JP7854841B2 - Resin compositions and their uses - Google Patents

Description

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.

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).

International Publication No. 2013/099876 Brochure Japanese Patent Publication No. 2013-122061 International Publication No. 2014/050817 Brochure

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.

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. While the applicant has proposed improving heat resistance by producing 4-methyl-1-pentene polymers using a specific catalyst (see Patent Document 3), a means for producing films with suppressed gas permeability has not been found, and further improvements were desired.

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

The inventors of this invention conducted diligent research to solve the above problems and, as a result, discovered that a 4-methyl-1-pentene polymer having a specific composition and specific properties can solve the above problems, thus completing the present invention.

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) The mesodiad fraction (m) measured by ^13¹C -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 4-methyl-1-pentene polymer (X) described in [1] above, further satisfying 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] A 4-methyl-1-pentene polymer (X) according to [1] or [2] above, which 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.

[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], 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], 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.

[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) The mesodiad fraction (m) measured by ^13¹C -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.

[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 to 850 kg/ ^m³ .
[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 5 kg load in accordance with ASTM D1238 is 0.1 to 500 g/10 min.

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.

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.

<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).

《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-olefin, more preferably has a content of more than 99.5 mol% 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%, 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-olefin, and particularly preferably has a content of more than 99.6 mol% 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-olefin.

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 that the content of α-olefin-derived constituent units is low and the degree of crystallinity is high, thereby suppressing gas permeation in molded articles such as films containing the 4-methyl-1-pentene polymer (X).

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 a single type or two or more types.

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. Examples of other polymerizable compounds include: vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or their derivatives such as maleic anhydride; conjugated dienes such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 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 typically 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.

《Requirement (b)》
(b) The 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.

《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 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.

《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.

《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 and are therefore preferable.

《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 preferable 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.

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)

Furthermore, the upper limit of ΔHm - (0.5 × Tm - 76) is not particularly limited, but for example, it is 20. Being within this range 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.

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 constituent units derived from at least one selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene). Furthermore, it has a relatively high mesodiad fraction (m) and high stereoregularity. In addition, it has a relatively low decane-soluble portion at 23°C. For these reasons, the 4-methyl-1-pentene polymer (X) has a higher degree of crystallinity compared to conventionally known 4-methyl-1-pentene polymers. Generally, because crystallized regions have low mobility, gases do not easily pass through them, so it is presumed that molded articles such as films containing the 4-methyl-1-pentene polymer (X) have suppressed gas permeability. Moreover, because the 4-methyl-1-pentene polymer (X) of the present invention has a relatively low content of constituent units derived from α-olefins and a high melting point (Tm), molded articles such as films containing the 4-methyl-1-pentene polymer (X) have excellent heat resistance. Furthermore, the intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) of the present invention makes it easy to obtain molded articles with excellent moldability and uniform thickness.
For the reasons stated above, it is presumed that the 4-methyl-1-pentene polymer (X) of the present invention can be used to obtain molded articles such as films that are heat-resistant, lightweight, and capable of suppressing gas permeation.

The 4-methyl-1-pentene polymer (X) of the present invention preferably satisfies one or more of the above requirements (a) to (f), as well as requirements (g) and (h).

《Requirement (g)》
(g) The density measured in accordance with the density gradient pipe method of JIS K7112 is preferably 815 to 850 kg/ ^m³ . The density of the 4-methyl-1-pentene polymer (X) of the present invention is more preferably 820 to 840 kg/ ^m³ , even more preferably 825 to 835 kg/ ^m³ , and particularly preferably 825 to 832 kg/ ^m³ .
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).

《Requirements (h)》
(h) The melt flow rate (MFR), measured at 260°C and under a 5 kg 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.

Furthermore, the 4-methyl-1-pentene polymer (X) of the present invention preferably has a Vicat softening temperature of 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.

<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. For example, it can be suitably produced by a production method having 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.

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 suitably produced.

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].

The olefin polymerization catalyst may be further used as needed.
(C) It is more preferable to contain a carrier.
Furthermore, the olefin polymerization catalyst may be used as needed.
(D) It may also contain organic compound components.

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

<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, the transition metal compound (A) encompasses all enantiomers of the transition metal compound [I], for example, the transition metal compound represented by general formula [I'], without departing from the spirit of the present invention.

