Resin compositions and their uses

Abstract

To provide: a 4-methyl-1-pentene polymer enabling manufacturing of a molded article such as a film which has high melting point, excellent heat resistance, light weight and is suppressed in gas transmission; a molded article including the 4-methyl-1-pentene polymer; and a method for manufacturing the film.SOLUTION: A 4-methyl-1-pentene polymer (X) satisfying all of the following requirements (a)-(f) is provided: (a) the content of a constitutional unit derived from 4-methyl-1-pentene is more than 99.4 mol% and 100 mol% or less, and the content of a constitutional unit derived from α-olefin is 0 mol% or more and less than 0.6 mol%; (b) a meso diad fraction (m) is 98.5% or more and 100% or less; (c) an intrinsic viscosity [η] is 0.1-6.0 dl / g; (d) the amount of a 23°C decane soluble part is 5.0 mass% or less; (e) a melting point (Tm) is 200-260°C; and (f) the amount of heat of fusion (ΔHm) is 45 J / g or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a 4-methyl-1-pentene polymer, molded articles such as films using the same, their applications, and a method for producing the film. [Background technology]

[0002] 4-methyl-1-pentene polymers, whose main constituent monomer is 4-methyl-1-pentene, are widely used in various applications because they have superior properties such as heat resistance, transparency, and electrical properties compared to polyethylene and polypropylene, as well as superior release properties and solvent resistance (see, for example, Patent Document 1). For example, films are used as FPC release films and release films for composite material molding, taking advantage of their good release properties, while molded articles are used in laboratory equipment and mandrels for rubber hose manufacturing, taking advantage of their chemical resistance, water resistance, and transparency. On the other hand, molded articles made from resin compositions containing known 4-methyl-1-pentene polymers may require further improvement in terms of heat resistance (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2013 / 099876 Brochure [Patent Document 2] Japanese Patent Publication No. 2013-122061 [Patent Document 3] International Publication No. 2014 / 050817 Pamphlet [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In packaging materials for food products and other applications, materials that suppress gas permeation are sometimes required. Polyolefin materials such as 4-methyl-1-pentene polymers generally have a relatively high degree of gas permeability, so when used in applications where gas permeation suppression is desired, a multilayer structure with other materials that form a gas barrier layer can be considered. However, from an environmental perspective, there is also a need to make packaging materials monomaterial to facilitate recycling. Furthermore, while increasing the thickness or density of the packaging material can be considered to suppress gas permeation in single-material packaging materials, there is also a need to lighten the packaging material from the perspective of reducing transportation energy. Furthermore, in packaging materials for fresh foods, there is a need to allow gaseous components emitted from the food to escape to the outside in order to maintain the freshness of the contents, thereby bringing the composition of the gas inside the food closer to that of the outside air. In packaging materials that meet this need, it is undesirable for the amount of gas permeation to differ depending on the type of gas.

[0005] As mentioned above, 4-methyl-1-pentene polymers are used in various films and molded articles, but depending on the application, higher heat resistance and reduced gas permeability are desired. The applicant has proposed improving heat resistance by producing 4-methyl-1-pentene polymers using a specific catalyst (see Patent Document 3), but a means for producing films with suppressed gas permeability has not been found, and further improvements have been desired.

[0006] The present invention aims to provide a 4-methyl-1-pentene polymer, a molded article such as a film containing the same, and a method for producing a film, which can be used to manufacture molded articles such as films that are excellent in heat resistance, lightweight, and capable of suppressing gas permeation. [Means for solving the problem]

[0007] The inventors of the present invention conducted diligent research to solve the above problems and found that a 4-methyl-1-pentene polymer having a specific composition and specific properties can solve the above problems, thus completing the present invention.

[0008] The present invention relates to the following [1] to

[12] . [1] A 4-methyl-1-pentene polymer (X) that satisfies all of the following requirements (a) to (f). (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) 13 The mesodiad fraction (m) measured by 13C-NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl / g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200-260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J / g or greater.

[0009] [2] The 4-methyl-1-pentene polymer (X) described in [1] above, further satisfying requirement (g) below. (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815-850 kg / m³ 3 That is the case. [3] A 4-methyl-1-pentene polymer (X) as described in [1] or [2] above, which further satisfies requirement (h) below. (h) The melt flow rate (MFR), measured under conditions of 260°C and a 5kg load in accordance with ASTM D1238, is 0.1 to 500 g / 10 min.

[0010] [4] A molded article comprising the 4-methyl-1-pentene polymer (X) described in any of [1] to [3] above. [5] The molded article according to [4] above, wherein the maximum wall thickness is 100 mm or less and the minimum wall thickness is 0.001 mm or more. [6] The molded article according to [4] or [5], which is an injection-molded article or an extruded article. [7] A molded article according to any one of [4] to [6] above, which is in the form of a film or a sheet. [8] A food packaging material or food storage container comprising a molded body as described in any of [4] to [7] above. [9] A laminate in which at least one layer is a layer containing the 4-methyl-1-pentene polymer (X) described in any of [1] to [3] above.

[0011]

[10] The process includes a step of forming a film containing a 4-methyl-1-pentene polymer (X) under film forming conditions of a die temperature of 200 to 320°C and a chill roll temperature of 70 to 120°C. A method for producing a film, wherein the 4-methyl-1-pentene polymer (X) satisfies all of the following requirements (a) to (f). (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) 13 The mesodiad fraction (m) measured by 13C-NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl / g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200-260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J / g or greater.

[0012]

[11] The method for producing the film according to

[10] , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (g). (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815-850 kg / m³ 3 That is the case.

[12] The method for producing a film according to

[10] or

[11] , wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (h). (h) The melt flow rate (MFR), measured under conditions of 260°C and a 5kg load in accordance with ASTM D1238, is 0.1 to 500 g / 10 min. [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a 4-methyl-1-pentene polymer and a molded article such as a film containing the same, which can be used to produce molded articles such as films that have excellent heat resistance, are lightweight, and can suppress gas permeation. Furthermore, according to the present invention, it is possible to provide a method for producing a film containing a 4-methyl-1-pentene polymer that has excellent heat resistance and can suppress gas permeation. [Modes for carrying out the invention]

[0014] The present invention will be described below. In this specification, the numerical range A to B means A or greater and B or less unless otherwise specified. Furthermore, unless otherwise specified, the terms "polymerization" and "(co)polymerization" are used to encompass both homopolymerization and copolymerization.

[0015] <4-methyl-1-pentene polymer (X)> The 4-methyl-1-pentene polymer (X) of the present invention satisfies all of the following requirements (a) to (f).

[0016] 《Requirement (a)》 (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (content of constituent units derived from α-olefins) is 0 mol% or more and less than 0.6 mol%. The 4-methyl-1-pentene polymer (X) of the present invention preferably has a content of 99.5 to 100 mol% of constituent units derived from 4-methyl-1-pentene and a content of 0 to 0.5 mol% of constituent units derived from α-olefins, more preferably has a content of 99.5 mol% or more and 100 mol% or less of constituent units derived from 4-methyl-1-pentene and a content of 0 mol% or more and less than 0.5 mol% of constituent units derived from α-olefins, even more preferably has a content of 99.6 to 100 mol% of constituent units derived from 4-methyl-1-pentene and a content of 0 to 0.4 mol% of constituent units derived from α-olefins, and particularly preferably has a content of 99.6 mol% or more and 100 mol% or less of constituent units derived from 4-methyl-1-pentene and a content of 0 mol% or more and less than 0.4 mol% of constituent units derived from α-olefins.

[0017] The 4-methyl-1-pentene polymer (X) of the present invention is preferable from the viewpoint of heat resistance and light weight when it satisfies the above-mentioned content of constituent units. Furthermore, it is preferable because it has a low content of α-olefin-derived constituent units and a high degree of crystallinity, thereby suppressing gas permeation of molded articles such as films containing the 4-methyl-1-pentene polymer (X).

[0018] Examples of ethylene and α-olefins having 3 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-eicosene. In this specification, ethylene is included in α-olefins. Among these, linear α-olefins having 5 to 20 carbon atoms are preferred from the viewpoint of imparting flexibility to molded articles obtained from 4-methyl-1-pentene polymers (X), linear α-olefins having 6 to 20 carbon atoms are more preferred, linear α-olefins having 8 to 20 carbon atoms are even more preferred, and linear α-olefins having 10 to 20 carbon atoms are particularly preferred. Specifically, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred, and 1-decene, 1-tetradecene, 1-hexadecene, and 1-octadecene are particularly preferred. When the 4-methyl-1-pentene polymer (X) has structural units derived from α-olefins, the structural units derived from α-olefins may be one type alone or two or more types.

[0019] The 4-methyl-1-pentene polymer (X) may further have constituent units derived from other polymerizable compounds other than 4-methyl-1-pentene and α-olefins having 2 to 20 carbon atoms, to the extent that it does not impair the objectives of the present invention. Other polymerizable compounds include, for example, vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or derivatives thereof such as maleic anhydride; conjugated dienes such as butadiene, isoprene, pentadiene, 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, Examples of non-conjugated polyenes include dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene. In the 4-methyl-1-pentene polymer (X), the content of constituent units derived from other polymerizable compounds is usually 0.5 mol% or less, preferably 0.3 mol% or less, and more preferably 0.1 mol% or less, out of 100 mol% of the total constituent units, and it is particularly preferable that they are not present.

[0020] 《Requirement (b)》 (b) 13The mesodiad fraction (m) measured by 13C-NMR is 98.5% or more and 100% or less. The mesodiad fraction (m) of the 4-methyl-1-pentene polymer (X) of the present invention is preferably 98.7 to 100%, more preferably 99.0 to 100%, even more preferably 99.3 to 100%, and particularly preferably 99.5 to 100%. When the mesodiad fraction (m) of the 4-methyl-1-pentene polymer (X) of the present invention satisfies the above range, the resulting molded article will have sufficient heat resistance and mechanical strength. In the present invention, the mesodiad fraction (m) of the 4-methyl-1-pentene polymer (X) can be adjusted, for example, by the type of olefin polymerization catalyst described later.

[0021] 《Requirement (c)》 (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl / g. The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) of the present invention is preferably 1.2 to 3.6 dl / g, more preferably 1.4 to 3.4 dl / g, and even more preferably 1.6 to 3.2 dl / g. If the intrinsic viscosity [η] is too high, the surface roughness and thickness unevenness of the resulting molded article, such as a film, tend to increase due to turbulence of the resin flow inside the die during molding and phenomena caused by melt fracture. Also, if the intrinsic viscosity [η] is too low, it is thought that the decrease in melt tension tends to cause ear wobble and lifting from the chill roll, resulting in greater thickness unevenness. When the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) of the present invention satisfies the above range, it is preferable because it is easy to obtain a molded article with excellent moldability and no thickness unevenness.

[0022] 《Requirement (d)》 (d) The 23°C decane-soluble portion is 5.0% by mass or less. The 4-methyl-1-pentene polymer (X) of the present invention preferably has a 23°C decane-soluble portion of 3.0% by mass or less, more preferably 1.0% by mass or less, even more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. When the 23°C decane-soluble portion of the 4-methyl-1-pentene polymer (X) of the present invention satisfies the above range, the crystallinity of the 4-methyl-1-pentene polymer (X) becomes high, and it is preferable that the molded article containing it can suppress gas permeation.

[0023] 《Requirement (e)》 (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200 to 260°C. The melting point (Tm) of the 4-methyl-1-pentene polymer (X) of the present invention is preferably 210 to 255°C, more preferably 220 to 250°C, and even more preferably 230 to 245°C. Since the 4-methyl-1-pentene polymer (X) of the present invention satisfies the above range, molded articles containing it have excellent heat resistance, which is preferable.

[0024] 《Requirement (f)》 (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J / g or more. The heat of fusion (ΔHm) of the 4-methyl-1-pentene polymer (X) of the present invention is preferably 48 J / g or more, more preferably 50 J / g or more, and even more preferably 52 J / g or more. The upper limit of this heat of fusion (ΔHm) is not particularly limited, but for example it is 70 J / g. The 4-methyl-1-pentene polymer (X) of the present invention is preferred because it satisfies the above range, has a high degree of crystallinity, and a molded article containing it has excellent heat resistance and can suppress gas permeation.

