups possessed by the polyol.

[0066] Examples of the said polyol include, for example, HO-(R AL -O) x -H ···[OL1] Examples include those having a structure represented by R. AL R is a divalent hydrocarbon group, HO- is an alcoholic hydroxyl group, and x is an integer of 1 or more, for example, 1 or 2. Here, R AL It may have one or more alcoholic hydroxyl groups, and may have one or more aryloxy groups, and one or more -(R AL '-O) x -H ···[OLa1] or -O-(R AL '-O) y -H ···[OLa2] It may have a group represented by R. Here, the R AL ' is a hydrocarbon group with two or more valent values, and y is an integer of 0 or 1 or more, for example, 0 or 1. The R AL ' may have one or more alcoholic hydroxyl groups, one or more aryloxy groups, or one or more groups represented by the above formula [OLa1] or [OLa2].

[0067] A preferred example of the polyol is a polyol having the structure represented by the above formula [OL1], in which x is 1, and a typical example of this is an alkane polyol. Specific examples of alkane polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and other alkanediols; glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, and other alkanetriols; and tetramethylolmethane, pentaerythritol, and other alkanetetraols. Among these alkane polyols, ethylene glycol is particularly preferred.

[0068] Furthermore, the polyol may be any polyol having the structure represented by the above formula [OL1] in which x is 2. Examples of such polyols include di(hydroxyalkyl) ethers such as diethylene glycol, diglycerin, ditrimethylol methane, ditrimethylolethane, ditrimethylolpropane, and di(polyhydroxyalkyl) ethers such as dipentaerythritol.

[0069] Furthermore, the polyol may be a polyalkylene glycol such as polyethylene glycol, in addition to those exemplified above. Here, the alkane polyol, di(hydroxyalkyl) ether, di(polyhydroxyalkyl) ether, and polyalkylene glycol may have an aromatic ring.

[0070] Specific examples of methacrylic acid esters and acrylic acid esters having alcoholic hydroxyl groups include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate; hydroxyalkyl (meth)acrylates having aromatic rings such as 2-hydroxy-3-phenoxypropyl (meth)acrylate; polyhydroxyalkyl (meth)acrylates such as glycerin mono(meth)acrylate and pentaerythritol mono(meth)acrylate; and polyethylene glycol mono(meth)acrylate. Among these, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate are preferred from the viewpoint of price and availability. In the modified ethylene-α-olefin copolymer (A), the amount of methacrylic acid ester having an alcoholic hydroxyl group or acrylic acid ester having an alcoholic hydroxyl group (more precisely, the amount of constituent units corresponding to methacrylic acid ester having an alcoholic hydroxyl group or acrylic acid ester having an alcoholic hydroxyl group) is, on average, 0.3 or more per molecule of the modified ethylene-α-olefin copolymer (A), preferably 0.4 or more, more preferably 0.5 or more, and even more preferably 0.8 or more. On the other hand, there is no particular upper limit to the above amount, but it is preferably 30 or less, and more preferably 10 or less. That is, the amount of methacrylic acid ester or acrylic acid ester having an alcoholic hydroxyl group in the modified ethylene-α-olefin copolymer (A) is 0.3 or more on average per molecule of the modified ethylene-α-olefin copolymer (A), preferably 0.4 to 30. The amount may be 0.5 to 30. In a preferred and exemplary embodiment of the present invention, the amount is 0.8 to 10.

[0071] Among methacrylic acid esters and acrylic acid esters, there are some for which attempts have been made to produce from biomass-derived raw materials, such as methyl methacrylate. One or more compounds (Y) selected from the group consisting of methacrylic acid derivatives and acrylic acid derivatives, which are monomers constituting the modified ethylene-α-olefin copolymer (A), may be, for example, monomers derived from fossil fuels or monomers derived from biomass, and these monomers may be used individually or in combination of two or more. In other words, the modified ethylene-α-olefin copolymer (A) may consist only of monomers derived from fossil fuels, or only of monomers derived from biomass, or may consist of monomers derived from fossil fuels and monomers derived from biomass in combination.

[0072] <Compound (Z) and other polymerization inhibitors> When reacting the compound (Y), such as the compound having an alcoholic hydroxyl group, with the modified ethylene-α-olefin copolymer (A''), the addition of a polymerization inhibitor is preferable from the viewpoint of improving reaction efficiency. Here, the modified ethylene-α-olefin copolymer (A) satisfies the above requirements (a1) to (a3), preferably satisfies requirements (a1) to (a4), and more preferably satisfies requirements (a1) to (a5). In obtaining such a modified ethylene-α-olefin copolymer (A), the inventors believe it is important to suppress the homopolymerization of the compounds (Y) when reacting the compound (Y) (especially the compound having the alcoholic hydroxyl group) with the modified ethylene-α-olefin copolymer (A''). Here, the inventors have found that when reacting the compound (Y) (especially the compound having the alcoholic hydroxyl group) with the modified ethylene-α-olefin copolymer (A'') in the presence of a specific compound (Z), a modified ethylene-α-olefin copolymer (A) that satisfies the above requirements (a1) to (a4) and also exhibits excellent curability can be obtained. In other words, in the present invention, the reaction between compound (Y) and the modified ethylene-α-olefin copolymer (A'') is carried out in the presence of compound (Z). Examples of such compounds (Z) include one or more selected from the group consisting of quinone derivatives and phenol derivatives, with specific examples including hydroquinone, p-benzoquinone, tert-butylhydroquinone, 4-tert-butylpyrocatechol, p-methoxyphenol, and 2,6-di-tert-butyl-4-methylphenol. The content of compound (Z) is 0.01 to 1.0 parts by mass, preferably 0.01 to 0.5 parts by mass, per 100 parts by mass of the modified ethylene-α-olefin copolymer (A''). Furthermore, in the present invention, in addition to compound (Z), a polymerization inhibitor other than compound (Z) (other polymerization inhibitors) may also be used as a polymerization inhibitor. The type of the other polymerization inhibitor is not particularly limited and may be a known polymerization inhibitor, but typical examples include phosphorus-based polymerization inhibitors, sulfur-based polymerization inhibitors, and amine-based polymerization inhibitors. The content of the other polymerization inhibitor is 0.01 to 1.0 parts by mass, preferably 0.1 to 0.5 parts by mass, per 100 parts by mass of the modified ethylene-α-olefin copolymer (A'').

[0073] <Method for producing ethylene-α-olefin copolymer (A')> The method for producing the ethylene-α-olefin copolymer (A') in the present invention is not particularly limited, but one example is the method using a vanadium-based catalyst consisting of a vanadium compound and an organoaluminum compound, 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. In the vanadium-based catalyst method, more chlorine compounds are used as co-catalysts compared to the metallocene catalyst method, so there is a possibility that trace amounts of chlorine may remain in the resulting ethylene-α-olefin copolymer (A').