In formula [I], ^R1 , ^R3 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , ^R12 , ^R13 , ^R14 , ^R15 , and ^R16 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group; ^R2 is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group; ^R4 is a hydrogen atom; and any two substituents from ^R1 to ^R16 , excluding ^R4 , may be bonded to each other to form a ring.

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, and j is an integer from 1 to 4. When j is an integer of 2 or greater, Q may be chosen in the same or different combinations.

In the notation of formulas [I] and [I'], the MQ _j portion is assumed to be in front of the page, and the bridging portion is in the background. That is, in the transition metal compound (A), there is a hydrogen atom (R ⁴ ) facing the central metal at the α position of the cyclopentadiene ring (relative to the carbon atom substituted by the bridging portion).

Because transition metal compound [I] has ^R2 which is not a hydrogen atom and ^R4 which is a hydrogen atom, it is possible to produce olefin polymers with high stereoregularity, high melting point, and high molecular weight even under economical polymerization conditions, which were difficult with conventionally known metallocene compounds.

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

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 higher 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.).

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

The transition state in β-hydrogen transfer to the monomer is a six-membered ring structure centered on M' (Equation (ii)). The monomer insertion reaction adopts a five-membered ring structure because the hydrogen at the α position coordinates to M' (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 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, the molecular weight of the resulting polymer is known to increase (see Macromolecules (1996), 29, 2729).

On the other hand, the transition state in β-hydrogen transfer to the central metal M adopts 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.

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, if a substituent larger than a hydrogen atom, i.e., a substituent other than a hydrogen atom, is introduced to ^R4 in a skeleton where ^R2 is not a hydrogen atom, the space around the central metal M becomes smaller. As a result, β-hydrogen transfer to the monomer via the transition state of the six-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 five-membered ring structure is reduced. For this reason, β-hydrogen transfer to the central metal M via the transition state of the four-membered ring structure is promoted, and the molecular weight does not become sufficiently large.

On the other hand, if ^R2 is not a hydrogen atom in the skeleton, and ^R4 is 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 weight.

For the reasons stated above, it is believed that a catalyst exhibiting superior performance is only possible when the bridging portion connecting the cyclopentadiene ring and the fluorene ring has a five-membered ring structure, and when ^R2 is not a hydrogen atom and ^R4 is a hydrogen atom.

< ^R1 to ^R16 >
Examples of hydrocarbon groups in ^R1 to ^R16 (excluding ^R4 ) 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 cyclic unsaturated hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

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.

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.

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.

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.

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.

Examples of heteroatom-containing hydrocarbon groups in ^R1 to ^R16 (excluding ^R4 ) include alkoxy groups such as methoxy and ethoxy groups, aryloxy groups such as phenoxy groups, and oxygen-containing hydrocarbon groups such as furyl groups; amino groups such as N-methylamino groups, N,N-dimethylamino groups, and N-phenylamino groups, and nitrogen-containing hydrocarbon groups such as pyryl groups; and sulfur-containing hydrocarbon groups such as thienyl groups. The number of carbon atoms in the 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 the heteroatom-containing hydrocarbon groups.

Examples of silicon-containing groups in ^R1 to ^R16 (excluding ^R4 ) include groups represented by the formula _-SiR3 (wherein 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.

Among the substituents ^R1 to ^R16 , excluding ^R4 , two adjacent substituents (e.g., ^R1 and ^R2 , R2 and R3, ^R5 and ^R7 , ^R6 and ^R8 , ^R7 and ^R8 , ^R9 and ^R10 , ^R10 and ^R11 , ^R11 and ^R12 , ^R13 and ^R14 , ^R14 and ^R15 , ^R15 and ^R16 ) may bond to each other to form ^a ring, or ^R6 and ^R7 may bond to each other to form a ring, or ^{R1 and R8} may bond to each other to form a ring, or ^R3 and ^R5 may bond to each other to form a ring. Such ring formations may exist in two or more locations within the molecule.

In this specification, examples of rings formed by the bonding of two substituents (additional rings) include alicyclic rings, aromatic rings, and heterocyclic rings. Specifically, examples include cyclohexane rings; benzene rings; hydrogenated benzene rings; cyclopentene rings; heterocyclic rings such as furan rings and thiophene rings, and their corresponding hydrogenated heterocyclic rings. Preferably, these are cyclohexane rings, benzene rings, and hydrogenated benzene rings. Furthermore, such ring structures may have substituents such as alkyl groups on the ring.