[0025] The 4-methyl-1-pentene polymer (X) of the present invention preferably satisfies the following formula (1), more preferably formula (2), even more preferably formula (3), and particularly preferably formula (4) for its melting point (Tm) and heat of fusion (ΔHm). ΔHm-(0.5×Tm-76)≧0 …(1) ΔHm-(0.5×Tm-76)>0 …(2) ΔHm-(0.5×Tm-76)≧6 …(3) ΔHm-(0.5×Tm-76)≧8 …(4)

[0026] Furthermore, while there are no particular limitations on the upper limit of ΔHm-(0.5×Tm-76), it is preferably 20. Within this range, it is preferable because it allows for excellent heat resistance, suppression of gas permeation, excellent moldability, and easier acquisition of molded articles with uniform thickness. A 4-methyl-1-pentene polymer (X) that satisfies the above formula has a larger heat of fusion (ΔHm) at a similar melting point (Tm) compared to conventionally known 4-methyl-1-pentene polymers, i.e., it has a higher degree of crystallinity.

[0027] The 4-methyl-1-pentene polymer (X) of the present invention satisfies all of the above requirements (a) to (f), thereby enabling the production of molded articles such as films that are heat-resistant, lightweight, and have suppressed gas permeability. The above effects are presumed to be due to the following reasons, but are not limited thereto. The 4-methyl-1-pentene polymer (X) of the present invention has a relatively low content of constitutional units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (content of constitutional units derived from α-olefins). Further, the meso diad fraction (m) is relatively high and the stereoregularity is high. In addition, the amount of the 23°C decane-soluble part is relatively small. Therefore, the 4-methyl-1-pentene polymer (X) has a higher crystallinity than conventionally known 4-methyl-1-pentene polymers. Generally, since the crystallized regions have low mobility and are difficult to permeate gas, it is presumed that the molded articles such as films containing the 4-methyl-1-pentene polymer (X) have suppressed gas permeation. Further, since the 4-methyl-1-pentene polymer (X) of the present invention has a relatively low content of constitutional units derived from α-olefins and a high melting point (Tm), the molded articles such as films containing the 4-methyl-1-pentene polymer (X) are excellent in heat resistance. Furthermore, according to the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) of the present invention, a molded article excellent in moldability and free from thickness unevenness can be easily obtained. For the above reasons, it is presumed that the 4-methyl-1-pentene polymer (X) of the present invention is excellent in heat resistance, lightweight, and can obtain a molded article such as a film capable of suppressing gas permeation.

[0028] In addition to the above requirements (a) to (f), the 4-methyl-1-pentene polymer (X) of the present invention preferably further satisfies one or more of the requirements (g) and (h).

[0029] 《Requirement (g)》 (g) The density measured in accordance with the density gradient tube method of JIS K7112 is preferably 815 to 850 kg / m 3 3. The density of the 4-methyl-1-pentene polymer (X) of the present invention is more preferably 820 to 840 kg / m 3 3, and even more preferably 825 to 835 kg / m 3 3, and particularly preferably 825 to 832 kg / m 3 3. When the density of the 4-methyl-1-pentene polymer (X) of the present invention satisfies the above range, it is preferable because the molded article containing it will be lightweight. The 4-methyl-1-pentene polymer (X) of the present invention that satisfies the above range will have excellent heat resistance and suppress gas permeation, even though the molded article containing it will be lightweight, by satisfying the above requirements (a) to (f).

[0030] 《Requirements (h)》 (h) The melt flow rate (MFR), measured at 260°C and under a 5kg load in accordance with ASTM D1238, is preferably 0.1 to 500 g / 10 min. The melt flow rate (MFR) of the 4-methyl-1-pentene polymer (X) of the present invention is more preferably 2 to 100 g / 10 min, and even more preferably 3 to 30 g / 10 min. A melt flow rate (MFR) within the above range is preferable in terms of resin fluidity during the production of molded articles. In the present invention, the melt flow rate (MFR) of the 4-methyl-1-pentene polymer (X) can be adjusted, for example, by co-existing hydrogen in the reactor during the polymerization reaction.

[0031] Furthermore, it is desirable that the 4-methyl-1-pentene polymer (X) of the present invention has a Vicat softening temperature of preferably 145 to 250°C, more preferably 150 to 230°C, even more preferably 190 to 230°C, and particularly preferably 195 to 230°C for injection-molded articles. The injection-molded articles used for measuring the Vicat softening temperature can be prepared by the method described in the examples below. A 4-methyl-1-pentene polymer (X) having such a Vicat softening temperature can provide molded articles with excellent heat resistance and dimensional stability.

[0032] <Method for producing 4-methyl-1-pentene polymer (X)> The 4-methyl-1-pentene polymer (X) of the present invention only needs to satisfy the above requirements (a) to (f), and the method of production is not particularly limited. However, it can be suitably produced by a method that includes the step of polymerizing 4-methyl-1-pentene and, if necessary, ethylene and at least one olefin selected from α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the presence of an olefin polymerization catalyst described later.

[0033] Catalysts for olefin polymerization In the production of the 4-methyl-1-pentene polymer (X), the olefin polymerization catalyst preferably used contains at least one transition metal compound (A) selected from the transition metal compound represented by the general formula [I] described later and its enantiomers. When a monomer mainly composed of 4-methyl-1-pentene is polymerized in the presence of this olefin polymerization catalyst containing the transition metal compound (A), a polymer with high stereoregularity is easily obtained, and the 4-methyl-1-pentene polymer (X) of the present invention, which has a high heat of fusion (ΔHm) relative to its melting point (Tm) and high crystallinity, can be preferably produced.

[0034] This olefin polymerization catalyst further, (B) At least one compound selected from (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) transition metal compounds (A) that react to form ion pairs (hereinafter also referred to as "compound (B)"). It is preferable that it contains [the specified ingredient].

[0035] The olefin polymerization catalyst may be further used as needed. (C) Carrier It is more preferable that it contains [the necessary ingredient / material]. Furthermore, the olefin polymerization catalyst may be used as needed. (D) Organic compound component It can also contain.

[0036] The preferred embodiments of each component—the transition metal compound (A), the compound (B), the carrier (C), and the organic compound component (D)—will be described in detail below.

[0037] <Transition metal compound (A)> The transition metal compound (A) used in the present invention is at least one selected from the transition metal compound represented by general formula [I] (hereinafter also referred to as transition metal compound [I]) and its enantiomers. Although enantiomers are not specifically mentioned in this specification, transition metal compound (A) encompasses all enantiomers of transition metal compound [I], for example, the transition metal compound represented by general formula [I'], without departing from the spirit of the present invention. [ka]

[0038] In formula [I], R 1 , R 3 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 Each of these is independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 2 R is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group. 4 R is a hydrogen atom, 4 Excluding R 1 From R 16 Any two of the substituents up to this point may be bonded to each other to form a ring.

[0039] In formula [I], M is a group 4 transition metal, Q is a halogen atom, hydrocarbon group, anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, j is an integer from 1 to 4, and when j is an integer of 2 or more, Q may be chosen in the same or different combinations.

[0040] Note that in the notation of formulas [I] and [I'], MQ j Assume that the portion is in front of the page and the bridging portion is in the background. That is, in the transition metal compound (A), a hydrogen atom (R) facing the central metal is located at the α position of the cyclopentadiene ring (relative to the carbon atom substituted by the bridging portion). 4 ) exists.

[0041] Transition metal compounds [I] are R 2 is not a hydrogen atom, and R 4 Because the atom is a hydrogen atom, it is possible to produce olefin polymers with high stereoregularity, a high melting point, and a high molecular weight, even under economical polymerization conditions, which were difficult with conventionally known metallocene compounds.

[0042] The reason why transition metal compounds [I] exhibit superior performance is explained below using the estimated polymerization reaction mechanism, citing their effect on the molecular weight of polymers as an example.

[0043] The large molecular weight of the polymer produced by the polymerization reaction means that the rate of the growth reaction, in which monomers are inserted between the central metal of the catalyst and the polymer chain, is significantly larger than the rate of the chain transfer reaction, in which polymer chain growth stops. In olefin polymerization reactions using metallocene catalysts, two main types of chain transfer reactions are known: β-hydrogen transfer, in which hydrogen atoms move to the central metal M of the catalyst, and β-hydrogen transfer, in which hydrogen atoms move to the monomer. The latter, β-hydrogen transfer, is considered to be dominant (see Chem. Rev. (2000), 100, 1253, et al.).

[0044] Schematic diagrams of each transition state are shown in equations (i) to (iii). Note that the ligands of the catalyst are omitted, and in equations (i) to (iii), M' represents the active center metal of the catalyst and P represents the polymer chain.

[0045] [ka]

[0046] The transition state in β-hydrogen transfer to the monomer is a six-membered ring structure centered on M' (Equation (ii)). In the monomer insertion reaction, the hydrogen at the α position coordinates to M', resulting in a five-membered ring structure (Equation (i)). When the space near M' is narrowed by the catalyst ligand, the transition state of the six-membered ring structure, which requires a larger space, becomes more unstable than the transition state of the five-membered ring structure. This means that the reaction rate of β-hydrogen transfer to the monomer decreases, and the reaction rate of the monomer insertion reaction increases relatively. As a result, it is known that the molecular weight of the resulting polymer increases (see Macromolecules (1996), 29, 2729).

[0047] On the other hand, the transition state in β-hydrogen transfer to the central metal M takes the form of a four-membered ring structure with an even smaller space than the transition state in the monomer insertion reaction (Equation (iii)). Therefore, if the space near M' becomes too small due to the ligand, the reaction rate of β-hydrogen transfer to the central metal M will relatively increase, and it is expected that the molecular weight of the resulting polymer will decrease.

[0048] The above reaction mechanism is applied to the transition metal compound [I]. This transition metal compound [I] has a five-membered ring structure in the bridging portion connecting the cyclopentadiene ring and the fluorene ring. Here, R 2 For a skeleton that is not a hydrogen atom, R 4 When substituents larger than hydrogen atoms, i.e., substituents other than hydrogen atoms, are introduced, the space around the central metal M becomes smaller. As a result, β-hydrogen transfer to the monomer via the transition state of the 6-membered ring structure can be suppressed, but at the same time, it is thought that the reaction rate of the insertion reaction of the monomer via the transition state of the 5-membered ring structure is reduced. Therefore, β-hydrogen transfer to the central metal M via the transition state of the 4-membered ring structure is promoted, and the molecular weight does not become sufficiently large.

[0049] On the other hand, R 2 For a skeleton that is not a hydrogen atom, R 4By replacing the atom with a hydrogen atom, it is possible to suppress only the β-hydrogen transfer to the monomer without inhibiting the monomer insertion reaction, thus enabling the production of polymers with higher molecular weights.

[0050] For the reasons stated above, the bridging portion connecting the cyclopentadiene ring and the fluorene ring has a 5-membered ring structure, R 2 is not a hydrogen atom, and R 4 It is believed that this catalyst exhibits superior performance only when the atom is a hydrogen atom.

[0051] 〈R 1 From R 16 〉 R 1 From R 16 (However, R 4 Examples of hydrocarbon groups in (excluding) include linear hydrocarbon groups, branched hydrocarbon groups, cyclic saturated hydrocarbon groups, cyclic unsaturated hydrocarbon groups, and groups obtained by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

[0052] Examples of linear hydrocarbon groups include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decanyl groups; and linear alkenyl groups such as allyl groups.

[0053] Examples of branched hydrocarbon groups include branched alkyl groups such as isopropyl group, tert-butyl group, tert-amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-dipropylbutyl group, 1,1-dimethyl-2-methylpropyl group, and 1-methyl-1-isopropyl-2-methylpropyl group.

[0054] Examples of cyclic saturated hydrocarbon groups include cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and methylcyclohexyl groups; and polycyclic groups such as norbornyl, adamantyl, and methyladamantyl groups.

[0055] Examples of cyclic unsaturated hydrocarbon groups include aryl groups such as phenyl, tolyl, naphthyl, biphenyl, phenanthryl, and anthracenyl groups; cycloalkenyl groups such as cyclohexenyl groups; and polycyclic unsaturated alicyclic groups such as 5-bicyclo[2.2.1]hepta-2-enyl groups.

[0056] Examples of groups formed by substituting one or more hydrogen atoms of a saturated hydrocarbon group with a cyclic unsaturated hydrocarbon group include groups formed by substituting one or more hydrogen atoms of an alkyl group such as a benzyl group, cumyl group, 1,1-diphenylethyl group, or triphenylmethyl group with an aryl group.

[0057] R 1 From R 16 (However, R 4 Examples of heteroatom-containing hydrocarbon groups in (excluding) include alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, oxygen atom-containing hydrocarbon groups such as furyl groups; amino groups such as N-methylamino groups, N,N-dimethylamino groups, and N-phenylamino groups, nitrogen atom-containing hydrocarbon groups such as pyryl groups; and sulfur atom-containing hydrocarbon groups such as thienyl groups. The number of carbon atoms in heteroatom-containing hydrocarbon groups is usually 1 to 20, preferably 2 to 18, and more preferably 2 to 15. However, silicon-containing groups are excluded from heteroatom-containing hydrocarbon groups.