[0074] 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 (A') 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.

[0075] In particular, by using the following methods, an ethylene-α-olefin copolymer (A') with a good balance of performance in terms of molecular weight control, molecular weight distribution, and amorphousness can be obtained.

[0076] The ethylene-α-olefin copolymer (A') according to the present invention can be produced by copolymerizing ethylene with an α-olefin having 3 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing a crosslinked metallocene compound (P) described below as "crosslinked metallocene compound (P)", and at least one compound (Q) selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the crosslinked metallocene compound (P) to form an ion pair.

[0077] ≪Cross-linked metallocene compounds (P)≫ A crosslinked metallocene compound (P) that can be used in the production of ethylene-α-olefin copolymer (A') has a structure represented by the following formula [I].

[0078] [ka] In the above formula [I], Y, M, R 1 ~R 14 Q, n, and j are explained below.

[0079] (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.

[0080] 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 Among those adjacent to each other Two or more adjacent substituents may be bonded to each other to form a ring, or they may not be bonded to each other.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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- unit is replaced by a nitrogen atom, groups in which the -CH2- 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 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.

[0090] 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- unit is replaced by an oxygen atom or a carbonyl group, or where the -CH3- 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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 14These elements may be bonded to each other to form a ring, or they may not be bonded to each other.

[0096] 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.

[0097] 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.

[0098] 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.

[0099] Among them, R 13 and R 14 A crosslinked metallocene compound (P) in which one or both of the groups are independently aryl groups is preferred, and a crosslinked metallocene compound (P) in which both are independently aryl groups is more preferred.

[0100] In particular, R 13 and R 14The crosslinked metallocene compound (P), in which both are independently aryl groups, exhibits high polymerization activity for copolymerization of ethylene and α-olefins. By using this crosslinked metallocene compound (P), polymerization is selectively terminated by introducing hydrogen to the molecular ends, resulting in fewer unsaturated bonds in the resulting ethylene-α-olefin copolymer (A'). Therefore, a highly saturated and heat-resistant ethylene-α-olefin copolymer (A) can be obtained simply by or without hydrogenation, and is also cost-effective. Furthermore, the ethylene-α-olefin copolymer (A') obtained from this compound (P) has a controlled molecular weight distribution due to its high random copolymerizability.

[0101] In the crosslinked metallocene compound (P) represented by the above formula [I], n is preferably 1. Such a crosslinked metallocene compound (hereinafter also referred to as "crosslinked metallocene compound (P-1)") is represented by the following general formula [II].

[0102] [ka] In equation [II], Y, M, R 1 ~R 14 The definitions of Q and j are as described above.

[0103] Compared to compounds in formula [I] where n is an integer between 2 and 4, the cross-linked metallocene compound (P-1) offers the advantages of a simplified manufacturing process, reduced manufacturing costs, and consequently, a reduction in the manufacturing cost of ethylene-α-olefin copolymer (A') by using this cross-linked metallocene compound (P-1).

[0104] In the crosslinked metallocene compound (P) represented by the above general formula [I] and the crosslinked metallocene compound (P-1) represented by the above general 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 crosslinked metallocene compound in which M is a zirconium atom, the polymerization activity is higher compared to when M is a titanium atom or a hafnium atom, and the advantage of reducing the production cost of the ethylene-α-olefin copolymer (A') is obtained.

[0105] Examples of such cross-linked metallocene compounds (P) include [dimethylmethylene(η)]. 5 -cyclopentadienyl)(η 5 -Fluorenyl) Zirconium dichloride, [Dimethylmethylene (η 5 -cyclopentadienyl)(η 5 [-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl)(η 5 [-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [dimethylmethylene (η 5 -cyclopentadienyl)(η 5 -Octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [dimethylmethylene(η) 5 -cyclopentadienyl)(η 5 -Tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride,[cyclohexylidene(η 5 -cyclopentadienyl)(η 5 -Fluorenyl) Zirconium dichloride, [Cyclohexylidene (η 5 -cyclopentadienyl)(η 5 [-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [cyclohexylidene (η 5 -cyclopentadienyl)(η 5 [-3,6-di-tert-butylfluorenyl)]zirconium dichloride, [cyclohexylidene (η5 -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 (η5-cyclopentadienyl) (η 5 [-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5[3,6-di-tert-butylfluorenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -Octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methylphenylmethylene (η 5 -cyclopentadienyl)(η 5 -Tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -Fluorenyl)] Zirconium dichloride, [Methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 [-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 [3,6-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -Octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(3-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -Tetramethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -Fluorenyl)] Zirconium dichloride, [Methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 [-2,7-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 [3,6-di-tert-butylfluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5-cyclopentadienyl)(η 5 -Octamethyloctahydrodibenzofluorenyl)]zirconium dichloride, [methyl(4-methylphenyl)methylene(η 5 -cyclopentadienyl)(η 5 -Tetramethyloctahydrodibenzofluorenyl)] Zirconium dichloride, [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 [η5 -(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 [η5 -(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-Jif [Ethyl-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)][η 5 -(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-tolyl)methylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](η 5 -Fluorenyl) zirconium dichloride, di(p-tolyl) methylene [η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5-(3,6-di-tert-butylfluorenyl)] zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)][η 5 -(2,7-di-tert-butylfluorenyl)] zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butyl-5-methylcyclopentadienyl)](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[η 5 -(3-tert-butylcyclopentadienyl)](octahydrodibenzofluorenyl)zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-diphenyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-tert-butylcyclopentadienyl)][η 5 -(2,7-dimethyl-3,6-di-tert-butylfluorenyl)]zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)](η 5 -Fluorenyl) zirconium dichloride, di(p-tolyl) methylene [η 5 -(3-n-butylcyclopentadienyl)][η 5 -(3,6-di-tert-butylfluorenyl)] zirconium dichloride, di(p-tolyl)methylene[η 5 -(3-n-butylcyclopentadienyl)][η 5 -(2,7-di-tert-butylfluorenyl)] zirconium dichloride, di(p-tolyl)methylene[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.

[0106] Examples of cross-linked metallocene compounds (P) include compounds in which the zirconium atoms of the above compound are replaced with hafnium atoms or titanium atoms, and compounds in which the chloro ligand is replaced with a methyl group. Note that the η component of the exemplified cross-linked metallocene compound (P) is also included. 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. The cross-linked metallocene compound (P) may be used alone or in combination of two or more types.

[0107] ≪Compound (Q)≫ The compound (Q) according to the present invention is at least one compound selected from the group consisting of an organometallic compound (Q-1), an organoaluminum oxy compound (Q-2), and a compound (Q-3) that reacts with the bridged metallocene compound (P) to form an ion pair. As the organometallic compound (Q-1), specifically, organometallic compounds (Q-1a), (Q-1b), and (Q-1c) of Groups 1, 2, 12, and 13 of the periodic table as described below are used.