From the viewpoint of stereoregularity, ^R1 and ^R3 are preferably hydrogen atoms.
At least one selected from ^R5 , ^R6 , and ^R7 is preferably a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group, more preferably ^R5 is a hydrocarbon group, even more preferably ^R5 is a linear alkyl group, a branched alkyl group, or other alkyl group having 2 or more carbon atoms, a cycloalkyl group, or a cycloalkenyl group, and particularly preferably ^R5 is an alkyl group having 2 or more carbon atoms. From a synthetic viewpoint, it is also preferable that ^R6 and ^R7 are hydrogen atoms. Furthermore, it is more preferable that ^R5 and ^R7 are bonded 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.

R ⁸ is preferably a hydrocarbon group, and particularly preferably an alkyl group.
From the viewpoint of stereoregularity, ^R2 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 especially preferably a substituent in which the carbon with free valence (the carbon bonded to the cyclopentadienyl ring) is a tertiary carbon.

Examples of ^R2 include methyl group, ethyl group, isopropyl group, tert-butyl group, tert-pentyl group, tert-amyl group, 1-methylcyclohexyl group, and 1-adamantyl group. More preferably, R2 is a substituent in which the carbon atom having a free valence is a tertiary carbon, such as tert-butyl group, tert-pentyl group, 1-methylcyclohexyl group, or 1-adamantyl group, and particularly preferably tert-butyl group or 1-adamantyl group.

In general formula [I], the fluorene ring portion is not particularly limited as long as it is a structure obtained from known fluorene derivatives, however, ^R9 , ^R12 , ^R13 , and ^R16 are preferably hydrogen atoms from the viewpoint of stereoregularity and molecular weight.

^R10 , ^R11 , ^R14 , and ^R15 are preferably a hydrogen atom, a hydrocarbon group, an oxygen atom-containing hydrocarbon group, or a nitrogen atom-containing hydrocarbon group, more preferably a hydrocarbon group, and even more preferably a hydrocarbon group having 1 to 20 carbon atoms.

^R10 and ^R11 may bond to each other to form a ring, and ^R14 and ^R15 may also bond 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.

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

Examples of halogen atoms in Q include fluorine, chlorine, bromine, and iodine.
Examples of hydrocarbon groups in Q include those similar to the hydrocarbon groups in ^R1 to ^R16 (excluding ^R4 ), and are preferably alkyl groups such as linear alkyl groups and branched alkyl groups.

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.

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.

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

The preferred embodiments of the transition metal compound [I], namely ^R1 to ^R16 , M, Q, and j, have been described above. In the present invention, any combination of each preferred embodiment is also a preferred embodiment. Specific examples of the transition metal compound [I] include the compounds described in Japanese Patent Application Publication No. 2015-183141.

The positional numbers used in naming 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 as shown in the following formulas [I-1] and [I-2].

[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, but the same applies to the method for producing its enantiomer.

A method for producing 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 corresponding to the desired stereochemistry of the transition metal compound [I] can be used.

In formula (1a), ^R1 , ^R3 , ^R5 , ^R6 , ^R7 , and ^R8 are each independently a hydrogen atom, a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group; ^R2 is a hydrocarbon group, a heteroatom-containing hydrocarbon group, or a silicon-containing group; ^R4 is a hydrogen atom; and any two substituents from ^R1 to ^R8 , excluding ^R4 , may be bonded to each other to form a ring. These preferred embodiments are the same as those described in general formula [I].

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 the transition metal compound [I], and step (3) of obtaining the transition metal compound [I] from the precursor compound (3a).

<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) with an aldehyde compound (1a-4) as shown in reaction [B].

In reaction [A], ^R1 to ^R6 and ^R8 are equivalent to the same symbols in general formula [I], and ^R7 is a hydrogen atom. In reaction [B], ^R1 to ^R8 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).

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. Only one of these isomers is illustrated in each reaction. The cyclopentadiene derivative (1a-1) and the fluorene derivative (2a) and precursor compound (3a), described later, may also be other isomers differing only in the position of the double bond in the cyclopentadienyl ring, or they may be mixtures thereof.

<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).

Furthermore, as a method for producing the pentalene compound (1a) according to reaction [A], there is also a method (Method A') in which a ketone or aldehyde is synthesized by treating a cyclopentadiene derivative (1a-1) with a base, then 1,4-adding it to an α,β-unsaturated carbonyl compound (1a-2), and then performing dehydration condensation.

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.