[0058] R 1 From R 16 (However, R 4Examples of silicon-containing groups in (excluding) include groups represented by the formula -SiR3 (wherein the formula, each of the multiple Rs is independently an alkyl group or phenyl group having 1 to 15 carbon atoms), such as trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, diphenylmethylsilyl group, and triphenylsilyl group.

[0059] R 4 Excluding R 1 From R 16 Of the substituents up to (e.g., R) 1 and R 2 , R 2 and R 3 , R 5 and R 7 , R 6 and R 8 , R 7 and R 8 , R 9 and R 10 , R 10 and R 11 , R 11 and R 12 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 ) may be bonded to each other to form a ring, R 6 and R 7 They may be bonded to each other to form a ring, R 1 and R 8 They may be bonded to each other to form a ring, R 3 and R 5 These elements may be bonded to each other to form a ring. Such ring formations may occur at two or more locations within the molecule.

[0060] In this specification, examples of the ring (additional ring) formed by two substituents bonding to each other include an alicyclic ring, an aromatic ring, and a heterocyclic ring. Specifically, a cyclohexane ring; a benzene ring; a hydrogenated benzene ring; a cyclopentene ring; heterocyclic rings such as a furan ring and a thiophene ring, and corresponding hydrogenated heterocyclic rings are included, and a cyclohexane ring; a benzene ring and a hydrogenated benzene ring are preferred. Further, such a ring structure may further have a substituent such as an alkyl group on the ring.

[0061] R 1 and R 3 are preferably hydrogen atoms from the viewpoint of stereoregularity. R 5 、R 6 and R 7 at least one selected from is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group or a silicon-containing group, and R 5 is more preferably a hydrocarbon group, and R 5 is more preferably an alkyl group having 2 or more carbon atoms such as a linear alkyl group or a branched alkyl group, a cycloalkyl group or a cycloalkenyl group, and R 5 is particularly preferably an alkyl group having 2 or more carbon atoms. Further, from the viewpoint of synthesis, R 6 and R 7 are also preferably hydrogen atoms. Further, it is more preferable that R 5 and R 7 bond to each other to form a ring, and it is particularly preferable that the ring is a 6-membered ring such as a cyclohexane ring.

[0062] R 8 is preferably a hydrocarbon group, and particularly preferably an alkyl group. R 2From the perspective of stereoregularity, it is preferably a hydrocarbon group, more preferably a hydrocarbon group having 1 to 20 carbon atoms, even more preferably not an aryl group, particularly preferably a linear hydrocarbon group, a branched hydrocarbon group or a cyclic saturated hydrocarbon group, and particularly preferably a substituent in which the carbon atom having a free valence (the carbon atom bonded to the cyclopentadienyl ring) is a tertiary carbon atom.

[0063] R 2 Specific examples of R include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a tert-pentyl group, a tert-amyl group, a 1-methylcyclohexyl group, and a 1-adamantyl group. More preferably, it is a substituent in which the carbon atom having a free valence, such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclohexyl group, a 1-adamantyl group, etc., is a tertiary carbon atom, and particularly preferably a tert-butyl group and a 1-adamantyl group.

[0064] In the general formula [I], the fluorene ring moiety is not particularly limited as long as it is a structure obtained from a known fluorene derivative, but R 9 、R 12 、R 13 and R 16 are preferably hydrogen atoms from the viewpoints of stereoregularity and molecular weight.

[0065] R 10 、R 11 、R 14 and R 15 are preferably a hydrogen atom, a hydrocarbon group, a hydrocarbon group containing an oxygen atom or a hydrocarbon group containing a nitrogen atom, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms.

[0066] R 10 and R 11 are bonded to each other to form a ring, and R 14 and R 15These groups may be bonded to each other to form a ring. Examples of such substituted fluorenyl groups include benzofluorenyl group, dibenzofluorenyl group, octahydrodibenzofluorenyl group, 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group, and 1,1,3,3,6,6,8,8-octamethyl-2,3,6,7,8,10 Examples include the -hexahydro-1H-dicyclopenta[b,h]fluorenyl group and the 1',1',3',6',8',8'-hexamethyl-1'H,8'H-dicyclopenta[b,h]fluorenyl group, with the 1,1,4,4,7,7,10,10-octamethyl-2,3,4,7,8,9,10,12-octahydro-1H-dibenzo[b,h]fluorenyl group being particularly preferred.

[0067] <M, Q, j> M is a Group 4 transition metal, preferably Ti, Zr, or Hf, more preferably Zr or Hf, and particularly preferably Zr.

[0068] Examples of halogen atoms in Q include fluorine, chlorine, bromine, and iodine. The hydrocarbon group in Q is R 1 From R 16 (However, R 4 Examples of groups similar to the hydrocarbon group in (excluding) include alkyl groups such as linear alkyl groups and branched alkyl groups.

[0069] Examples of anionic ligands in Q include alkoxy groups such as methoxy and tert-butoxy; aryloxy groups such as phenoxy; carboxylate groups such as acetate and benzoate; sulfonate groups such as mesylate and tosylate; and amide groups such as dimethylamide, diisopropylamide, methylanilide, and diphenylamide.

[0070] Examples of neutral ligands that can coordinate with the lone pair of electrons in Q include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine; and ethers such as tetrahydrofuran, diethyl ether, dioxane, and 1,2-dimethoxyethane.

[0071] Q is preferably at least one halogen atom or alkyl group. j is preferably 2.

[0072] The above describes the composition of transition metal compounds [I], namely R 1 ~R 16 Preferred embodiments of M, Q, and j have been described. In the present invention, any combination of each preferred embodiment is also a preferred embodiment. Specific examples of transition metal compounds [I] include the compounds described in Japanese Patent Application Publication No. 2015-183141.

[0073] The positional indices used in the naming of transition metal compounds [I] are as follows, taking as examples [1-(1',1',4',4',7',7',10',10'-octamethyloctahydrodibenzo[b,h]fluoren-12'-yl)(5-tert-butyl-1-methyl-3-iso-propyl-1,2,3,4-tetrahydropentalene)] zirconium dichloride and [8-(1',1',4',4',7',7',10',10'-octamethyloctahydrodibenzo[b,h]fluoren-12'-yl)(2-tert-butyl-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)] zirconium dichloride and one of its enantiomers, they are shown in the following formulas [I-1] and [I-2].

[0074] [ka]

[0075] [Method for producing transition metal compound (A)] The transition metal compound (A) that constitutes the olefin polymerization catalyst used in the present invention can be produced by known methods, and the production method is not particularly limited. Below, an example of a method for producing the transition metal compound [I] preferably used in the present invention will be described, and the same applies to the method for producing its enantiomer.

[0076] A method for producing a transition metal compound [I] includes, for example, a step (1) of preparing a pentalene compound represented by general formula (1a). In the pentalene compound (1a), isomers can be used depending on the stereochemistry of the desired transition metal compound [I].

[0077] [ka]

[0078] In formula (1a), R 1 , R 3 , R 5 , R 6 , R 7 and R 8 Each of these is independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, and R 2 R is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group. 4 R is a hydrogen atom, 4 Excluding R 1 From R 8 Any two of the substituents up to 1 may be bonded to each other to form a ring. These preferred embodiments are the same as those described in general formula [I].

[0079] One embodiment includes, following step (1), step (2) of reacting a pentalene compound (1a) with a fluorene derivative (2a) to obtain a precursor compound (3a) of a transition metal compound [I], and step (3) of obtaining the transition metal compound [I] from the precursor compound (3a).

[0080] <Process (1)> The pentalene compound (1a) can be synthesized, for example, by reacting a cyclopentadiene derivative (1a-1) with an α,β-unsaturated carbonyl compound (1a-2), as shown in reaction [A]; or by reacting a cyclopentadiene derivative (1a-1) with a carbonyl compound (1a-3) and an aldehyde compound (1a-4), as shown in reaction [B].

[0081] [ka]

[0082] During reaction [A], R 1 ~R 6 , R 8 These are equivalent to the same symbols in general formula [I], and R 7 R is a hydrogen atom. In reaction [B], 1 ~R 8 These terms are equivalent to the same symbols in general formula [I]. These preferred embodiments are the same as those described in general formula [I]. In the above starting material compound, isomers can be used depending on the stereochemistry of the target pentalene compound (1a).

[0083] Furthermore, the cyclopentadiene derivative (1a-1) and the fluorene derivative (2a) and precursor compound (3a), described later, may have isomers that differ only in the position of the double bond in the cyclopentadienyl ring, and only one of these isomers is shown as an example in each reaction. The cyclopentadiene derivative (1a-1) and the fluorene derivative (2a) and precursor compound (3a), described later, may also be other isomers that differ only in the position of the double bond in the cyclopentadienyl ring, or they may be mixtures thereof.

[0084] <Reaction [A]> The pentalene compound (1a) based on reaction [A] can be prepared from a cyclopentadiene derivative (1a-1) and an α,β-unsaturated carbonyl compound (1a-2) under known conditions (see, for example, J. Org. Chem. 1989, 54, 4981-4982).

[0085] Another method for producing the pentalene compound (1a) following reaction [A] involves treating a cyclopentadiene derivative (1a-1) with a base, then 1,4-adding it to an α,β-unsaturated carbonyl compound (1a-2) to synthesize a ketone or aldehyde, followed by dehydration condensation (Method A').

[0086] The base used in Method A' can be any known base, such as alkali metals like sodium, potassium, and lithium; alkali metal or alkaline earth metal salts like potassium hydroxide, sodium hydroxide, potassium carbonate, sodium bicarbonate, barium hydroxide, sodium alkoxide, potassium alkoxide, magnesium hydroxide, magnesium alkoxide, potassium hydrogenated, and sodium hydrogenated; nitrogen-containing bases like diethylamine, ammonia, pyrrolidine, piperidine, aniline, methylaniline, triethylamine, lithium diisopropylamide, and sodium amide; organoalkali metal compounds like butyllithium, methyllithium, and phenyllithium; and Grignard reagents such as methylmagnesium chloride, methylmagnesium bromide, and phenylmagnesium chloride.

[0087] In Method A', a catalyst may be added to further improve the efficiency of the reaction. Known catalysts can be used, such as crown ethers like 18-crown-6-ether and 15-crown-5-ether; cryptants; quaternary ammonium salts like tetrabutylammonium fluoride, methyltrioctylammonium chloride, and tricaprylmethylammonium chloride; phosphonium salts like methyltriphenylphosphonium bromide and tetrabutylphosphonium bromide; and phase-transfer catalysts represented by linear polyethers. Alternatively, halides of magnesium, calcium, lithium, zinc, aluminum, titanium, iron, zirconium, hafnium, boron, tin, and rare earth elements, as well as Lewis acids like triflate, and acids like acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and paratolylsulfonic acid may be used. For the 1,4-addition reaction in Method A', copper halides such as copper chloride and copper iodide may be used.

[0088] <Reaction [B]> In reaction [B], the reaction can be carried out more efficiently by adding a base or catalyst. Examples of bases and catalysts that can be used in reaction [B] are those listed above in reaction [A].

[0089] In reaction [B], the cyclopentadiene derivative (1a-1) may be reacted simultaneously with the carbonyl compound (1a-3) and the aldehyde compound (1a-4), or one of the carbonyl compound (1a-3) or the aldehyde compound (1a-4) may be reacted first, followed by the other. In this case, the carbonyl compound (1a-3) or the aldehyde compound (1a-4) may be converted to an enolate form using lithium propylamide or the like before the reaction, or the enolates corresponding to the carbonyl compound (1a-3) or the aldehyde compound (1a-4) may be synthesized by known methods and then reacted. Furthermore, the carbonyl compound (1a-3) and the aldehyde compound (1a-4) may be reacted under different conditions.

[0090] Other methods for synthesizing the pentalene compound (1a) include those described in Angew. Chem. internal. Edit. 1970, 9, 892-893, J. Am. Chem. SOC. 1985, 107, 5308-5309, J. Org. Chem. 1990, 55, 4504-4506, etc.