[0108] (Q-1a) General formula Ra m Al(ORb) n H p X q An organoaluminum compound represented by (In the formula, Ra and Rb may be the same or different from each other and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m ≦ 3, n is 0 ≦ n < 3, p is 0 ≦ p < 3, q is 0 ≦ q < 3, and m + n + p + q = 3.) 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; general formula (i-C4H9) x Al y (C5H 10 ) zAlkenyl aluminum such as isoprenyl aluminum, 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, represented by the general formula Ra 2.5 Al(ORb) 0.5 Examples include partially alkoxylated alkylaluminum having an average composition represented by the above formula Ra, 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. m Al(ORb) n H p X qCompounds similar to the compound represented by can also be used. For example, organoaluminum compounds in which two or more aluminum compounds are bonded via a nitrogen atom can be mentioned. Specific examples of such compounds include (C2H5)2AlN(C2H5)Al(C2H5)2 and the like.

[0109] (Q-1b) A complex alkylate of a Group 1 metal of the periodic table and aluminum represented by the general formula M2AlRa4. (In the formula, M2 represents Li, Na or K, and Ra represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.) Examples of such compounds include LiAl(C2H5)4, LiAl(C7H 15 )4 and the like.

[0110] (Q-1c) A dialkyl compound of a Group 2 or Group 12 metal of the periodic table represented by the general formula RaRbM3. (In the formula, Ra and Rb may be the same or different from each other, and represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn or Cd.) As the organoaluminum oxy compound (Q-2), conventionally known aluminoxane can be used as it is. Specifically, compounds represented by the following general formula [III] and compounds represented by the following general formula [IV] can be mentioned.

[0111] [Chemical formula] 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.

[0112] Particularly, methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more, is used. These aluminoxanes may be mixed with a small amount of organoaluminum compounds.

[0113] In the present invention, when copolymerization of ethylene with α-olefins having 3 or more carbon atoms is carried out at high temperatures, benzene-insoluble organoaluminum oxy compounds, such as those exemplified in Japanese Patent Publication No. 2-78687, can also be used. Furthermore, organoaluminum oxy compounds described in Japanese Patent Publication No. 2-167305, aluminoxanes having two or more alkyl groups described in Japanese Patent Publication No. 2-24701 and Japanese Patent Publication No. 3-103407 can also be suitably used. The "benzene-insoluble organoaluminum oxy compounds" used in the present invention are compounds in which the Al component that dissolves in benzene at 60°C is usually 10% or less, preferably 5% or less, and particularly preferably 2% or less in terms of Al atoms, and are insoluble or sparingly soluble in benzene.

[0114] Furthermore, examples of organoaluminum oxy compounds (Q-2) include modified methylaluminoxanes represented by the following general formula [V].

[0115] [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.

[0116] Methylaluminoxane, an example of an organoaluminum oxy compound (Q-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)).

[0117] Furthermore, as organoaluminum oxy compounds (Q-2), organoaluminum oxy compounds containing boron represented by the following general formula [VI] can also be mentioned.

[0118] [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.

[0119] Compounds (Q-3) that react with crosslinked metallocene compounds (P) to form ion pairs (hereinafter sometimes abbreviated as "ionized ionic compounds" or simply "ionic compounds") 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.

[0120] The ionized ionic compound preferably used in the present invention is a boron compound represented by the following general formula [VII].

[0121] [ka] 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.

[0122] 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.

[0123] Specific examples of the ammonium cation include trialkyl-substituted ammonium cations such as trimethylammonium cation, triethylammonium cation, tri(n-propyl)ammonium cation, triisopropylammonium cation, tri(n-butyl)ammonium cation, and triisobutylammonium cation; N,N-dialkylanilinium cations such as N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and N,N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.

[0124] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris(4-methylphenyl)phosphonium cation, and tris(3,5-dimethylphenyl)phosphonium cation.

[0125] R e+ Among the above specific examples, carbocation, ammonium cation, etc. are preferred, and particularly triphenylcarbocation, N,N-dimethylanilinium cation, and N,N-diethylanilinium cation are preferred.

[0126] Among the ionizable ionic compounds preferably used in the present invention, examples of the compound containing a carbocation include triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis{3,5-di-(trifluoromethyl)phenyl}borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl)borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl)borate.

[0127] <## Among the ionized ionic compounds preferably used in the present invention, 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-(trif Examples include diuromethyl)phenyl borate, tri(n-butyl)ammonium tetrakis{3,5-di(trifluoromethyl)phenyl} borate, tri(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.

[0128] Examples of ionized ionic compounds preferably used in the present invention include compounds containing an N,N-dialkylanilinium cation, 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.

[0129] Examples of ionized ionic compounds that are preferably used in the present invention include di-n-propylammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate, which contain a dialkylammonium cation.

[0130] In addition, ionic compounds exemplified in Japanese Patent Publication No. 2004-51676 can also be used without limitation. The above-mentioned ionic compound (Q-3) may be used alone or as a mixture of two or more.

[0131] Examples of the configuration of the catalyst system include, for example, the following [1] to [4]. [1] Includes crosslinked metallocene compound (P) and compound (Q-2) [2] Includes a crosslinked metallocene compound (P), compound (Q-1), and compound (Q-2). [3] Includes crosslinked metallocene compound (P), compound (Q-1), and compound (Q-3) [4] Includes crosslinked metallocene compound (P), compound (Q-2), and compound (Q-3) The cross-linked metallocene compound (P) and compounds (Q-1) to (Q-3) can be introduced into the reaction system in any order.

[0132] ≪Carrier(R)≫ In the present invention, a support (R) may be used as a component of the olefin polymerization catalyst, if necessary.

[0133] The carrier (R) that may be used in the present invention is an inorganic or organic compound, and is 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.

[0134] 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. The properties of such porous oxides vary depending on the type and manufacturing method, but the carrier preferably used in the present invention has a particle size of 0.5 to 300 μm, preferably 1.0 to 200 μm, and a specific surface area of ​​50 to 1000 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.

[0135] 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.

[0136] 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 are not limited to natural products; artificially synthesized materials can also be used. Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, 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. It is also preferable to subject the clays and clay minerals used in this invention 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. Specifically, chemical treatments include acid treatment, alkali treatment, salt treatment, and organic matter treatment.