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 (e.g., 18-crown-6-ether, 15-crown-5-ether); cryptants; quaternary ammonium salts (e.g., tetrabutylammonium fluoride, methyltrioctylammonium chloride, tricaprylmethylammonium chloride); phosphonium salts (e.g., methyltriphenylphosphonium bromide, 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 (e.g., triflate), and acids (e.g., acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, paratolylsulfonic acid) may be used as catalysts for the 1,4-addition reaction in Method A'.

<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] include those mentioned above in reaction [A].

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.

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

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 suitable 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, particularly aldehydes and ketones themselves used as substrates; organic solvents such as water and ionic liquids; and non-organic solvents such as water and ionic liquids; or solvents obtained by mixing two or more of these. Furthermore, the reaction temperatures for reactions [A] and [B] are preferably -100 to 150°C, more preferably -40 to 120°C.

<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].

In the above reaction, ^R1 to ^R16 are equivalent to the same symbols in general formula [I], and L is an alkali metal or alkaline earth metal. Examples of alkali metals include lithium, sodium, or potassium, and examples of alkaline earth metals include magnesium and calcium.

For example, due to differences in the size of ^R4 (hydrogen atom) and ^R5 , a precursor compound (3a) can be obtained in which a hydrogen atom ( ^R4 ) facing the central metal side is obtained at the α-position of the cyclopentadiene ring when a complex is formed.
Fluorene derivatives (2a) can be obtained by conventionally known methods.

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.

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.

<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.

<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.

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.

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.

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.

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.

<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].

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].

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 complexes thereof with tetrahydrofuran, diethyl ether, dioxane or ethers such as 1,2-dimethoxyethane.

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.

<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.

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 these methods can be identified using analytical techniques such as proton nuclear magnetic resonance spectroscopy, ^13C -nuclear magnetic resonance spectroscopy, mass spectrometry, and elemental analysis.

<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) transition metal compounds (A) that react to form ion pairs.

《Organometallic compound (B-1)》
Examples of organometallic compounds (B-1) include organoaluminum compounds represented by general formula (B-1a), complex alkylates of group 1 metals and aluminum represented by general formula (B-1b), and dialkyl compounds of group 2 or group 12 metals represented by general formula (B-1c), as well as organometallic compounds of groups 1, 2, 12, and 13.

(B-1a):Ra _m Al(ORb) _n H _p X _q
In 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 is a number satisfying 0 < m ≤ 3, n is a number satisfying 0 ≤ n < 3, p is a number satisfying 0 ≤ p < 3, and q is a number satisfying 0 ≤ q < 3, and m + n + p + q = 3. Examples of organoaluminum compounds (B-1a) include trialkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, dialkylaluminum hydrides such as diisobutylaluminum hydride, and tricycloalkylaluminum.

(B-1b): M2AlRa ₄
In 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 alkyl complex (B- _1b ) include LiAl( _C2H5 ) ₄ and LiAl( _C7H15 ) ₄ .

(B-1c):RaRbM3
In 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 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.

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 Application 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.

(1) A method of reacting an organoaluminum compound, such as trialkylaluminum, with an organoaluminum compound by adding it to a hydrocarbon medium suspension 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.

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

(3) A method for reacting organoaluminum compounds such as trialkylaluminum with organotin oxides such as dimethyltin oxide and dibutyltin oxide in a medium such as decane, benzene, or toluene.

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

Furthermore, the above-mentioned aluminoxane may contain small amounts of organometallic components. Alternatively, after removing the solvent or unreacted organoaluminum compounds from the recovered aluminoxane solution by distillation, the solution may be redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specifically, the 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.

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. Furthermore, aluminoxanes prepared using trimethylaluminum and triisobutylaluminum, where R is an isobutyl group, are commercially produced under names such as MMAO and TMAO by companies like Tosoh Finechem.

Such MMAOs are aluminoxanes with improved solubility in various solvents and storage stability. Specifically, unlike those that are insoluble or sparingly soluble in benzene, they are characterized by their solubility in aliphatic and alicyclic hydrocarbons.

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.

Compound (B-3) that reacts with transition metal compound (A) to form an ion pair.
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, US Publication No. 5321106, 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).

In formula (B-3a), R ^e+ can be, for example, H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, or ferrocenium cation having a transition metal. ^{R f} to R ⁱ are each independently an organic group, preferably an aryl group.

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

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.