[0091] Solvents that can be used in reactions [A] and [B] include, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; carboxylic acids such as formic acid, acetic acid, and trifluoroacetic acid; esters such as ethyl acetate and methyl acetate; triethylamine, pyrrolidine, piperidine, aniline, pyridine, and acetonitrile. Examples of solvents include amines, nitriles, or nitrogen-containing compounds; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, ethylene glycol, and methoxyethanol; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylimidazolidinone, and N-methylpyrrolidone; dimethyl sulfoxides; sulfur-containing compounds such as carbon disulfide; ketones such as acetone and methyl ethyl ketone, especially aldehydes and ketones themselves used as substrates; organic solvents such as water and ionic liquids; non-organic solvents such as water and ionic liquids; or solvents obtained by mixing two or more of these. The reaction temperatures for reactions [A] and [B] are preferably -100 to 150°C, more preferably -40 to 120°C.

[0092] <Process (2)> One embodiment includes step (2), following step (1), in which a pentalene compound (1a) and a fluorene derivative (2a) are reacted to obtain a precursor compound (3a) of a transition metal compound [I].

[0093] [ka]

[0094] During the above reaction, R 1 ~R 16 Each of these is equivalent to the same symbol in general formula [I], where L is an alkali metal or an alkaline earth metal. Examples of alkali metals include lithium, sodium, or potassium, while examples of alkaline earth metals include magnesium and calcium.

[0095] For example, R 4 (Hydrogen atom) and R 5 Due to differences in size, etc., when a complex is formed, the hydrogen atom (R) at the α-position of the cyclopentadiene ring faces the central metal side. 4 A precursor compound (3a) having the above can be obtained. Fluorene derivatives (2a) can be obtained by conventionally known methods.

[0096] Examples of organic solvents that can be used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; or solvents obtained by mixing two or more of these.

[0097] The reaction between the pentalene compound (1a) and the fluorene derivative (2a) is preferably carried out in a molar ratio of 10:1 to 1:10, more preferably 2:1 to 1:2, and particularly preferably 1.2:1 to 1:1.2. The reaction temperature is preferably -100 to 150°C, more preferably -40 to 120°C.

[0098] <Process (3)> An example of producing the transition metal compound [I] from the precursor compound (3a) is shown below. This does not limit the scope of the present invention, and the transition metal compound [I] may be produced by any known method.

[0099] <Synthesis of dialkali metal salts> A dialkali metal salt is obtained by contacting a precursor compound (3a) with at least one metal component selected from alkali metals, hydrogenated alkali metals, alkali metal alkoxides, organoalkali metals, and organoalkaline earth metals in an organic solvent.

[0100] Examples of alkali metals that can be used in the above reaction include lithium, sodium, and potassium; examples of atomized alkali metals include atomized sodium and atomized potassium; examples of alkali metal alkoxides include sodium methoxide, potassium ethoxide, sodium ethoxide, and potassium tert-butoxide; examples of organoalkali metals include methyllithium, butyllithium, and phenyllithium; examples of organoalkaline metals include methylmagnesium halide, butylmagnesium halide, and phenylmagnesium halide; or two or more of these may be used in combination.

[0101] Examples of organic solvents used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as tetrahydrofuran, diethyl ether, dioxane, 1,2-dimethoxyethane, tert-butyl methyl ether, and cyclopentyl methyl ether; halogenated hydrocarbons such as dichloromethane and chloroform; or solvents obtained by mixing two or more of these.

[0102] The reaction between the precursor compound (3a) and the metal component is preferably carried out in a molar ratio (precursor compound (3a):metal component) of 1:1 to 1:20, more preferably 1:1.5 to 1:4, and particularly preferably 1:1.8 to 1:2.5. The reaction temperature is preferably -100 to 200°C, more preferably -80 to 120°C.

[0103] To accelerate the above reaction, Lewis bases such as tetramethylethylenediamine, or α-methylstyrene, as described in International Publication No. 2009 / 072505, can also be used.

[0104] <Synthesis of transition metal compounds> The dialkali metal salt obtained in the above reaction is reacted with the compound represented by general formula (4a) in an organic solvent to synthesize the transition metal compound [I].

[0105] MZ k …(4a) In formula (4a), M is a group 4 transition metal, each of the multiple Zs is independently a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that can coordinate with a lone pair of electrons, and k is an integer from 3 to 6. The atoms or groups listed as M and Z are the same as M and Q described in the section on general formula [I].

[0106] Examples of compound (4a) include trivalent or tetravalent titanium fluoride, chloride, bromide, and iodide; tetravalent zirconium fluoride, chloride, bromide, and iodide; tetravalent hafnium fluoride, chloride, bromide, and iodide; or these combined with ethers such as tetrahydrofuran, diethyl ether, dioxane, or 1,2-dimethoxyethane. A complex with the following is an example.

[0107] The organic solvents used in the above reaction are those listed in the section on "Synthesis of Dialkali Metal Salts." The reaction between the dialkali metal salt and compound (4a) is preferably carried out in a molar ratio of 10:1 to 1:10, more preferably 2:1 to 1:2, and particularly preferably 1.2:1 to 1:1.2. The reaction temperature is preferably -80 to 200°C, more preferably -75 to 120°C.

[0108] <Other methods> Alternatively, the precursor compound (3a) may be directly reacted with organometallic reagents such as tetrabenzyl titanium, tetrabenzyl zirconium, tetrabenzyl hafnium, tetrakis(trimethylsilylmethylene) titanium, tetrakis(trimethylsilylmethylene) zirconium, tetrakis(trimethylsilylmethylene) hafnium, dibenzyl dichlorotitanium, dibenzyl dichlorozirconium, dibenzyl dichlorohafnium, or amide salts of titanium, zirconium, or hafnium.

[0109] The transition metal compound [I] obtained from the above reaction can be isolated and purified by methods such as extraction, recrystallization, and sublimation. The transition metal compound [I] obtained by such methods can be analyzed for proton nuclear magnetic resonance spectroscopy. 13 It is identified using analytical techniques such as 13C nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis.

[0110] <Compound (B)> Compound (B) which may be included in the catalyst for olefin polymerization is at least one compound selected from (B-1) organometallic compounds, (B-2) organoaluminum oxy compounds, and (B-3) compounds that react with transition metal compounds (A) to form ion pairs.

[0111] 《Organometallic compound (B-1)》 Examples of the organometallic compound (B-1) include organometallic compounds of Groups 1, 2, 12, and 13 such as an organoaluminum compound represented by the general formula (B-1a), a complex alkylated product of a Group 1 metal and aluminum represented by the general formula (B-1b), and a dialkyl compound of a Group 2 or Group 12 metal represented by the general formula (B-1c).

[0112] (B-1a): Ra m Al(ORb) n H p X q In the formula (B-1a), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X is a halogen atom, m satisfies 0 < m ≦ 3, n satisfies 0 ≦ n < 3, p satisfies 0 ≦ p < 3, q satisfies 0 ≦ q < 3, and m + n + p + q = 3. Examples of the organoaluminum compound (B-1a) include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

[0113] (B-1b): M2AlRa4 In the formula (B-1b), M2 is Li, Na, or K, and Ra is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the complex alkylated product (B-1b) include LiAl(C2H5)4 and LiAl(C7H 15 )4.

[0114] (B-1c): RaRbM3 In the formula (B-1c), Ra and Rb are each independently a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M3 is Mg, Zn, or Cd. Examples of the compound (B-1c) include dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium, ethyl-n-butylmagnesium, diphenylmagnesium, dimethylzinc, diethylzinc, di-n-butylzinc, and diphenylzinc. <​Among organometallic compounds (B-1), organoaluminum compounds (B-1a) are preferred. The organometallic compound (B-1) may be used alone or in combination of two or more.

[0116] Organoaluminum oxy compounds (B-2) The organoaluminum oxy compound (B-2) may be, for example, a conventionally known aluminoxane, or an organoaluminum oxy compound that is insoluble or sparingly soluble in benzene, as exemplified in Japanese Patent Publication No. 2-78687. Conventionally known aluminoxanes can be produced, for example, by the following methods (1) to (4), and are usually obtained as a solution in a hydrocarbon solvent.

[0117] (1) A method of reacting the adsorbed water or crystal water with the organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to a suspension of a hydrocarbon medium containing a compound or salt containing crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, or cerium chloride hydrate.

[0118] (2) A method of directly reacting an organoaluminum compound such as trialkylaluminum with water, ice, or water vapor in a medium such as benzene, toluene, diethyl ether, or tetrahydrofuran.

[0119] (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene, or toluene.

[0120] (4) A method for non-hydrolytic conversion, such as thermal decomposition, of compounds produced by reacting organoaluminum such as trialkylaluminum with organic compounds having a carbon-oxygen bond, such as tertiary alcohols, ketones, and carboxylic acids.

[0121] Furthermore, the aluminoxane may contain small amounts of organometallic components. Alternatively, the recovered aluminoxane solution may be distilled to remove the solvent or unreacted organoaluminum compounds, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

[0122] Specific examples of organoaluminum compounds used in preparing aluminoxanes include those exemplified as organoaluminum compound (B-1a). Among these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred.

[0123] Other examples of organoaluminum oxy compounds (B-2) include modified methylaluminoxanes. Modified methylaluminoxanes are aluminoxanes prepared using trimethylaluminum and alkylaluminum other than trimethylaluminum. Such compounds are generally called MMAOs. MMAOs can be prepared by the methods described in US Publication No. 4960878 and US Publication No. 5041584. In addition, aluminoxanes prepared using trimethylaluminum and triisobutylaluminum, where R is an isobutyl group, are commercially produced by companies such as Tosoh Finechem under names such as MMAO and TMAO.

[0124] Such MMAOs are aluminoxanes with improved solubility in various solvents and storage stability. Specifically, unlike those that are insoluble or poorly soluble in benzene as described above, they are characterized by their solubility in aliphatic and alicyclic hydrocarbons.

[0125] Furthermore, examples of organoaluminum oxy compounds (B-2) include organoaluminum oxy compounds containing boron atoms, halogen-containing aluminoxanes as exemplified in International Publication No. 2005 / 066191 and International Publication No. 2007 / 131010, and ionic aluminoxanes as exemplified in International Publication No. 2003 / 082879. Compound (B-2) may be used alone or in combination of two or more compounds.

[0126] Compounds (B-3) that react with transition metal compounds (A) to form ion pairs. Examples of compounds (B-3) that react with transition metal compounds (A) to form ion pairs (hereinafter also referred to as "ionic compounds (B-3)") 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, US5321106, etc. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned. The ionic compound (B-3) is preferably a compound represented by the general formula (B-3a).

[0127] [ka]

[0128] In formula (B-3a), R e+ For example, H + Examples include carbenium cations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations, and ferrocenium cations having transition metals. f ~R i Each of these is independently an organic group, preferably an aryl group.

[0129] Examples of carbenium cations include trisubstituted carbenium cations such as triphenylcarbenium cation, tris(methylphenyl)carbenium cation, and tris(dimethylphenyl)carbenium cation.

[0130] Examples of ammonium cations include trialkylammonium 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.

[0131] Examples of phosphonium cations include triarylphosphonium cations such as triphenylphosphonium cation, tris(methylphenyl)phosphonium cation, and tris(dimethylphenyl)phosphonium cation.

[0132] R e+ For example, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

[0133] Examples of carbenium salts include triphenylcarbenium tetraphenyl borate, triphenylcarbenium tetrakis(pentafluorophenyl) borate, triphenylcarbenium tetrakis(3,5-ditrifluoromethylphenyl) borate, tris(4-methylphenyl)carbenium tetrakis(pentafluorophenyl) borate, and tris(3,5-dimethylphenyl)carbenium tetrakis(pentafluorophenyl) borate.

[0134] Examples of ammonium salts include trialkylsubstituted ammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

[0135] Examples of trialkyl-substituted ammonium salts include triethylammonium tetraphenyl borate, tripropylammonium tetraphenyl borate, tri(n-butyl)ammonium tetraphenyl borate, trimethylammonium tetrakis(p-tolyl) borate, trimethylammonium tetrakis(o-tolyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(2,4-dimethylphenyl) borate, tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl) borate, tri(n-butyl)ammonium tetrakis(4-trifluoromethylphenyl) borate, tri( Examples include n-butylammonium tetrakis(3,5-ditrifluoromethylphenyl) borate, tri(n-butyl)ammonium tetrakis(o-tolyl) borate, dioctadecylmethylammonium tetraphenyl borate, dioctadecylmethylammonium tetrakis(p-tolyl) borate, dioctadecylmethylammonium tetrakis(o-tolyl) borate, dioctadecylmethylammonium tetrakis(pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis(2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis(3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis(4-trifluoromethylphenyl) borate, and dioctadecylmethylammonium tetrakis(3,5-ditrifluoromethylphenyl) borate.