[0137] Ion-exchangeable layered compounds may be layered compounds in which the interlayers are expanded by utilizing ion exchange properties and exchanging the exchangeable ions between layers with other large, bulky ions. Such bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance (guest compound) between the layers of a layered compound in this way is called intercalation. Guest compounds include cationic inorganic compounds such as TiCl4 and ZrCl4, metal alkoxides such as Ti(OR)4, Zr(OR)4, PO(OR)3, and B(OR)3 (where R is a hydrocarbon group, etc.), and [Al 13 O4(OH) 24 ] 7+ [Zr4(OH) 14 ] 2+ [Fe3O(OCOCH3)6] + Examples include metal hydroxide ions. These compounds can be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolysis and polycondensation of metal alkoxides (where R is a hydrocarbon group, etc.) such as Si(OR)4, Al(OR)3, and Ge(OR)4, or colloidal inorganic compounds such as SiO2 can also be present. As pillars, examples include oxides produced by heating and dehydrating after intercalating the above-mentioned metal hydroxide ions between layers.

[0138] Of these, clay or clay minerals are preferred, with montmorillonite, vermiculite, pectolite, teniolite, and synthetic mica being particularly preferred. Examples of organic compounds used as a support (R) include granular or particulate solids with a particle size 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, or (co)polymers produced mainly from vinylcyclohexane and styrene, and modified versions thereof.

[0139] The method of use and the order of addition of each component of the polymerization catalyst can be chosen arbitrarily. Furthermore, at least two of the components in the catalyst may be in contact with each other beforehand. The cross-linked metallocene compound (P) (hereinafter also referred to as "component (P)") is typically 10 per liter of reaction volume. -9 ~10 -1 moles, preferably 10 -8 ~10 -2 It is used in quantities that equal moles.

[0140] The organometallic compound (Q-1) (hereinafter also referred to as "component (b-1)") is used in an amount such that the molar ratio [(Q-1) / M] of component (Q-1) to the transition metal atom (M) in component (P) is usually 0.01 to 50,000, preferably 0.05 to 10,000.

[0141] The organoaluminum oxy compound (Q-2) (hereinafter also referred to as "component (Q-2)") is used in an amount such that the molar ratio [(Q-2) / M] of aluminum atoms in component (Q-2) to transition metal atoms (M) in component (P) is usually 10 to 5,000, preferably 20 to 2,000.

[0142] The ionic compound (Q-3) (hereinafter also referred to as "component (Q-3)") is used in an amount such that the molar ratio [(Q-3) / M] of component (Q-3) to the transition metal atom (M) in component (P) is usually 1 to 10,000, preferably 1 to 5,000.

[0143] The polymerization temperature is typically -50°C to 300°C, preferably 30°C to 250°C, more preferably 100°C to 250°C, and even more preferably 130°C to 200°C. In the polymerization temperature range described above, as the temperature increases, the viscosity of the solution during polymerization decreases, and the heat of polymerization is also easily removed. The polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure (MPa-G) (i.e., above atmospheric pressure (atmospheric pressure + 10 MPa) or below), preferably atmospheric pressure to 8 MPa-G (i.e., above atmospheric pressure (atmospheric pressure + 8 MPa) or below).

[0144] 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 component (Q) used. When hydrogen is added, an appropriate amount is approximately 0.001 to 5,000 NL per kilogram of the resulting copolymer.

[0145] 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.

[0146] 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.

[0147] The resulting ethylene-α-olefin copolymer (A') may be used alone, or two or more copolymers with different molecular weights or different monomer compositions may be combined.

[0148] The modified copolymer (A'') according to the present invention can be produced by modifying the above-mentioned ethylene-α-olefin copolymer (A'). Specifically, it can be produced by modifying the ethylene-α-olefin copolymer (A') by various conventionally known methods described in Japanese Patent Publication No. 61-126120 and Japanese Patent No. 2593264, or by methods such as (1) and (2) below. (1) A method of modifying copolymer (A') by charging it into an extruder, batch reactor, etc., and adding a compound having a carbon-carbon unsaturated bond or a reactive gas or liquid to be reacted with. (2) A method of denaturing copolymer (A') by dissolving it in a solvent and adding a compound having a carbon-carbon unsaturated bond or a reactive gas or liquid.

[0149] In any of the above methods, it is preferable to carry out graft copolymerization in the presence of one or more radical initiators in order to efficiently graft compounds having carbon-carbon unsaturated bonds, reactive gases, or liquids.

[0150] 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.

[0151] 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.

[0152] The amount of radical initiator used is usually 0.001 to 5 parts by mass, preferably 0.01 to 4 parts by mass, and more preferably 0.05 to 3 parts by mass, per 100 parts by mass of the copolymer (A) before modification.

[0153] In particular, when the reaction is carried out by an oxidation reaction using air and / or oxygen, 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, in order to promote the reaction.

[0154] 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.

[0155] The reaction temperature in the aforementioned denaturation reaction is typically 20 to 350°C, preferably 60 to 300°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.

[0156] [Composition] The above-mentioned modified ethylene-α-olefin copolymer (A) may also be in the form of a composition. That is, the composition of the present invention contains the above-mentioned modified ethylene-α-olefin copolymer (A). A preferred example of the composition of the present invention is a composition comprising the above-mentioned modified ethylene-α-olefin copolymer (A) and monomers other than the above-mentioned modified ethylene-α-olefin copolymer (A). A preferred example of monomers other than the above-mentioned modified ethylene-α-olefin copolymer (A) is (meth)acrylic monomer and polyfunctional (meth)acrylic monomer. Furthermore, the composition of the present invention often comprises the above-mentioned modified ethylene-α-olefin copolymer (A) and a photoinitiator. In this case, the composition may further contain monomers other than the above-mentioned modified ethylene-α-olefin copolymer (A). Furthermore, in addition to the modified ethylene-α-olefin copolymer (A), optional (meth)acrylic monomer, optional polyfunctional (meth)acrylic monomer, and optional photoinitiator, the composition of the present invention may further contain other components that do not fall under any of the (meth)acrylic monomer, polyfunctional (meth)acrylic monomer, or photoinitiator categories.

[0157] [(meth)acrylic monomers, and polyfunctional (meth)acrylic monomers] Examples of (meth)acrylic monomers that may be included in the composition of the present invention include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, isododecyl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2- Hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-hydroxy-3-phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, p-nonylphenyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclo[5.2.1.0 2,6 Examples include decanyl (meth)acrylate, 2,2,6,6-tetramethylpiperidinyl (meth)acrylate, 1,2,2,6,6-pentamethylpiperidinyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, p-cumylphenyl (meth)acrylate, and diethylaminoethyl (meth)acrylate. Among these, the (meth)acrylic monomer is preferably a compound that does not have polar groups other than the (meth)acryloyl group, such as isobornyl (meth)acrylate and dicyclopentenyl (meth)acrylate. Among these, isobornyl (meth)acrylate is preferred from the viewpoint of the physical properties of the resulting UV-curable resin composition after curing.

[0158] Furthermore, the (meth)acrylic monomers exemplified above are sometimes called monofunctional (meth)acrylic monomers to distinguish them from the polyfunctional (meth)acrylic monomers described below, since they contain only one (meth)acryloyl group within the molecule.