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

For Re ⁺ , for example, carbenium cations and ammonium cations are preferred, and triphenylcarbenium cations, N,N-dimethylanilinium cations, and N,N-diethylanilinium cations are particularly preferred.

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.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N,N-dialkylanilinium salts, and dialkylammonium salts.

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.

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.

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

As the ionic compound (B-3), other ionic compounds disclosed by the applicant (e.g., Japanese Patent Application 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.

<Carrier (C)>
Examples of the carrier (C) include inorganic compounds 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).

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

As porous oxides, for example, oxides such as _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.

The properties of porous oxides vary depending on the type and manufacturing method. The carriers preferably used in the present invention have a particle size of preferably 1 to 300 μm, more preferably 3 to 100 μm; a specific surface area of preferably 50 to 1300 ^m² /g, more preferably 200 to 1200 ^m² /g; and a pore volume of preferably 0.3 to 3.0 ^cm³ /g, more preferably 0.5 to 2.0 ^cm³ /g. Such carriers are used after drying and/or calcining at 100 to 1000°C, preferably 150 to 700°C, as needed. There are no particular restrictions on particle shape, but spherical is particularly preferred.

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 may be dissolved in a solvent such as alcohol, and then precipitated into fine particles using a precipitating agent.

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.

Examples of clays and clay minerals include kaolin, bentonite, kibushi clay, gylome clay, allophane, hisingerite, pyrophyllite, ummo group, montmorillonite group, vermiculite, lyokdiite group, palygorskite, kaolinite, nacrolite, dickite, halloysite, pectolite, and teniolite.

Examples of ion-exchangeable layered compounds include crystalline acidic salts of polyvalent metals such as α-Zr( _HAsO₄ ) _₂ · _H₂O , α-Zr( _HPO₄ ) _₂ , α-Zr( _KPO₄ ) _₂ · _3H₂O , α-Ti( _HPO₄ ) _₂ , α-Ti( _HAsO₄ ) _₂ · _H₂O , α-Sn( _HPO₄ ) _₂ · _H₂O , γ-Zr( _HPO₄ ) _₂ , γ-Ti( _HPO₄ ) _₂ , _and γ-Ti( _NH₄PO₄ ) _₂ · _H₂O .

It is also preferable to subject 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 matter treatment.

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.

Examples of guest compounds for intercalation 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 metal hydroxide ions such as [ _Al₁₃O₄ (OH) _₂₄ ] _⁷ ⁺ , [ _Zr₄ (OH) _₁₄ ] ^²+ , and [ _Fe₃O ( _OCOCH₃ ) _₆ ] ⁺ . These compounds may be used individually or in combination of two or more. Furthermore, when intercalating these compounds, polymers obtained by hydrolysis of metal alkoxides such as Si(OR) _₄ , Al(OR) _₃ , and Ge(OR) _₄ (where R is a hydrocarbon group, etc.), and colloidal inorganic compounds such as _SiO₂ can also be present.

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

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.

《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.

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

<How to use each ingredient and the order of addition>
During 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 of 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 method of adding a catalyst component, in which component (A) and component (B) are supported on component (C), to a polymerizer.

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 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 components (A) and (B) are supported on component (C), the olefin may be prepolymerized, and further catalyst components may be supported on the prepolymerized solid catalyst component.

In this manufacturing method, "polymerization" is used to refer collectively to both homopolymerization and copolymerization. Furthermore, "polymerizing olefins in the presence of an olefin polymerization catalyst" includes methods (1) to (5) above, where each component of the olefin polymerization catalyst is added to the polymerizer by any method to polymerize the olefin.

In this manufacturing method, polymerization can be carried out using either liquid-phase polymerization methods such as solution polymerization or suspension polymerization, or 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 in mixtures of two or more. Furthermore, a so-called bulk polymerization method, in which the liquefied olefin itself, which can be supplied to polymerization, is used as the solvent, can also be employed.

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.

Component (A) is used in an amount such that it is typically ^10⁻¹⁰ to ^10⁻² moles, preferably ^10⁻⁸ to ^10⁻³ moles, per liter of reaction volume. Component (B-1) can be used in an amount such that the molar ratio [(B-1)/M] of component (B-1) to the total transition metal atoms (M) in component (A) is typically 1 to 50,000, preferably 10 to 20,000, and particularly preferably 50 to 10,000. Component (B-2) can be used in an amount such that the molar ratio [Al/M] of aluminum atoms in component (B-2) to the total transition metal atoms (M) in component (A) is typically 10 to 5,000, preferably 20 to 2,000. Component (B-3) can be used in an amount such that the molar ratio [(B-3)/M] of component (B-3) to the total transition metal atoms (M) in component (A) is usually 1 to 1000, preferably 1 to 200.