[0136] Examples of N,N-dialkylanilinium salts include N,N-dimethylanilinium tetraphenyl borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl) borate, N,N-diethylanilinium tetraphenyl borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(3,5-ditrifluoromethylphenyl) borate, N,N-2,4,6-pentamethylanilinium tetraphenyl borate, and N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl) borate.

[0137] Examples of dialkylammonium salts include di(1-propyl)ammonium tetrakis(pentafluorophenyl)borate and dicyclohexylammonium tetraphenylborate.

[0138] As ionic compounds (B-3), other ionic compounds disclosed by the applicant (e.g., Japanese Patent Publication No. 2004-51676) may also be used without limitation. The ionic compound (B-3) may be used alone or in combination of two or more types.

[0139] <Carrier (C)> Examples of the carrier (C) include inorganic or organic compounds, which may be in the form of granular or fine particles. The transition metal compound (A) is preferably used in a form supported on the carrier (C).

[0140] 《Inorganic compounds》 As the inorganic compound in the support (C), porous oxides, inorganic chlorides, clays, clay minerals, or ion-exchangeable layered compounds are preferred.

[0141] As porous oxides, for example, oxides of SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or composites or mixtures containing these can be used. For example, natural or synthetic zeolites, SiO2-MgO, SiO2-Al2O3, SiO2-TiO2, SiO2-V2O5, SiO2-Cr2O3, and SiO2-TiO2-MgO can be used. Among these, porous oxides containing SiO2 and / or Al2O3 as the main component are preferred.

[0142] The properties of porous oxides vary depending on the type and manufacturing method. The carrier preferably used in the present invention has a particle size of 1 to 300 μm, more preferably 3 to 100 μm; and a specific surface area of ​​50 to 1300 m². 2 / g, more comfortably 200~1200m 2 The pore volume is preferably 0.3 to 3.0 cm³ / g. 3 / g, more preferably 0.5~2.0cm 3 The particle size is / g. Such carriers are used after being dried and / or calcined at 100-1000°C, preferably 150-700°C, as needed. There are no particular restrictions on the particle shape, but spherical is particularly preferred.

[0143] Examples of inorganic chlorides that can be 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 can be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

[0144] Clay is usually composed mainly of clay minerals. Ion-exchangeable layered compounds are compounds that have a crystalline structure in which planes formed by ionic bonds are stacked parallel to each other with weak bonding forces, 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, but artificially synthesized products can also be used. Examples of clays, clay minerals, or ion-exchangeable layered compounds include clays, clay minerals, or ionic crystalline compounds having layered crystalline structures such as hexagonal close-packed type, antimony type, CdCl2 type, and CdI2 type.

[0145] Examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingelite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrite, dickite, halloysite, pectolite, and teniolite.

[0146] 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.

[0147] It is also preferable to subject clay and clay minerals to chemical treatment. Chemical treatments can include surface treatments to remove impurities adhering to the surface, and treatments that affect the crystalline structure of the clay. Specific examples of chemical treatments include acid treatment, alkali treatment, salt treatment, and organic treatment.

[0148] Ion-exchangeable layered compounds may be layered compounds in which the interlayers are expanded by utilizing ion exchange properties to exchange exchangeable ions between layers with other large, bulky ions. These bulky ions play a supporting role in the layered structure and are usually called pillars. The introduction of another substance between the layers of a layered compound in this way is called intercalation.

[0149] Examples of interpolated 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 of metal hydroxide ions include those listed above. These compounds may be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolyzing metal alkoxides such as Si(OR)4, Al(OR)3, and Ge(OR)4 (where R is a hydrocarbon group, etc.), or colloidal inorganic compounds such as SiO2 may also be present.

[0150] Examples of pillars include oxides produced by intercalating the above-mentioned metal hydroxide ions between layers and then heating and dehydrating them.

[0151] Among the support materials (C), porous oxides containing SiO2 and / or Al2O3 as the main component are preferred. Clay or clay minerals are also preferred, with montmorillonite, vermiculite, pectolite, teniolite, and synthetic unmol are particularly preferred.

[0152] 《Organic compounds》 Examples of organic compounds in the support (C) include granular or particulate solids with a particle size in the range of 5 to 300 μm. Specifically, examples include (co)polymers produced mainly from α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene; (co)polymers produced mainly from vinylcyclohexane and styrene; and modified versions thereof.

[0153] <Organic compound component (D)> In the present invention, the organic compound component (D) is used as needed to improve polymerization performance and the physical properties of the resulting polymer. Examples of the organic compound (D) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0154] <How to use each ingredient and the order of addition> In olefin polymerization, the method of use and the order of addition of each component can be chosen arbitrarily, but the following methods are examples. Hereinafter, the transition metal compound (A), compound (B), support (C), and organic compound component (D) will also be referred to as "components (A) to (D)," respectively. (1) A method of adding component (A) alone to the polymerizer. (2) A method of adding component (A) and component (B) to a polymerizer in any order. (3) A catalyst component in which component (A) is supported on component (C), A method for adding component (B) to a polymerization reactor in any order. (4) A catalyst component in which component (B) is supported on component (C), A method for adding component (A) to a polymerization reactor in any order. (5) A catalyst component in which components (A) and (B) are supported on component (C) A method of adding to a polymerization reactor.

[0155] In each of the methods described in (2) to (5) above, at least two of the catalyst components may be in contact with each other beforehand. In each of the methods described in (4) and (5) above, in which component (B) is supported, unsupported component (B) may be added in any order as needed. In this case, component (B) may be the same or different. Furthermore, in the solid catalyst component in which component (A) is supported on component (C), and in the solid catalyst component in which component (A) and component (B) are supported on component (C), the olefin may be prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

[0156] In this manufacturing method, "polymerization" is used to refer collectively to homopolymerization and copolymerization. Furthermore, "polymerizing olefins in the presence of an olefin polymerization catalyst" includes methods (1) to (5) above, in which the components of the olefin polymerization catalyst are added to the polymerizer by any method to polymerize the olefin.

[0157] In this manufacturing method, polymerization can be carried out by either liquid-phase polymerization methods such as solution polymerization or suspension polymerization, or by gas-phase polymerization methods. Examples of inert hydrocarbon media used in liquid-phase polymerization include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, and xylene; and halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane. The inert hydrocarbon media may be used alone or as a mixture of two or more. Furthermore, a so-called bulk polymerization method can also be used, in which the liquefied olefin itself, which can be supplied to polymerization, is used as the solvent.

[0158] When polymerizing olefins using an olefin polymerization catalyst, the amounts of each component that can constitute the olefin polymerization catalyst used are as follows. Furthermore, the content of each component in the olefin polymerization catalyst can be adjusted as follows.

[0159] Component (A) is typically 10 per liter of reaction volume. -10 ~10 -2 moles, preferably 10 -8 ~10 -3 It is used in amounts that are molars. Component (B-1) can be used in amounts such that the molar ratio [(B-1) / M] of component (B-1) to all transition metal atoms (M) in component (A) is usually 1 to 50,000, preferably 10 to 20,000, and particularly preferably 50 to 10,000. Component (B-2) can be used in amounts such that the molar ratio [Al / M] of aluminum atoms in component (B-2) to all transition metal atoms (M) in component (A) is usually 10 to 5,000, preferably 20 to 2,000. Component (B-3) can be used in amounts such that the molar ratio [(B-3) / M] of component (B-3) to all transition metal atoms (M) in component (A) is usually 1 to 1,000, preferably 1 to 200.

[0160] When component (C) is used, it can be used in an amount such that the weight ratio of component (A) to component (C) [(A) / (C)] is preferably 0.0001 to 1, more preferably 0.0005 to 0.5, and even more preferably 0.001 to 0.1.

[0161] When using component (D), if component (B) is component (B-1), it can be used in an amount such that the molar ratio [(D) / (B-1)] is usually 0.01 to 10, preferably 0.1 to 5. If component (B) is component (B-2), it can be used in an amount such that the molar ratio [(D) / (B-2)] is usually 0.005 to 2, preferably 0.01 to 1. If component (B) is component (B-3), it can be used in an amount such that the molar ratio [(D) / (B-3)] is usually 0.01 to 10, preferably 0.1 to 5.

[0162] In this manufacturing method, the polymerization temperature of the olefin is usually -50 to 200°C, preferably 0 to 180°C; the polymerization pressure is usually atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out by batch, semi-continuous, or continuous methods. Furthermore, polymerization can be carried out in two or more stages with different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen or the like in the polymerization system, by changing the polymerization temperature, or by the amount of component (B) used.

[0163] This manufacturing method makes it possible to produce olefin polymers with high stereoregularity, high melting point, and high molecular weight while maintaining high catalytic activity even under high-temperature conditions advantageous in industrial manufacturing. Under such high-temperature conditions, the polymerization temperature is usually 40°C or higher, preferably 40 to 200°C, more preferably 45 to 150°C, and particularly preferably 50 to 150°C (in other words, particularly preferably a temperature at which industrialization is feasible).

[0164] Hydrogen, in particular, can be a desirable additive because it can improve the polymerization activity of catalysts and increase or decrease the molecular weight of polymers. When adding hydrogen to the system, an appropriate amount is approximately 0.00001 to 100 NL per mole of olefin. In addition to adjusting the amount of hydrogen supplied, the hydrogen concentration in the system can also be adjusted by carrying out reactions that generate or consume hydrogen within the system, by separating hydrogen using a membrane, or by releasing some of the hydrogen-containing gas outside the system.

[0165] The olefin polymer obtained by the above manufacturing method may be subjected to post-treatment steps such as known catalyst deactivation steps, catalyst residue removal steps, and drying steps, as necessary, after synthesis by the above method.

[0166] <Molded body> The molded article of the present invention is a molded article containing the 4-methyl-1-pentene polymer (X) of the present invention described above. Such a molded article of the present invention may be molded solely from a 4-methyl-1-pentene polymer (X), or it may be molded from a resin composition containing a 4-methyl-1-pentene polymer (X).

[0167] When the molded article of the present invention is molded from a resin composition containing a 4-methyl-1-pentene polymer (X), the resin composition may contain one or more resin components selected from various resin additives and resin components other than the 4-methyl-1-pentene polymer (X), to the extent that the objectives of the present invention are not impaired.

[0168] Examples of resin components other than the 4-methyl-1-pentene polymer (X) that may be included in the aforementioned resin composition include the following thermoplastic resins. Thermoplastic polyolefin resins, such as low-density, medium-density, and high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, 4-methyl-1-pentene-α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resins obtained by modifying these olefin resins; Thermoplastic polyamide resins, for example, aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612); Thermoplastic polyester resins; for example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomers; Thermoplastic vinyl aromatic resins, such as polystyrene, ABS resin, AS resin, and styrene-based elastomers (styrene-butadiene-styrene block polymer, styrene-isoprene-styrene block polymer, styrene-isobutylene-styrene block polymer, and the aforementioned hydrogenated materials); Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymer; ionomer; ethylene-vinyl alcohol copolymer; polyvinyl alcohol; fluorinated polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyethersulfone; rosin-based resin; terpene-based resin and petroleum resin; Copolymer rubbers include, for example, ethylene-α-olefin-diene copolymer, propylene-α-olefin-diene copolymer, 1-butene-α-olefin-diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber, and the like.

[0169] Examples of polypropylene include isotactic polypropylene and syndiotactic polypropylene. Isotactic polypropylene may be homopolypropylene, a random copolymer of propylene and α-olefins having 2 to 20 carbon atoms (excluding propylene), or a propylene block copolymer. Poly-4-methyl-1-pentene and 4-methyl-1-pentene·α-olefin copolymers are polymers distinct from 4-methyl-1-pentene polymers (X), and are either homopolymers of 4-methyl-1-pentene or random copolymers of 4-methyl-1-pentene·α-olefin. In the case of random copolymers of 4-methyl-1-pentene·α-olefin, examples of α-olefins copolymerized with 4-methyl-1-pentene include α-olefins having 2 to 20 carbon atoms, preferably 6 to 20, such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. These can be used individually or in combination of two or more. The melt flow rate (MFR; ASTMD1238, 260°C, 5.0 kg load) is preferably 0.1 to 200 g / 10 min, and more preferably 1 to 150 g / 10 min. Commercially available poly-4-methyl-1-pentene can be used, such as TPX (trademark name) manufactured by Mitsui Chemicals, Inc. Poly-4-methyl-1-pentene from other manufacturers can also be preferably used if it meets the above requirements.