[0159] Examples of polyfunctional (meth)acrylic monomers that may be included in the composition of the present invention include polyfunctional (meth)acrylic monomers having two or more (meth)acryloyl groups in the molecule, such as 2,2-bis[4-(meth)acryloyloxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxypolyethoxyphenyl]propane, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol di(meth)acrylate, 1,2-bis(3-methacryloyloxy-2-hydroxypropoxy)ethane, and [2,2,4-trimethylhexamethylene] Examples of (meth)acrylate monomers include difunctional (meth)acrylate monomers such as bis(2-carbamoyloxyethyl) dimethacrylate and 1,3-di(meth)acryloryloxy-2-hydroxypropane, as well as trifunctional or more (meth)acrylate monomers such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, N,N'-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetramethacrylate and 1,7-diacryloyloxy-2,2,6,6-tetraacryloyloxymethyl-4-oxyheptane. Among these, 1,6-hexanediol di(meth)acrylate and tricyclodecanedimethanol di(meth)acrylate are even more preferred in the present invention. These can be used individually or in combination of two or more types.

[0160] [Photoinitiator] Examples of photoinitiators that may be included in the composition of the present invention include 2-hydroxy-2-methyl-1-phenyl-propan-1-one [2-hydroxy-2-methylpropiophenone], 1-hydroxycyclohexyl phenyl ketone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, acetophenone, benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzyl, and 2-chlorothioxanthone. These may be used individually or in combination of two or more. The amount of photoinitiator used is usually 0.01 to 20 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total amount of modified ethylene-α-olefin copolymer (A), optional (meth)acrylic monomer, and optional polyfunctional (meth)acrylic monomer. If the amount of photoinitiator used is less than 0.01 parts by mass per 100 parts by mass of the total amount of modified ethylene-α-olefin copolymer (A), optional (meth)acrylic monomer, and optional polyfunctional (meth)acrylic monomer, the curing performance may be insufficient. On the other hand, if it is more than 20 parts by mass, there is no significant improvement in curing performance, which may impair economic efficiency.

[0161] [Other ingredients] The composition according to the present invention may contain other components, such as various known compounding agents commonly used in general rubber compositions, to the extent that they do not impair the objectives of the present invention, depending on the desired performance, etc. For example, compounding agents other than the modified copolymer (A) may include softeners, antioxidants, processing aids, alkoxysilane compounds, surfactants, reaction inhibitors, colorants, dispersants, flame retardants, plasticizers, antioxidants, scorch inhibitors, antistatic agents, lubricants, antifungal agents, trowel accelerators, tackifiers, various dyes such as disperse dyes and acid dyes, inorganic and organic pigments, surfactants, and paints, and optionally, foaming agents, foaming aids, and other compounds for foaming, and defoaming agents.

[0162] [Method for preparing the composition] The compositions of the present invention can be prepared by known methods of compounding. For example, they can be prepared by mixing using conventional mixing means, such as mixing with a stirring blade or a kneader.

[0163] [Application] The composition of the present invention is used in molded articles, adhesives, and sealants for a wide range of applications, from household goods to industrial products. In other words, the composition of the present invention can be used as a raw material for molded articles, an adhesive, or a sealant. Such raw materials for molded articles, adhesives, and sealants all contain the composition of the present invention. When the composition of the present invention is used as a raw material for molded articles, the composition of the present invention can be photocured to form a molded article. In other words, the molded article of the present invention is made by photocuring the composition of the present invention, and can be said to contain a photocured product of the composition of the present invention. Here, the light used for photocuring is not particularly limited as long as it can sufficiently cure the composition of the present invention, but examples include ultraviolet light.

[0164] Main applications of the compositions of the present invention include electrical and electronic components, automotive parts, mechanical components, food containers, films, sheets, and fibers. Specific examples include office and OA equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, mobile phones, smartphones, tablet devices, WiFi routers, facsimile machines, photocopiers, ECRs (electronic cash registers), calculators, electronic organizers, electronic dictionaries, cards, holders, and stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu (heated tables); AV equipment such as TVs, VTRs, video cameras, digital cameras, SLR cameras, portable audio players, boomboxes, tape recorders, MiniDiscs, CD players, speakers, and liquid crystal displays; and electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulating materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks.

[0165] Examples of applications include materials for automobiles, vehicles, ships, aircraft, and buildings such as seats (filling, upholstery, etc.), belts, headliners, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, wheel covers, tires, mattress covers, airbags, insulating materials, handrails, handrail straps, wire insulation materials, electrical insulating materials, paints, coatings, upholstery materials, flooring materials, corner walls, deck panels, covers, plywood, ceiling boards, partition boards, side walls, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, soundproofing boards, insulation boards, window materials, etc.; as well as lifestyle and sports goods such as clothing, curtains, sheets, plywood, synthetic boards, carpets, doormats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments, etc.

[0166] Furthermore, examples of uses include bottles for shampoo, detergent, and cosmetics; bottles for cooking oil and condiments such as soy sauce; bottles for beverages such as mineral water and juice; heat-resistant food containers such as lunch boxes and chawanmushi bowls; tableware such as plates and chopsticks; and various other food containers, as well as packaging films, packaging bags, and handles for toothbrushes and knives. [Examples]

[0167] The present invention will be described in more detail below based on the examples, but the present invention is not limited to these examples. The raw material components used in the examples and comparative examples are as follows.

[0168] [Modified ethylene-α-olefin copolymer (A)] The methods for measuring various physical properties of modified ethylene-α-olefin copolymer (A) are as follows. <Kinematic viscosity at 100°C> The kinematic viscosity (100°C kinematic viscosity) of the ethylene-α-olefin copolymer (A') at 100°C was measured and calculated according to the method described in JIS K 2283.

[0169] <Ethylene content (mol%)> The ethylene molar content of ethylene-α-olefin copolymer (A') and modified ethylene-α-olefin copolymer (A) was determined using a JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer, with orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120 °C, and the observed nucleus as follows: 13 Measurements were performed using a C (125 MHz) frequency, a single-pulse proton decoupling sequence, a pulse width of 4.7 μ / s (45° pulse), a repetition time of 5.5 seconds, an integration count of over 10,000 cycles, and a chemical shift reference value of 27.50 ppm.

[0170] The ethylene molar content of the modified ethylene-α-olefin copolymer (A) was measured as described above. 13 The 13C-NMR spectra were determined based on the "Handbook of Polymer Analysis" (Asakura Shoten, pp. 163-170), and reports by G.J. Ray (Macromolecules, 10, 773 (1977)), J.C. Sandall (Macromolecules, 15, 353 (1982)), and K. Kimura (Polymer, 25, 4418 (1984)).