When using component (C), 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.

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.

In this manufacturing method, the polymerization temperature of the olefin is typically -50 to 200°C, preferably 0 to 180°C; the polymerization pressure is typically atmospheric pressure to 10 MPa gauge pressure, preferably atmospheric pressure to 5 MPa gauge pressure. The polymerization reaction can be carried out using 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 other elements in the polymerization system, by changing the polymerization temperature, or by the amount of component (B) used.

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 typically 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, a temperature at which industrialization is feasible).

Hydrogen, in particular, can improve the polymerization activity of catalysts and increase or decrease the molecular weight of polymers, making it a desirable additive. When adding hydrogen to the system, an appropriate amount is approximately 0.00001 to 100 NL per mole of olefin. The hydrogen concentration in the system can be adjusted not only by adjusting the hydrogen supply, but also 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.

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

<Molded product>
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).

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), as long as the objectives of the present invention are not impaired.

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 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.

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 satisfies the above requirements.

As for polyethylene, low-density polyethylene, medium-density polyethylene, high-density polyethylene, and high-pressure low-density polyethylene, which are manufactured by 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.

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.
Examples of rosin-based resins include natural rosin, polymerized rosin, modified rosin obtained by modifying maleic acid, fumaric acid, (meth)acrylic acid, etc., and rosin derivatives. Examples of these rosin derivatives include esterified products of the aforementioned natural rosin, polymerized rosin, or modified rosin, phenol-modified products, and their esterified products. Furthermore, hydrogenated versions of these can also be mentioned.

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.

Examples of petroleum resins include aliphatic petroleum resins primarily derived from the C5 fraction of tar naphtha, aromatic petroleum resins primarily 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 C5-C9 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.

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

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.

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 of the above thermoplastic resin can be used alone, 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).

Examples of resin additives 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.

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 dibenzylidene sorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, rosin-based nucleating agents, metal benzoate salt-based nucleating agents, fluorinated polyethylene, 2,2-methylenebis(4,6-di-t-butylphenyl) sodium phosphate (trade name "ADEKA Stab NA-11," manufactured by ADEKA Corporation), pimelic acid and 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.

As antiblocking agents, known antiblocking agents can be used. Specifically, examples 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.

Examples of pigments include inorganic pigments (titanium dioxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of dyes include azo type, anthraquinone type, triphenylmethane type, etc. The amount of these pigments and dyes added is not particularly limited, but is usually 5% by mass or less, preferably 0.1 to 3% by mass, relative to the total mass of the resin composition containing the 4-methyl-1-pentene polymer (X).

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

Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetyl ricinolate), aliphatic dialbonate esters (such as adipic acid-propylene glycol polyesters), aliphatic tricarboxylic acid esters (such as triethyl citrate), phosphate triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

Examples of mold release agents include lower (C1-C4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4-C30) (such as hydrogenated castor oil), glycol esters of fatty acids, and liquid paraffin.

As antioxidants, known antioxidants can be used. Specifically, these include phenolic antioxidants (e.g., 2,6-di-t-butyl-4-methylphenol), polycyclic phenolic antioxidants (e.g., 2,2'-methylenebis(4-methyl-6-t-butylphenol)), phosphorus-based antioxidants (e.g., tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate), sulfur-based antioxidants (e.g., dilauryl thiodipropionate), amine-based antioxidants (e.g., N,N-diisopropyl-p-phenylenediamine), and lactone-based antioxidants. Several of these can also be used in combination.

Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.) and inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.).
Examples of UV absorbers include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based types.

Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.
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 alkylhydroxyethyl betaine.

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 each additive, such as the filler, lubricant, plasticizer, mold release agent, antioxidant, flame retardant, ultraviolet absorber, antibacterial agent, surfactant, and antistatic agent, 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).

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 can 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.

For example, the cylinder temperature in the mixing section of the kneading machine is typically 220 to 320°C, preferably 250 to 300°C. If the temperature is lower than 220°C, insufficient melting leads to inadequate mixing, and no improvement in the physical properties of the resin composition is 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.

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, they can be obtained 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 forming, calendering, filament molding, foam molding, and powder slush molding. Alternatively, the molded articles of the present invention may be 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.