[0170] As for polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and high-pressure low-density polyethylene, which are manufactured using conventionally known methods, can be used. Examples of polybutenes include homopolymers of 1-butene, or copolymers of 1-butene and olefins excluding 1-butene. Examples of olefins copolymerized with polybutene include the α-olefins mentioned above as α-olefins copolymerized with 4-methyl-1-pentene, and these olefins can be used individually or in mixtures of two or more. Examples of copolymers include 1-butene-ethylene random copolymers, 1-butene-propylene random copolymers, 1-butene-methylpentene copolymers, 1-butene-methylbutene copolymers, and 1-butene-propylene-ethylene copolymers. In such copolymers, from the viewpoint of heat resistance, it is preferable that the content of constituent units derived from 1-butene is 50 mol% or more, more preferably 70 mol% or more, and particularly preferable 85% or more.

[0171] Modified polyolefin resins can be obtained by graft-modifying the above-mentioned polyolefin resin with ethylenically unsaturated bond-containing monomers using organic peroxides. Examples of functional groups that modified polyolefins may possess include halogen atoms, carboxyl groups, acid anhydride groups, epoxy groups, hydroxyl groups, amino groups, amide groups, imide groups, ester groups, alkoxysilane groups, acid halide groups, and nitrile groups. Rosin-based resins include natural rosin, polymerized rosin, modified rosin obtained by modifying with maleic acid, fumaric acid, (meth)acrylic acid, etc., and rosin derivatives. Rosin derivatives include esters of the aforementioned natural rosin, polymerized rosin, or modified rosin, phenol-modified products, and their esters. Furthermore, hydrogenated versions of these can also be included.

[0172] Examples of terpene resins include resins composed of α-pinene, β-pinene, limonene, dipentene, terpene phenol, terpene alcohol, and terpene aldehyde. Aromatically modified terpene resins, obtained by polymerizing aromatic monomers such as styrene onto α-pinene, β-pinene, limonene, or dipentene, are also included. Hydrogenated versions of these resins can also be considered.

[0173] Examples of petroleum resins include aliphatic petroleum resins mainly derived from the C5 fraction of tar naphtha, aromatic petroleum resins mainly derived from the C9 fraction, and copolymer petroleum resins thereof. Specifically, these include C5 petroleum resins (resins polymerized from the C5 fraction of naphtha cracked oil), C9 petroleum resins (resins polymerized from the C9 fraction of naphtha cracked oil), and C5C9 copolymer petroleum resins (resins copolymerized from the C5 and C9 fractions of naphtha cracked oil). Other examples include coumarone-indene resins containing styrenes, indenes, coumarone, and other dicyclopentadienes from the tar naphtha fraction, alkylphenol resins represented by condensates of p-tert-butylphenol and acetylene, and xylene resins obtained by reacting o-xylene, p-xylene, or m-xylene with formalin.

[0174] Furthermore, one or more resins selected from the group consisting of rosin resins, terpene resins, and petroleum resins are preferably hydrogenated derivatives due to their excellent weather resistance and colorfastness. The softening point of the resin by the ring-spherical method is preferably in the range of 40 to 180°C. In addition, the number-average molecular weight (Mn) of the resin measured by GPC is preferably in the range of approximately 100 to 10,000. Commercially available rosin resins, terpene resins, and petroleum resins can also be used.

[0175] Among these thermoplastic resins, preferred are low-density, medium-density, and high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, styrene-based elastomer, vinyl acetate copolymer, ethylene-methacrylate copolymer, ionomer, fluoropolymer, rosin-based resin, terpene-based resin, and petroleum resin. More preferred in terms of improved heat resistance, improved low-temperature resistance, and flexibility are polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, vinyl acetate copolymer, styrene-based elastomer, rosin-based resin, terpene-based resin, and petroleum resin.

[0176] Preferably, the thermoplastic resins include poly-3-methyl-1-pentene and poly-3-methyl-1-butene, which act as nucleating agents for the 4-methyl-1-pentene polymer (X) of the present invention, thereby contributing to improved rigidity of the resulting film and the like. As for the thermoplastic resin, one type can be used alone from the above thermoplastic resins, or two or more types can be used in combination. The amount of these thermoplastic resins or other resin or polymer components added is preferably 0.1 to 30% by mass relative to the total mass of the resin composition containing the 4-methyl-1-pentene polymer (X).

[0177] Examples of additives for resins include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents, weather stabilizers, heat stabilizers, anti-slip agents, foaming agents, crystallization aids, anti-fogging agents, anti-aging agents, hydrochloric acid absorbers, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, and processing aids. These additives can be used individually or in combination of two or more as appropriate.

[0178] As a nucleating agent, known nucleating agents can be used to further improve the moldability of the 4-methyl-1-pentene polymer (X), that is, to increase the crystallization temperature and accelerate the crystallization rate. Specifically, examples include dibenzylidenesorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, rosin-based nucleating agents, metal benzoate salt-based nucleating agents, fluorinated polyethylene, sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate (trade name "ADEKA Stab NA-11", manufactured by ADEKA Corporation), pimelic acid or its salts, and 2,6-naphthalene dicarboxylic acid dicyclohexylamide. The amount of nucleating agent is not particularly limited, but is preferably 0.1 to 1 part by mass per 100 parts by mass of the 4-methyl-1-pentene polymer (X). The nucleating agent can be added as appropriate at various stages, such as during polymerization, after polymerization, or during molding.

[0179] Known antiblocking agents can be used. Specifically, these include finely powdered silica, finely powdered aluminum oxide, finely powdered clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely powdered crosslinked resin, such as crosslinked acrylic or methacrylic resin powder. Of these, finely powdered silica and crosslinked acrylic or methacrylic resin powder are preferred.

[0180] Examples of pigments include inorganic pigments (such as titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (such as azo lake pigments, thioindigo pigments, phthalocyanine pigments, anthraquinone pigments). Examples of dyes include azo dyes, anthraquinone dyes, triphenylmethane dyes, etc. The addition amounts of these pigments and dyes are not particularly limited, but the total amount is usually 5% by mass or less, preferably 0.1 - 3% by mass, based on the total mass of the resin composition containing the 4-methyl-1-pentene-based polymer (X).

[0181] Examples of fillers include glass fibers, carbon fibers, silica fibers, metal (such as stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates (such as calcium silicate, talc, clay, etc.), metal oxides (such as iron oxide, titanium oxide, alumina, etc.), metal carbonates (such as calcium sulfate, barium sulfate), and various metal (such as magnesium, silicon, aluminum, titanium, copper, etc.) powders, mica, glass flakes, etc. These fillers may be used alone or in combination of two or more. Examples of lubricants include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), higher fatty acid amides (such as stearic acid amide), etc.

[0182] Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methyl acetyl ricinoleate), aliphatic dicarboxylic acid esters (such as adipic acid-propylene glycol-based polyester), aliphatic tricarboxylic acid esters (such as triethyl citrate), triester phosphates (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), petroleum resins, etc.

[0183] Examples of mold release agents include lower (C1 - 4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4 - 30) (such as hydrogenated castor oil), glycol esters of fatty acids, liquid paraffin, etc.

[0184] As the antioxidant, known antioxidants can be used. Specifically, phenolic antioxidants (such as 2,6-di-t-butyl-4-methylphenol), polycyclic phenolic antioxidants (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)), phosphorus-based antioxidants (such as tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate), sulfur-based antioxidants (such as dilauryl thiodipropionate), amine-based antioxidants (such as N,N-diisopropyl-p-phenylenediamine), lactone-based antioxidants, etc. can be mentioned, and several of these can be used in combination.

[0185] As the flame retardant, organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.) can be mentioned. As the ultraviolet absorber, benzotriazole-based, benzophenone-based, salicylic acid-based, acrylate-based, etc. can be mentioned.

[0186] As the antibacterial agent, quaternary ammonium salts, pyridine-based compounds, organic acids, organic acid esters, halogenated phenols, organic iodine, etc. can be mentioned. Examples of surfactants include nonionic, anionic, cationic, or amphoteric surfactants. Examples of nonionic surfactants include polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts; polyhydric alcohol-type nonionic surfactants such as fatty acid esters of polyethylene oxide and glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of anionic surfactants include sulfate esters of alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate esters such as higher alcohol phosphate esters. Examples of cationic surfactants include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyl hydroxyethyl betaine.

[0187] Examples of antistatic agents include the surfactants mentioned above, fatty acid esters, and polymeric antistatic agents. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides. The amount of various additives such as the fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, and antistatic agents added is not particularly limited as long as it does not impair the purpose of the present invention, but is preferably 0.1 to 30% by mass of each additive based on the total mass of the resin composition containing the 4-methyl-1-pentene polymer (X).

[0188] The method for producing the resin composition containing the 4-methyl-1-pentene polymer (X) according to the present invention is not particularly limited, but for example, it may be obtained by mixing the 4-methyl-1-pentene polymer (X) with other optional components as needed in the above-mentioned addition ratios, and then melt-kneading the mixture. The method of melt mixing is not particularly limited and can generally be carried out using commercially available melt mixing equipment such as extruders.

[0189] For example, the cylinder temperature in the mixing section of a kneader is typically 220 to 320°C, preferably 250 to 300°C. If the temperature is lower than 220°C, insufficient melting will result in inadequate mixing, and no improvement in the physical properties of the resin composition will be observed. On the other hand, if the temperature is higher than 320°C, thermal decomposition of the 4-methyl-1-pentene polymer (X) may occur. The mixing time is typically 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the mixing time is less than 0.1 minutes, sufficient melting and mixing will not occur, and if the mixing time exceeds 30 minutes, thermal decomposition of the 4-methyl-1-pentene polymer (X) may occur, which is undesirable.

[0190] The molded articles of the present invention can be manufactured by molding a 4-methyl-1-pentene polymer (X), or a resin composition containing a 4-methyl-1-pentene polymer (X), into a desired shape by known methods, for example, by known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, vacuum molding, calendering, filament molding, foam molding, and powder slush molding. Alternatively, the molded articles of the present invention may be molded articles obtained by further processing a primary molded article obtained by methods such as extrusion molding, injection molding, or solution casting, using methods such as blow molding or stretching. Among these, injection molded articles or extruded articles are preferred.

[0191] Examples of applications for the molded articles of the present invention include packaging containers, packaging films, food packaging materials, food packaging containers, food packaging films, food films, food storage containers, various packaging materials, automotive parts (front end, fan shroud, cooling fan, engine under cover, engine cover, radiator box, side door, back door inner, back door outer, exterior panel, roof rail, door handle, luggage box, wheel cover, handle, cooling module, air cleaner, spoiler, fuel tank, platform and side member, motor connector housing, bumper, instrument panel surface material, control cable sheathing material, wire sheathing material), home appliance materials and parts, electrical and electronic components, building materials, civil engineering materials, agricultural materials, and daily necessities.

[0192] In this invention, since it is possible to manufacture a molded article with suppressed gas permeation, in one embodiment of the molded article, for example, a molded article having a maximum wall thickness of 100 mm or less and a minimum wall thickness of 0.001 mm or more (1 μm or more) is preferred. Furthermore, the 4-methyl-1-pentene polymer (X) of the present invention described above can achieve excellent heat resistance and suppression of gas permeation even when molded alone, and the molded articles of the present invention are suitable as food packaging materials, food storage containers, and the like. Furthermore, the molded article of the present invention is preferably a laminate in which at least one layer is a layer containing the 4-methyl-1-pentene polymer (X) of the present invention, and is also preferably a laminated film as described later.

[0193] "film" In one embodiment, a film (a molded article in the form of a film or sheet) is preferred as the molded article of the present invention. The film of this embodiment has the characteristics of conventional 4-methyl-1-pentene copolymers, such as mechanical properties, electrical properties (dielectric breakdown voltage, etc.), and release properties, and also has an excellent balance of heat resistance and gas permeation suppression. The film of this embodiment comprises the 4-methyl-1-pentene polymer (X) of the present invention and can be obtained, for example, by melt molding in the range of 180 to 320°C. The thickness of the film of this embodiment is, for example, 1 to 1000 μm, preferably 2 to 500 μm, and more preferably 10 to 500 μm.

[0194] The film of this embodiment may be, for example, a single-layer film obtained from a 4-methyl-1-pentene polymer (X) or a resin composition containing a 4-methyl-1-pentene polymer (X), or a laminated film having a layer obtained from a 4-methyl-1-pentene polymer (X) or a resin composition containing it. In this invention, "film" is a general term for planar molded products, and this includes sheets, membranes, tapes, and the like. The film of this embodiment is not particularly limited in its molding method, but it is preferably manufactured by extrusion molding.