[0171] <Number-average molecular weight (Mn), Mw / Mn, and presence or absence of polymers with Mn 100,000 or more> The molecular weights (Mn) and Mw / Mn of ethylene-α-olefin copolymer (A'), modified ethylene-α-olefin copolymer (A''), and modified ethylene-α-olefin copolymer (A) were measured using the high-speed GPC analyzer described below. High-speed GPC measurement device: Tosoh Corporation HLC8320GPC Mobile phase: THF (manufactured by Wako Pure Chemical Industries, Ltd., stabilizer-free, liquid chromatography grade) Column: Two TSKgel Super Multipore HZ-M columns manufactured by Tosoh Corporation, connected in series. Sample concentration: 5 mg / mL Mobile phase flow rate: 0.35mL / min Measurement temperature: 40℃ Standard sample for calibration curve: PStQuick MP-M manufactured by Tosoh Corporation Detector: RI (Differential Refraction) detector

[0172] The chromatograms obtained from the above measurements were analyzed using a calibration curve with standard polystyrene samples by known methods to determine the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn). Specifically, a calibration curve showing the relationship between the common logarithm of molecular weight and retention time was created using the aforementioned standard samples for the calibration curve. The chromatogram was then converted into a differential molecular weight distribution curve using this calibration curve, and the weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined from this differential molecular weight distribution curve. On the other hand, the presence or absence of polymers with a number-average molecular weight (Mn) of 100,000 or more in the modified ethylene-α-olefin copolymer (A) was determined by whether or not a peak corresponding to a polymer with a number-average molecular weight (Mn) of 100,000 or more was detected in the differential molecular weight distribution curve obtained by performing the above measurements on the modified ethylene-α-olefin copolymer (A).

[0173] <Internal olefin content (particles / 1000C), terminal olefin content (particles / molecule)> The internal olefin content (particles / 1000C) and terminal olefin content (particles / 1000C) of ethylene-α-olefin copolymer (A') and modified ethylene-α-olefin copolymer (A) were determined using a Bruker BioSpin AVANCE III cryo-500 nuclear magnetic resonance spectrometer, with an orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120°C, and the observed nucleus as follows: 1 Measurements were taken using H (500 MHz), a single-pulse proton decoupling sequence, a pulse width of 5.0 μ / s (45° pulse), a repetition time of 35 seconds, 16 integration cycles, and a chemical shift reference value of 1.2 ppm.

[0174] Here, the terminal olefin content (number / molecule) was calculated by dividing the terminal olefin content (number / 1000C) by the average number of carbons per molecule (number / molecule) calculated from the number average molecular weight (Mn) measured by a high-speed GPC measuring device. The number average molecular weight (Mn) was determined by the method described in the above "Number average molecular weight (Mn), Mw / Mn, and presence or absence of polymers with Mn of 100,000 or more".

[0175] <BF viscosity> The BF viscosity (Brookfield viscosity) of the modified ethylene-α-olefin copolymer (A) was measured at 45°C using a Brookfield viscometer in accordance with ASTM D2983.

[0176] <Modified monomer content (mass%)> The modified monomer content (primary modification species, secondary modification species) of the modified ethylene-α-olefin copolymer (A) was measured by the same method as the ethylene content.

[0177] The amount of secondary modification (number / molecule) for the secondary modification species was calculated using the modified monomer content (secondary modification species) of the modified ethylene-α-olefin copolymer (A) and the number average molecular weight (Mn) measured by a high-speed GPC measuring device. The number average molecular weight (Mn) was determined by the method described in the above "Number average molecular weight (Mn), Mw / Mn, and presence or absence of polymers with Mn of 100,000 or more".

[0178] [Production of modified ethylene-α-olefin copolymer (A)] The production method of the modified ethylene-α-olefin copolymer (A) used in the examples is shown below.

[0179] [Production Example 1] Production of modified ethylene-propylene copolymer (A-1) A 2L stainless steel autoclave, thoroughly purged with nitrogen, was charged with 760ml of heptane and 120g of propylene. After raising the temperature of the system to 150°C, the total pressure was increased to 3MPaG by supplying 0.85MPa of hydrogen and 0.19MPa of ethylene. Next, 0.4 mmol of triisobutylaluminum and diphenylmethylene [η] were added. 5 -(3-n-butylcyclopentadienyl)][η 5 Polymerization was initiated by introducing 0.0002 mmol of -(2,7-di-tert-butylfluorenyl) zirconium dichloride and 0.002 mmol of N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate under pressure with nitrogen and stirring at 400 rpm. The total pressure was then maintained at 3 MPaG by continuously supplying 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 copolymer 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 over magnesium sulfate, and the solvent was removed by vacuum distillation. The resulting ethylene-propylene copolymer (A-1') was dried at 80°C under reduced pressure for 10 hours. The obtained ethylene-propylene copolymer (A-1') had an ethylene content of 49.5 mol%, a manganese content of 2,900, a Mw / Mn ratio of 1.7, an internal olefin content of <0.1 particles / 1000°C, a pour point of -30°C, and a kinematic viscosity of 150 mmHg at 100°C. 2 It was / s.

[0180] 100 g of ethylene-propylene copolymer (A-1') was placed in a 500 mL glass flask that had been thoroughly purged with nitrogen. 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 to each over 5 hours. After the supply was complete, the mixture was allowed to react for 1 hour. Next, the temperature was further raised to 175 °C, and after depressurizing the system, impurities (decomposition products of unreacted maleic anhydride and di-tert-butyl peroxide) were removed by gradually supplying nitrogen using a vacuum pump under reduced pressure for 1 hour. Through these operations, maleic anhydride-modified ethylene-propylene copolymer (A-1'') was obtained. The obtained maleic anhydride-modified ethylene-propylene copolymer (A-1'') had a manganese content of 3,100, a Mw / Mn ratio of 1.9, a BF viscosity of 7.0 Pa·s at 45°C, and a maleic anhydride content of 5% by mass.

[0181] 100 g of maleic anhydride-modified ethylene-propylene copolymer (A-1'') was placed in a 500 mL glass flask, and the temperature inside the system was raised to 100°C. Then, 13 g of 2-hydroxyethyl methacrylate, in which 50 mg of hydroquinone had been dissolved as compound (Z) beforehand, was added, and the mixture was stirred and the esterification reaction was carried out over 8 hours. The resulting esterified product of maleic anhydride-modified ethylene-propylene copolymer and 2-hydroxyethyl methacrylate (hereinafter, modified ethylene-propylene copolymer (A-1)) had an ethylene content of 49.5 mol%, a Mn of 3,200, a Mw / Mn of 1.9, a BF viscosity of 7.0 Pa·s at 45°C, an internal olefin content of <0.1 groups / 1000°C, a pour point of -15°C, and an average of 0.8 methacryloyl groups per molecule derived from the esterified 2-hydroxyethyl methacrylate.