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.

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.

"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.

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 articles, 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.

The film according to the present invention may be a stretched film. For example, a stretched film can be obtained by further uniaxial or biaxial stretching a primary molded article, which is formed into a film or sheet by T-die extrusion molding or the like using the 4-methyl-1-pentene polymer (X) of the present invention or a resin composition containing the same. The stretching ratio can be 2 to 20 times, independently in the MD direction and the TD direction. Specific applications of the stretched film include, for example, films for capacitors.

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). In the case of a laminated film, it is preferable that at least one surface layer contains the 4-methyl-1-pentene polymer (X).

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 forming 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 individually or in appropriate combinations as the base layer.

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 containing unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides, and more specifically, resins containing modified poly-4-methyl-1-pentene polymers.

There are no particular restrictions on the method for obtaining the laminated film, but examples include laminating a surface layer film obtained beforehand 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 them 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 it.

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, more preferably a die temperature of 250 to 300°C, more preferably a chill roll temperature of 75 to 110°C, even more preferably a die temperature of 260 to 290°C, and even more preferably a chill roll temperature of 80 to 110°C.

If the die temperature is higher than the above range, resin degradation can cause deposits to form, impairing the appearance and potentially reducing the mechanical properties of the film, such as its tensile strength. If the die temperature is lower than the above range, the resin viscosity increases, leading to turbulence in the resin flow inside the die during molding and melt fracture, which tends to increase the surface roughness and thickness variations of the resulting molded product, such as the film. If the chill roll temperature is higher than the above range, the film tends to wrap around the chill roll without peeling, making molding difficult. If the chill roll temperature is lower than the above range, wrinkles tend to form in the film, reducing thickness accuracy.

Uses of film
The applications of the film of this embodiment are not particularly limited, but for example,
Stretched film: For example, film for capacitors;
Semiconductor process films: for example, dicing tapes, backgrind tapes, die bonding films, polarizing film films;
Packaging films: for example, food packaging films, stretch films, wrap films, breathable films, shrink films, easy-peel films;
Separators: For example, battery separators, lithium-ion battery separators, electrolyte membranes for fuel cells, adhesive separators;
Films for electronic components: for example, diffusion films, reflective films, radiation-resistant films, gamma-ray-resistant films, porous films;
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 and 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.

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

The various physical properties were measured as follows:

[Content of constituent units]
The content of constituent units derived from 4-methyl-1-pentene in the 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) were calculated from ^13C -NMR spectra using the following apparatus and conditions.

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, the observed nucleus was ¹³ °C (125 MHz), the sequence was single-pulse proton broadband decoupling, the pulse width was 5.0 μs (45° pulse), the repetition time was 5.5 seconds, and the number of integrations was 64. 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.

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.

[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 have the same direction of isobutyl branching when represented as a planar zigzag structure, and was determined from the ^13C -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.)

^13C -NMR spectra were measured using a Valqua BioSpin AVANCEIII 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 60 mg/0.6 mL, the measurement temperature was 120°C, the observed nucleus was ^13C (125 MHz), 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, and the peak profile was divided into two regions: the high-field region (Region 1) and the low-field region (Region 2).

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.

[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 the formula below).
[η]=lim(ηsp/C) (C→0)

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

[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 left 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] x 100

[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 commercially available monodisperse standard polystyrene to create a calibration curve, and then calculated 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: TSKgel GMH6-HT (2 columns), TSKgel GMH6-HTL (2 columns) (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml/min; Sample: 0.15 mg/mL o-dichlorobenzene solution; Temperature: 140°C
Molecular weight conversion: PS conversion / general calibration method. The coefficients of the Mark-Houwink viscosity equation were used for the general calibration calculation. The Mark-Houwink coefficients for PS were taken from the values listed in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970)).

[density]
The density (kg/ ^m³ ) was measured in accordance with JIS K7112 (density gradient pipe method).
Here, low density indicates that the polymer and the resulting molded product are lightweight.

[Melting point (Tm), heat of fusion (ΔHm)]
Using a Seiko Instruments DSC measuring instrument (DSC220C), approximately 5 mg of the sample was placed in an aluminum measuring 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 was observed 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.

[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 at a heating rate of 50°C per hour and a test load of 10N.

[High-temperature modulus of elasticity at 170°C (E'170°C)]
The test film was measured using an RSA-III 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.