[0195] The film according to the present invention may be a stretched film, for example, a stretched film obtained by further uniaxially or biaxially stretching a primary molded article obtained by forming a film or sheet from the 4-methyl-1-pentene polymer (X) of the present invention or a resin composition containing the same by T-die extrusion molding or the like. The stretching ratio can be 2 to 20 times, independently in the MD direction and the TD direction. A specific application of the stretched film is, for example, a film for capacitors.

[0196] The film according to the present invention may be a single-layer film containing the 4-methyl-1-pentene polymer (X) described above, or a laminated film in which at least one layer contains the 4-methyl-1-pentene polymer (X). Preferably, in the laminated film, at least one surface layer contains the 4-methyl-1-pentene polymer (X).

[0197] If the laminated film has a base layer other than the layer containing the 4-methyl-1-pentene polymer (X), the base layer may be made of any material, such as resin, paper, or metal. Examples of resins that make up the base layer include polyolefin resins such as low-density polyethylene, linear low-density polyethylene, high-density polyethylene, propylene homopolymer, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, butene homopolymer, ethylene-butene copolymer, propylene-butene copolymer, poly4-methyl-1-pentene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, and cyclic olefin copolymer. In addition, resins obtained by graft-modifying these resins with unsaturated carboxylic acids or their derivatives may also be used. Alternatively, examples include polyamide resins such as polyamide 6, polyamide 11, polyamide 12, polyamide 612, polyamide 66, polyamide 610, polyamide 46, polyamide MXD6, polyamide 6T, polyamide 6I, and polyamide 9T; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; or polycarbonate resins, vinyl chloride, vinylidene chloride, and polyurethane. Furthermore, examples include ethylene-acrylic acid ester copolymers, ethylene-methacrylic acid ester copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and partially ion crosslinked products thereof. The above resins can be used as the base layer, either individually or in appropriate combinations.

[0198] The laminated film may have each layer directly laminated, or it may be laminated via an adhesive layer. Examples of adhesive layers include modified polyolefin resins with unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides, and more specifically, resins containing modified poly-4-methyl-1-pentene polymers.

[0199] There are no particular restrictions on the method for obtaining the laminated film, but examples include laminating a surface layer film obtained in advance by T-die molding, extrusion casting, or inflation molding using known lamination methods such as extrusion lamination or extrusion coating; laminating multiple films by dry lamination after molding multiple films independently; and co-extrusion molding, in which multiple components are subjected to a multi-layer extruder for molding. Of these, co-extrusion molding, in which multiple components are subjected to a multi-layer extruder for molding, is preferred from the viewpoint of productivity. The surface layer film is, for example, a layer obtained from a 4-methyl-1-pentene polymer (X) or a resin composition containing the same.

[0200] Film manufacturing method The film of this embodiment is not limited by its molding method and can be manufactured by known manufacturing methods such as extrusion molding and inflation molding, and preferably by a method involving extrusion molding. The present invention relates to a method for producing a film, preferably involving extrusion molding, and comprises the step of molding a 4-methyl-1-pentene polymer (X) under film molding conditions of a die temperature of 200 to 320°C and a chill roll temperature of 70 to 120°C. Here, the 4-methyl-1-pentene polymer (X) is the 4-methyl-1-pentene polymer (X) of the present invention that satisfies all of the above requirements (a) to (f), and preferably, it is the 4-methyl-1-pentene polymer (X) of the present invention that further satisfies one or more of the above requirements (g) and (h). The film forming conditions are preferably a die temperature of 200 to 320°C and a chill roll temperature of 70 to 120°C as described above. More preferably, the die temperature is 250 to 300°C, and more preferably, the chill roll temperature is 75 to 110°C. Even more preferably, the die temperature is 260 to 290°C, and even more preferably, the chill roll temperature is 80 to 110°C.

[0201] If the die temperature is higher than the above range, surface gloss due to resin deterioration may occur, damaging the appearance, and the mechanical properties such as the tensile breaking strength of the film may decrease. If the die temperature is lower than the above range, the resin viscosity increases, and resin flow disturbance and melt fracture may occur inside the die during molding, resulting in an increase in the surface roughness and thickness unevenness of the molded body such as the obtained film. If the chill roll temperature is higher than the above range, molding tends to be difficult because the film wraps around the chill roll without peeling off. If the chill roll temperature is lower than the above range, the film tends to wrinkle and the thickness accuracy decreases.

[0202] 《Uses of the Film》 The uses of the film of this embodiment are not particularly limited. For example, Stretched film: For example, film for capacitors; Semiconductor process film: For example, dicing tape, back grinding tape, die bonding film, film for polarizing plates; Packaging film: For example, food packaging film, stretch film, wrap film, breathable film, shrink film, easy peel film; Separator: For example, battery separator, separator for lithium ion batteries, electrolyte membrane for fuel cells, separator for adhesives; Film for electronic components: For example, diffusion film, reflection film, radiation resistant film, gamma ray resistant film, porous film; Release films: For example, release films for flexible printed circuit boards, ACM substrates, rigid-flexible substrates, advanced composite materials, carbon fiber composite curing, glass fiber composite curing, aramid fiber composite curing, nanocomposite curing, filler curing, urethane curing, epoxy curing, semiconductor encapsulation, polarizing plates, diffusion sheets, prism sheets, reflective sheets, fuel cells, or various rubber sheets; Surface protection films: For example, protective films and masking films for polarizing plates, LCD panels, optical components, lenses, electrical components / appliances, mobile phones, personal computers, or touch panels; Building material films: For example, window films for building materials, films for laminated glass, bulletproof materials, films for bulletproof glass, heat-shielding sheets, heat-shielding films; These are some examples. [Examples]

[0203] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0204] Measurement method Various physical properties were measured as follows.

[0205] [Content of constituent units] The content of constituent units derived from 4-methyl-1-pentene in a 4-methyl-1-pentene polymer, and the content of constituent units derived from at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (content of constituent units derived from α-olefins) are determined using the following apparatus and conditions: 13 The result was obtained from the 1C-NMR spectrum.

[0206] Using a Bruker BioSpin AVANCE III Cryo-500 nuclear magnetic resonance spectrometer, the solvent was a mixed solvent of o-dichlorobenzene / benzene-d6 (4 / 1 v / v), the sample concentration was 55 mg / 0.6 mL, the measurement temperature was 120°C, and the observed nucleus was 13The measurement was performed using C (125 MHz), a single-pulse proton broadband decoupling sequence, a pulse width of 5.0 μs (45° pulse), a repetition time of 5.5 seconds, and 64 integration cycles. Benzene-d6 at 128 ppm was used as the reference value for the chemical shift. The content of α-olefin-derived constituent units was calculated using the integral value of the main chain methine signal and the following formula.

[0207] Content of α-olefin-derived constituent units (%) = [P / (P+M)] × 100 Here, P represents the total peak area of ​​the α-olefin main chain methine signal, and M represents the total peak area of ​​the 4-methyl-1-pentene main chain methine signal.

[0208] [Mesodiad fraction (m)] The mesodyad isotacticity (mesodyad fraction (m)) of 4-methyl-1-pentene polymers is defined as the proportion of any two head-to-tail linked 4-methyl-1-pentene unit chains in the polymer chain that, when represented as a planar zigzag structure, have the same direction of isobutyl branching. 13 The result was obtained from the 1C-NMR spectrum using the following formula. Isodiadic tacticity (%) = [m / (m+r)] × 100 (In the formula, m and r represent the absorption intensity derived from the main chain methylene of the 4-methyl-1-pentene unit linked at the head-to-tail position, as shown in the formula below.)

[0209] 13 The 1C-NMR spectrum was obtained using a Valcar BioSpin AVANCEIIIcryo-500 nuclear magnetic resonance spectrometer, with o-dichlorobenzene / benzene-d6 (4 / 1 v / v) mixed solvent, a sample concentration of 60 mg / 0.6 mL, a measurement temperature of 120°C, and the observed nuclei were 13 The C (125 MHz) transistor was used, the sequence was single-pulse proton broadband decoupling, the pulse width was 5.0 μs (45° pulse), and the repetition time was 5.5 seconds. Benzene-d6 at 128 ppm was used as the reference value for the chemical shift. The peak region was divided into two areas: the 41.5–43.3 ppm region, separated by the minimum point of the peak profile. The high-field side was classified as the first region, and the low-field side as the second region.

[0210] In the first region, the main chain methylene in the two-chain of 4-methyl-1-pentene units, represented by (m), resonates, and the integrated value, considered as a 4-methyl-1-pentene homopolymer, was defined as "m". In the second region, the main chain methylene in the two-chain of 4-methyl-1-pentene units, represented by (r), resonates, and its integrated value was defined as "r". A concentration of less than 0.01% was considered below the detection limit.

[0211] [Intrinsic viscosity [η]] The intrinsic viscosity [η] was measured at 135°C using decalin solvent. Specifically, approximately 20 mg of polymerization powder, pellets, or resin mass was dissolved in 15 mL of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity ηsp was measured again in the same manner. This dilution procedure was repeated two more times, and the value of ηsp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see formula below). [η] = lim(ηsp / C) (C→0)

[0212] [Melt Flow Rate (MFR)] The melt flow rate (MFR) was measured under conditions of 260°C and a 5kg load, in accordance with ASTM D1238.

[0213] [Decane-soluble portion] 5 g of each polymer was mixed with 200 mL of n-decane and heated at 145°C for 1 hour until dissolved. The mixture was cooled to 23°C and allowed to stand for 30 minutes. The precipitate (n-decane-insoluble portion) was then filtered off. The filtrate was placed in approximately three times its volume of acetone to precipitate the components dissolved in the n-decane. The precipitate was filtered off the acetone and dried. The mass of the precipitate was measured. No residue was observed even after concentrating the filtrate to dryness. The amount of n-decane-soluble portion was determined by the following formula. Amount of n-decane soluble portion (mass%) = [amount of precipitated substance / polymer mass] × 100

[0214] [Molecular weight distribution (Mw / Mn)] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured by GPC (gel permeation chromatography), and the molecular weight distribution (Mw / Mn) was determined. The GPC measurements were performed under the following conditions. Furthermore, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were determined using a calibration curve created with commercially available monodisperse standard polystyrene, based on the conversion method described below. (Measurement conditions) Equipment: Gel permeation chromatograph HLC-8321 GPC / HT type (manufactured by Tosoh Corporation) Organic solvent: o-dichlorobenzene Columns: 2 x TSKgel GMH6-HT columns, 2 x TSKgel GMH6-HTL columns (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140℃ Molecular weight conversion: PS conversion / General calibration method For the general calibration calculation, the coefficients of the Mark-Houwink viscosity equation were used. The Mark-Houwink coefficients for PS were those listed in the reference (J.Polym.Sci., Part A-2, 8, 1803 (1970)).

[0215] [density] Density (kg / m 3 The values ​​were measured in accordance with JIS K7112 (density gradient pipe method). Here, low density indicates that the polymer and the resulting molded product are lightweight.

[0216] [Melting point (Tm), heat of fusion (ΔHm)] Using a Seiko Instruments DSC analyzer (DSC220C), approximately 5 mg of the sample was placed in an aluminum pan and heated to 280°C at a rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 20°C at a rate of 10°C / min. After holding at 20°C for 5 minutes, the temperature was raised to 280°C at a rate of 10°C / min. The temperature at which the peak of the crystal melting peak observed during the second heating cycle appeared was defined as the melting point (Tm). The heat of fusion (ΔHm) was calculated from the integrated value of this crystal melting peak. In cases where multiple peaks were detected during measurement, the temperature and integrated value of the peak detected at the highest temperature were defined as the melting point and heat of fusion, respectively.

[0217] [Vicat softening temperature] For injection-molded products, a Vicat softening temperature test was conducted in accordance with ASTM D1525 using a testing machine manufactured by Yasuda Seiki Co., Ltd., in silicone oil, with a heating rate of 50°C per hour and a test load of 10N.

[0218] [High-temperature modulus of elasticity at 170°C (E'170°C)] The test film was measured using an RSA-III measuring device manufactured by TA instruments, in tensile mode, under the conditions of a heating rate of 4°C per minute, a frequency of 1 Hz, and a strain of 0.1%, from -20°C to 250°C, and the value of the storage modulus E' at 170°C was read.