[0182] [Manufacturing Example 2] Production of Modified Ethylene-Propylene Copolymer (A-2) 100 g of ethylene-propylene copolymer (A-1') was placed in a 500 mL glass flask that had been thoroughly purged with nitrogen. After raising the temperature, nitrogen bubbling was started at 120 °C and the system was maintained at 160 °C. Then, 14.1 g of maleic anhydride (heated to around 70 °C to make it liquid) and 2.8 g of di-tert-butyl peroxide, which had been pre-loaded into two dropping funnels, were added to each over 5 hours. After the supply was complete, the mixture was allowed to react for 1 hour. Next, the temperature was further raised to 175 °C, and after depressurizing the system, impurities (decomposition products of unreacted maleic anhydride and di-tert-butyl peroxide) were removed by gradually supplying nitrogen using a vacuum pump under reduced pressure for 1 hour. Through these operations, maleic anhydride-modified ethylene-propylene copolymer (A-2'') was obtained. The obtained maleic anhydride-modified ethylene-propylene copolymer (A-2'') had a manganese content of 3,100, a Mw / Mn ratio of 2.4, a BF viscosity of 270 Pa·s at 45°C, and a maleic anhydride content of 10% by mass.

[0183] 100 g of maleic anhydride-modified ethylene-propylene copolymer (A-2'') was placed in a 500 mL glass flask, and the temperature inside the system was raised to 100°C. Then, 26 g of 2-hydroxyethyl methacrylate, in which 100 mg of hydroquinone had been dissolved as compound (Z) beforehand, was added, and the mixture was stirred and the esterification reaction was carried out over 8 hours. The resulting esterified product of maleic anhydride-modified ethylene-propylene copolymer and 2-hydroxyethyl methacrylate (hereinafter, modified ethylene-propylene copolymer (A-1)) had an ethylene content of 49.5 mol%, a Mn of 3,300, a Mw / Mn of 1.9, a BF viscosity of 270 Pa·s at 45°C, an internal olefin content of <0.1 groups / 1000°C, a pour point of -15°C, and an average of 2.0 methacryloyl groups per molecule derived from the esterified 2-hydroxyethyl methacrylate.

[0184] [Manufacturing Example 3] Production of Modified Ethylene-Propylene Copolymer (A-3) 100 g of the maleic anhydride-modified ethylene-propylene copolymer (A-1'') obtained in Production Example 1 was placed in a 500 mL glass flask, and the temperature inside the system was raised to 100°C. After shielding the glass flask from light with aluminum foil, 6.5 g of 2-hydroxyethyl methacrylate, in which 25 g of hydroquinone had been dissolved as compound (Z) beforehand, was added, and the mixture was stirred and the esterification reaction was carried out over 8 hours. The esterified product of the obtained maleic anhydride-modified ethylene-propylene copolymer and 2-hydroxyethyl methacrylate (hereinafter referred to as modified ethylene-propylene copolymer (A-1)) had an ethylene content of 49.5 mol%, a Mn of 3,200, a Mw / Mn ratio of 1.9, a BF viscosity of 7.0 Pa·s at 45°C, an internal olefin content of <0.1 groups / 1000°C, a pour point of -15°C, and an average of 0.4 methacryloyl groups per molecule derived from the esterified 2-hydroxyethyl methacrylate.

[0185] [Manufacturing Example 4] Production of ethylene-propylene copolymer (A-4) 100 g of the maleic anhydride-modified ethylene-propylene copolymer (A-2'') obtained in Production Example 2 was placed in a 500 mL glass flask, and the temperature inside the system was raised to 100°C. Then, 8.8 g of 2-hydroxyethyl methacrylate was added, and the mixture was stirred and the esterification reaction was carried out over 2 hours. Here, the 2-hydroxyethyl methacrylate was added without being mixed with a compound (Z) such as hydroquinone beforehand. The esterified product of the obtained maleic anhydride-modified ethylene-propylene copolymer and 2-hydroxyethyl methacrylate (hereinafter referred to as modified ethylene-propylene copolymer (A-1)) had an ethylene content of 49.5 mol%, a Mn of 3,200, a Mw / Mn ratio of 2.5, an unmeasurable BF viscosity at 45°C, an internal olefin content of <0.1 groups / 1000°C, a pour point of -15°C, and an average of 2.0 methacryloyl groups per molecule derived from the esterified 2-hydroxyethyl methacrylate.

[0186] [Manufacturing Example 5] Production of ethylene-propylene copolymer (A-5) 100 g of the maleic anhydride-modified ethylene-propylene copolymer (A-2'') obtained in Production Example 2 was placed in a 500 mL glass flask, and the temperature inside the system was raised to 100°C. Then, 7.9 g of 2-hydroxyethyl acrylate was added dropwise while stirring, and the esterification reaction was carried out over 2 hours. Here, the 2-hydroxyethyl acrylate was added without first mixing it with a compound (Z) such as hydroquinone. The esterified product of the obtained maleic anhydride-modified ethylene-propylene copolymer and 2-hydroxyethyl methacrylate (hereinafter referred to as modified ethylene-propylene copolymer (A-1)) had an ethylene content of 49.5 mol%, a Mn of 3,200, a Mw / Mn ratio of 2.5, a BF viscosity at 45°C that could not be measured, an internal olefin content of <0.1 groups / 1000°C, a pour point of -15°C, and an average of 2.0 acryloyl groups per molecule derived from the esterified 2-hydroxyethyl methacrylate.

[0187] In the comparative example, the following commercially available modified diene polymers (A-6) to (A-9) were used. A-6: Modified liquid polyisoprene manufactured by Kuraray Co., Ltd. (product name Kuraprene UC-102M, methacryloyl group content 2 / molecule, Mn 16,000, Mw / Mn 1.0, viscosity at 38℃ 30,000 mPas, internal olefin content >10 / 1000C) A-7: Modified liquid polyisoprene manufactured by Kuraray Co., Ltd. (product name Kuraprene UC-203M, methacryloyl group content 3 / molecule, Mn 31,000, Mw / Mn 1.0, viscosity at 38℃ 160,000 mPas, internal olefin content >10 / 1000C) A-8: Modified liquid polybutadiene manufactured by Nippon Soda Co., Ltd. (product name NISSO-PB TE-2000, methacryloyl group content 2 / molecule, Mn 4,800, Mw / Mn 1.6, viscosity at 45℃ 150,000 mPas, internal olefin content >10 / 1000C) A-9: Modified liquid polybutadiene manufactured by Nippon Soda Co., Ltd. (product name NISSO-PB TEAI-1000, methacryloyl group content 2 / molecule, Mn 3,600, Mw / Mn 1.4, viscosity at 45℃ 300,000 mPas, internal olefin content >1 / 1000C) Table 1 shows the physical properties of the modified ethylene-α-olefin copolymers (A-1) to (A-5) and the modified diene polymers (A-6) to (A-9).