[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. Under conditions of 23°C and 0% RH, the permeation rates of hydrogen ( _H₂ ), oxygen ( _O₂ ), nitrogen ( _N₂ ), and carbon dioxide ( _CO₂ ) were measured using a ⁷ cm² test film, and the values were divided by the measurement area to determine the permeation rate 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.

[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.

[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.

(Preparation of solid catalyst components)
At 30°C, a 100 mL three-necked flask equipped with a stirrer was thoroughly purged with nitrogen. Under a nitrogen stream, 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 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%.

(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%.

[ 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. After raising the temperature to 45°C over 30 minutes from the start of polymerization, the temperature was maintained at 45°C for 4 hours. 47 N mL of hydrogen was charged 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.

(Preparation of evaluation pellets)
Polymerization was carried out multiple times 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-resistant stabilizer. Thereafter, evaluation pellets were obtained by granulation using a twin-screw extruder BT-30 (screw diameter 30 mmφ, L/D 46) manufactured by Plastics Engineering Research Institute 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.

(Manufacturing of injection-molded parts)
Using the aforementioned evaluation pellets, an injection-molded body in the shape of an IS dumbbell (ISO 3167:93) with a thickness of 4 mm and a parallel section of 80 mm was obtained by performing a primary injection at 320 kg/ ^cm² for 5 seconds, followed by a secondary injection at 260 kg/ ^cm² for 3 seconds, under the conditions of a cylinder temperature of 300°C and a mold temperature of 65°C using an injection molding machine M70B manufactured by Meiki Seisakusho Co., Ltd.
The Vicat softening temperature of the obtained injection-molded articles was measured using the method described above. The results are shown in Table 1.

(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.

[ Reference example 2]
(Production and evaluation of polymer [A-2])
Polymer [A-2] was obtained in the same manner as the production of polymer [A-1] in Reference Example 1, except that the amount of hydrogen added was changed from 47 mL each in three separate additions to 39 mL each. The analysis results are shown in Table 1. Furthermore, using the obtained polymer [A-2], evaluation pellets, injection-molded articles, and test films were prepared in the same manner as in Reference Example 1, and each was evaluated using the method described above. The results are shown in Table 1.

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

[Example 4]
(Manufacturing and evaluation of polymer [A-4])
Polymer [A-4] was obtained in the same manner as the production of polymer [A-1] in Reference Example 1, except that the amount of hydrogen added was changed from 47 mL each in three separate additions to 48 mL each. The analytical results are shown in Table 1.
Evaluation pellets were prepared in the same manner as in Reference Example 1, except that 0.1 parts by mass of sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate (ADEKA Corporation, ADEKA Stub NA-11) was added to 100 parts by mass of the obtained polymer [A-4].
Using the evaluation pellets described above, injection-molded bodies and test films were prepared in the same manner as in Reference Example 1, and each was evaluated using the method described above. The results are shown in Table 1.

[ Reference example 5]
(Manufacturing and evaluation of polymer [A-5])
Polymer [A-5] was obtained in the same manner as the production of polymer [A-1] in Reference Example 1, except that the amount of hydrogen added was changed from 47 mL each in three separate additions to 51 mL each. The analysis results are shown in Table 1. Furthermore, using the obtained polymer [A-5], evaluation pellets, injection-molded articles, and test films were prepared in the same manner as in Reference Example 1, and each was evaluated using the method described above. The results are shown in Table 1.

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

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

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

[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, evaluation pellets, injection-molded articles, and test films were prepared using each of the obtained polymers in the same manner as in Reference Example 1, and evaluated using the methods described above. The results are shown in Table 1.

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 the 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 (16)

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) The mesodiad fraction (m) measured by ^13¹C -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. 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. 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). 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 . 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 at 260°C and under a 5 kg load in accordance with ASTM D1238, is 0.1 to 500 g/10 min. A molded article comprising the resin composition described in claim 1. 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. The molded article according to claim 6 , which is an injection-molded article or an extruded article. The molded article according to claim 6 , which is in the form of a film or a sheet. A food packaging material or food storage container comprising a molded body according to any one of claims 6 to 9 . A laminate in which at least one layer comprises the resin composition described in any one of claims 1 to 5 . 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) The mesodiad fraction (m) measured by ^13¹C -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. 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. 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). 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 . 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 at 260°C and under a 5 kg load in accordance with ASTM D1238, is 0.1 to 500 g/10 min.