[0219] [Gas permeation rate and standard deviation of gas permeation rate] A differential pressure method gas permeability measuring device BT-3 (Toyo Seiki Seisakusho) was used. The test was performed under conditions of 23°C and 0%RH using a 7cm test film. 2 Using this method, the permeation rates of hydrogen (H2), oxygen (O2), nitrogen (N2), and carbon dioxide (CO2) were measured, and the values ​​obtained by dividing these measurements by the measurement area were defined as the permeation rates for each gas. Furthermore, the standard deviation of the gas permeation rate was calculated using the following formula and obtained as the standard deviation of the gas permeation rate.

number

[0220] [Film thickness and standard deviation of film thickness] Ten measurements were taken in the direction of the film's flow, at the center of the film's width, using a micrometer. The average value of these measurements was used to determine the average film thickness. Furthermore, the standard deviation of the film was calculated using the above formula, similar to the standard deviation of the gas permeation rate, and was determined as the standard deviation of the film thickness.

[0221] [Manufacturing Example 1] Catalyst preparation (Production of transition metal compound (A)) (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride (transition metal compound (A)) was synthesized according to Synthesis Example 4 of International Publication No. 2014 / 050817.

[0222] (Preparation of solid catalyst components) At 30°C, 32 mL of purified decane and 14.65 mmol (in terms of aluminum atoms) of solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) were charged into a 100 mL three-necked flask equipped with a stirrer under a nitrogen stream to form a suspension. To this suspension, 50 mg (0.059 mmol (in terms of zirconium atoms) of the previously synthesized transition metal compound (A) was dissolved in a 4.6 mmol / L toluene solution, and 12.75 mL of this solution was added while stirring. After 1.5 hours, stirring was stopped, and the resulting catalyst component was washed three times with 50 mL of decane by decantation, and then suspended in decane to obtain 50 mL of slurry (B). The Zr loading rate in this catalyst component was 100%.

[0223] (Preparation of prepolymerization catalyst components) To the slurry (B) prepared above, 2.0 mL of a decane solution of diisobutylaluminum hydride (2.0 mmol / mL in terms of aluminum atoms) and 7.5 mL (5.0 g) of 4-methyl-1-pentene were added under a nitrogen stream. After 1.5 hours, stirring was stopped, and the obtained prepolymerization catalyst component was washed three times with 50 mL of decane by decantation. This prepolymerization catalyst component was suspended in decane to obtain 50 mL of decane slurry (C). The concentration of the prepolymerization catalyst component in decane slurry (C) was 20 g / L, 1.05 mmol-Zr / L, and the Zr recovery rate was 90%.

[0224] [ reference Example 1] (Production of polymer [A-1]) At room temperature and under a nitrogen atmosphere, 425 mL of purified decane and 0.5 mL (1 mol) of a decane solution of diisobutylaluminum hydride (2.0 mmol / mL in terms of aluminum atoms) were charged into a SUS polymerizer equipped with a stirrer with an internal volume of 1 L. Next, 0.0005 mmol (in terms of zirconium atoms) of the previously prepared decane slurry solution (C) of the pre-polymerization catalyst component was added, and 47 N mL of hydrogen was charged. Then, 250 mL of 4-methyl-1-pentene was continuously charged into the polymerizer at a constant rate over 2 hours. This charging start point was defined as the start of polymerization. The temperature was raised to 45°C over 30 minutes from the start of polymerization, and then maintained at 45°C for 4 hours. 47 N mL of hydrogen was charged again at 1 hour and 2 hours after the start of polymerization. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, the pressure was removed, and the polymerization solution containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80°C for 8 hours to obtain polymer [A-1]. The yield was 131 g. The analytical results of the obtained polymer [A-1] are shown in Table 1.

[0225] (Preparation of evaluation pellets) Multiple polymerization steps were performed as needed to prepare a sufficient amount of polymer for pellet production. To 100 parts by mass of the polymer obtained above, 0.1 parts by mass of tri(2,4-di-t-butylphenyl) phosphate was added as a secondary antioxidant, and 0.1 parts by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate was added as a heat stabilizer. Subsequently, evaluation pellets were obtained by granulation using a twin-screw extruder BT-30 (screw diameter 30 mmφ, L / D 46) manufactured by Plastics Engineering Laboratory Co., Ltd., under the conditions of a set temperature of 260°C, a resin extrusion rate of 60 g / min, and a rotation speed of 200 rpm. Using the obtained evaluation pellets, MFR measurements, density measurements, and DSC measurements were performed using the method described above. The results are shown in Table 1.

[0226] (Fabrication of injection-molded parts) Using the aforementioned evaluation pellets, a primary injection of 320 kg / cm² was performed on a Meiki Seisakusho Co., Ltd. M70B injection molding machine under the conditions of a cylinder temperature of 300°C and a mold temperature of 65°C. 2 This is done over 5 seconds, followed by a secondary injection of 260 kg / cm². 2 By performing this process over 3 seconds, an injection-molded body with an IS dumbbell shape (ISO3167:93) with a thickness of 4 mm and a parallel section of 80 mm was obtained. The Vicat softening temperature of the obtained injection-molded articles was measured using the method described above. The results are shown in Table 1.

[0227] (Preparation of test film) Using the evaluation pellets described above, a coat hanger type T-die (lip shape 270 x 0.8 mm) was mounted on a single-screw extruder (screw diameter 20 mmφ, L / D 28) manufactured by Thermo Plastics Co., Ltd. A 100 mmφ take-up chill roll was used. Under conditions of cylinder and die temperature of 280°C, molding was performed at the chill roll temperature and winding speed of 1.0 m / min as described in Table 1 to obtain test films. The obtained test films were used to evaluate their average thickness, high-temperature modulus, and gas permeability using the method described above. The results are shown in Table 1.

[0228] [ reference Example 2] (Production and evaluation of polymer [A-2]) Aside from changing the amount of hydrogen added from 47 mL each in three separate additions to 39 mL each, reference Polymer [A-2] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [A-2], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0229] [ reference Example 3] (Manufacturing and evaluation of polymer [A-3]) Except for using a mixed solution of 250 mL of 4-methyl-1-pentene and 0.86 mL of 1-decene as the inserted raw material, reference Polymer [A-3] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [A-3], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0230] [Example 4] (Manufacturing and evaluation of polymer [A-4]) Aside from changing the amount of hydrogen added from 47 mL each in three separate additions to 48 mL each, reference Polymer [A-4] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Except for the addition of 0.1 parts by mass of sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate (ADEKA Corporation, ADEKA Stab NA-11) to 100 parts by mass of the obtained polymer [A-4], the following conditions were met: reference Evaluation pellets were prepared in the same manner as in Example 1. Using the evaluation pellets, reference Similar to Example 1, injection-molded articles and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0231] [ reference Example 5] (Manufacturing and evaluation of polymer [A-5]) Aside from changing the amount of hydrogen added from 47 mL each in three separate additions to 51 mL each, reference Polymer [A-5] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [A-5], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0232] [Comparative Example 1] (Production and evaluation of polymer [B-1]) Aside from the fact that the inserted raw material was a mixed solution of 250 mL of 4-methyl-1-pentene and 1.3 mL of 1-decene, reference Polymer [B-1] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [B-1], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0233] [Comparative Example 2] (Production and evaluation of polymer [B-2]) Aside from the fact that the inserted raw material was a mixed solution of 250 mL of 4-methyl-1-pentene and 2.4 mL of 1-decene, reference Polymer [B-2] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [B-2], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0234] [Comparative Example 3] (Production and evaluation of polymer [B-3]) Except for using a mixed solution of 250 mL of 4-methyl-1-pentene and 6.7 mL of 1-decene as the inserted raw material, reference Polymer [B-3] was obtained in the same manner as the production of polymer [A-1] in Example 1. The analytical results are shown in Table 1. Furthermore, using the obtained polymer [B-3], reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0235] [Comparative Examples 4-9] (Manufacturing and evaluation of polymers [B-4] to [B-6]) Polymers [B-4], [B-5], and [B-6] were obtained by changing the proportions of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, and hydrogen, respectively, according to the methods of Comparative Examples 7 and 9 in International Publication No. 2006 / 054613. The analytical results are shown in Table 1. Furthermore, using each of the obtained polymers, reference Similar to Example 1, evaluation pellets, injection-molded bodies, and test films were prepared and evaluated using the method described above. The results are shown in Table 1.

[0236] [Table 1]

[0237] Table 1, which shows the results for each example and comparative example, indicates that in the examples using the 4-methyl-1-pentene polymer of the present invention, the permeation rates of hydrogen (H2), oxygen (O2), nitrogen (N2), and carbon dioxide (CO2) in the resulting films were all lower than those of the comparative examples, demonstrating that gas permeation was suppressed. Furthermore, in each example, the standard deviation of the gas permeation rate with respect to the type of gas was smaller than that of each comparative example, indicating that the degree of suppression of permeation rate differed depending on the type of gas. This result differed from the expectation that the standard deviation of gas permeation rate would not change easily. From this, it is considered that the molded articles such as films and containers of the present invention can be used more suitably than those made of conventional 4-methyl-1-pentene polymers in applications where a small difference in composition between the outside air and the gas inside is required. Furthermore, the results for each example and comparative example showed that when the heat of fusion (ΔHm) of the 4-methyl-1-pentene polymer was large, the variation in film thickness was relatively large, and the standard deviation of thickness was large. This suggests that at the moment the molten resin exiting the die adheres to the chill roll and solidifies, the higher the ΔHm level, the more likely it is to lift off the chill roll, resulting in poor stable adhesion. By increasing the chill roll temperature, adhesion to the chill roll improved, and the variation in film thickness and its standard deviation were reduced.

Claims

1. A 4-methyl-1-pentene polymer (X) that satisfies all of the following requirements (a) to (f), Phosphate ester salt-based nuclear agents and Includes, A resin composition comprising 0.1 to 1 part by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X). (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) 13 The mesodiad fraction (m) measured by 13C-NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl / g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200 to 260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J / g or more.

2. The resin composition according to claim 1, wherein the phosphate ester salt nucleating agent comprises sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate.

3. The resin composition according to claim 1, comprising 0.1 parts by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X).

4. The resin composition according to claim 1, wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (g). (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815 to 850 kg / m³ 3 That is the case.

5. The resin composition according to claim 1, wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (h). (h) The melt flow rate (MFR) measured under conditions of 260°C and a 5 kg load in accordance with ASTM D1238 is 0.1 to 500 g / 10 min.

6. A molded article comprising the resin composition described in claim 1.

7. The molded article according to claim 6, wherein the maximum wall thickness is 100 mm or less and the minimum wall thickness is 0.001 mm or more.

8. The molded article according to claim 6, which is an injection-molded article or an extruded article.

9. The molded article according to claim 6, which is in the form of a film or a sheet.

10. A food packaging material or food storage container comprising a molded body according to any one of claims 6 to 9.

11. A laminate in which at least one layer comprises the resin composition described in any one of claims 1 to 5.

12. The process includes a step of forming a film made of a resin composition containing a 4-methyl-1-pentene polymer (X) and a phosphate ester salt nucleating agent under film forming conditions of a die temperature of 200 to 320°C and a chill-roll temperature of 70 to 120°C. The resin composition contains 0.1 to 1 part by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X), A method for producing a film, wherein the 4-methyl-1-pentene polymer (X) satisfies all of the following requirements (a) to (f). (a) The content of constituent units derived from 4-methyl-1-pentene is greater than 99.4 mol% and less than or equal to 100 mol%, and the content of constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 mol% or more and less than 0.6 mol%. (b) 13 The mesodiad fraction (m) measured by 13C-NMR is between 98.5% and 100%. (c) The intrinsic viscosity [η] measured in decalin solvent at 135°C is 0.1 to 6.0 dl / g. (d) The decane-soluble portion at 23°C is 5.0% by mass or less. (e) The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200 to 260°C. (f) The heat of fusion (ΔHm) measured by differential scanning calorimetry (DSC) is 45 J / g or more.

13. The method for producing a film according to claim 12, wherein the phosphate ester salt nucleating agent comprises sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate.

14. The method for producing a film according to claim 12, wherein the resin composition contains 0.1 parts by mass of the phosphate ester salt nucleating agent per 100 parts by mass of the 4-methyl-1-pentene polymer (X).

15. The method for producing a film according to claim 12, wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (g). (g) The density measured in accordance with the density gradient pipe method of JIS K7112 is 815 to 850 kg / m³ 3 That is the case.

16. A method for producing a film according to any one of claims 12 to 15, wherein the 4-methyl-1-pentene polymer (X) further satisfies the following requirement (h). (h) The melt flow rate (MFR) measured under conditions of 260°C and a 5 kg load in accordance with ASTM D1238 is 0.1 to 500 g / 10 min.

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