[0188] [Table 1]

[0189] [Examples A1-A3, B1 and B2, and Comparative Examples 1-4] For each of the modified ethylene-α-olefin copolymers (A-1) to (A-5) and the modified diene polymers (A-6) to (A-9), a resin composition was prepared by adding 5 g of 2-hydroxy-2-methylpropiophenone as a photoinitiator to 100 g of copolymer and mixing.

[0190] Each of the obtained resin compositions was evaluated for the following properties: "UV curability," "product appearance," and "heat resistance." The results are shown in Table 2.

[0191] <UV curable> Using a rheometer (AR2000ex) manufactured by T.A. Instruments, the following conditions were met: 25°C, 25mm plate, 300μm gap, 25rpm rotation speed, and a high-pressure mercury lamp at 40mW / cm². 2 The resin composition was irradiated with ultraviolet light under the specified conditions, and its viscosity was measured 3 seconds and 90 seconds after the start of irradiation. Specifically, a 25 mm plate was placed on a rheometer (AR2000ex), and a geometry was placed on top of the plate in the rheometer, facing the plate. The resin composition was placed on the plate, and the resin composition was sandwiched between the plate and the geometry in such a way that there was a gap of 300 μm between the plate and the geometry. Then, while rotating the geometry at 25 rpm, 40 mW / cm² of ultraviolet light was applied to the resin composition using a high-pressure mercury lamp. 2 The resin composition was irradiated with ultraviolet light under the following conditions. Here, the viscosity of the resin composition was measured starting immediately after the start of ultraviolet irradiation and continued for 90 seconds from the start of irradiation. Based on the time-dependent changes in viscosity obtained from the aforementioned measurements, the viscosity ratio was calculated by dividing the viscosity at each measurement time by the viscosity at 3 seconds. Based on this, the time required for the viscosity ratio to reach 2 or more after the start of ultraviolet irradiation was calculated and evaluated according to the following criteria. ◎: The time required for the viscosity ratio to reach 2 or higher after the start of UV irradiation is less than 10 seconds (shows rapid and sufficient curing upon UV irradiation). ○: The time required for the viscosity ratio to reach 2 or higher after the start of UV irradiation is 10 seconds or more (it shows sufficient curing over time with UV irradiation).

[0192] <Product appearance> The obtained resin composition was poured into a 1.0 mm thick mold, and the surface of the composition was covered with a 50 μm thick polyester film. Then, ultraviolet light was irradiated using an ultra-high pressure mercury lamp (40 W / cm) for 90 seconds to obtain a cured product. The appearance of the cured product after peeling off the polyester film was evaluated according to the following criteria. Here, a smaller number of air bubbles may result in a better product appearance and superior mechanical properties. ○: 1cm 2 Less than 5 bubbles per unit △: 1cm 2 More than 5 bubbles per unit

[0193] <Heat resistance> After evaluating the UV curability of the resin composition as described above, the resin composition was placed in a hot air oven heated to 180°C and left to stand for 24 hours. The Gardner color number of the recovered resin composition was then measured and evaluated according to the following criteria. Here, the Gardner color number was measured according to the method in accordance with JIS K0071-2. Specifically, 18 standard color glasses with the same transmitted color as Gardner color number standard solutions (numbers 1 to 18) were prepared, and the color of the resin composition was compared with the color of these 18 standard color glasses. The number of the standard color glass with the color closest to the color of the resin composition was then taken as the Gardner color number of the resin composition, and it was evaluated according to the following criteria. Here, the smaller the Gardner color number of the resin composition, the less the resin composition yellows due to heating and the better its heat resistance.

[0194] Table 2

Claims

1. Modified ethylene-α-olefin copolymer (A) that satisfies the following requirements (a1) to (a3) ​​and contains an average of 0.3 or more (meth)acryloyl groups per molecule: (a1) The content of constituent units derived from ethylene is in the range of 15 to 85 mol%, when the sum of the content of constituent units derived from ethylene and the content of constituent units derived from α-olefins having 3 to 20 carbon atoms is taken as 100 mol%; (a2) The number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene is in the range of 400 to 40,000; (a3) The internal olefin content per 1,000 carbon atoms is 2 or less on average, based on the number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC) and converted to polystyrene equivalent.

2. The modified ethylene-α-olefin copolymer (A) according to claim 1, satisfying the following requirement (a4): (a4) No peaks were observed in the number-average molecular weight (Mn) of 100,000 or more, as measured by gel permeation chromatography (GPC) and converted to polystyrene equivalent.

3. The modified ethylene-α-olefin copolymer (A) according to claim 1, wherein the Brookfield viscosity at 45°C is 350 Pa·s or less.

4. The modified ethylene-α-olefin copolymer (A) according to claim 1, wherein the α-olefin is propylene.

5. The modified ethylene-α-olefin copolymer (A) according to claim 1, comprising a structural unit corresponding to one or more compounds selected from the group consisting of methacrylic acid esters and acrylic acid esters.

6. A step (S1) involves graft-modifying an ethylene-α-olefin copolymer (A') with one or more compounds (X) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid derivatives, Following the above step (S1), a graft modification step (S2) is performed with one or more compounds (Y) selected from the group consisting of methacrylic acid derivatives and acrylic acid derivatives, in the presence of one or more compounds (Z) selected from the group consisting of quinone derivatives and phenol derivatives. A method for producing a modified ethylene-α-olefin copolymer (A) containing the above.

7. The method for producing a modified ethylene-α-olefin copolymer (A) according to claim 6, wherein step (S2) includes step (S2-1) of adding a mixture of compound (Y) and compound (Z) to the modified ethylene-α-olefin copolymer (A'') obtained in step (S1).

8. A method for producing a modified ethylene-α-olefin copolymer (A) according to claim 6, wherein the compound (X) is maleic anhydride.

9. A method for producing a modified ethylene-α-olefin copolymer (A) according to any one of claims 6 to 8, wherein the compound (Y) is one or more compounds selected from the group consisting of 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate.

10. A composition comprising a (meth)acrylic monomer and the modified ethylene-α-olefin copolymer (A) described in claim 1.

11. A composition comprising a polyfunctional (meth)acrylic monomer having two or more (meth)acryloyl groups in the molecule and the modified ethylene-α-olefin copolymer (A) according to claim 1.

12. A molded article comprising a modified ethylene-α-olefin copolymer (A) according to any one of claims 1 to 5, or the composition according to claim 10 or 11.

13. A raw material for a molded article comprising a modified ethylene-α-olefin copolymer (A) according to any one of claims 1 to 5, or the composition according to claim 10 or 11.

14. An adhesive comprising a modified ethylene-α-olefin copolymer (A) according to any one of claims 1 to 5, or the composition according to claim 10 or 11.

15. A sealing material comprising a modified ethylene-α-olefin copolymer (A) according to any one of claims 1 to 5, or the composition according to claim 10 or 11.

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