3-methyl-1-butene copolymer, 3-methyl-1-butene-based polymer particles, and method for producing 3-methyl-1-butene-based polymer particles

Abstract

One embodiment of the present disclosure relates to a 3-methyl-1-butene copolymer, said copolymer comprising a constituent unit which is derived from 3-methyl-1-butene and a constituent unit which is derived from an α-olefin (excluding 3-methyl-1-butene), and having at least one melting point Tm(°C) as measured by differential scanning calorimetry, wherein expression (1) is satisfied.　Expression (1): Tm1≥-1.8α+300 (In expression (1), Tm1 indicates the melting point when there is one melting point Tm(°C), or the lowest melting point (°C) among a plurality of melting points when there are two or more melting points Tm(°C), and α indicates the content ratio (mol%) of the constituent unit which is derived from the α-olefin as calculated with an FT-IR calibration curve.)

Description

3-methyl-1-butene copolymer, 3-methyl-1-butene polymer particles, and method for producing 3-methyl-1-butene polymer particles

[0001] This disclosure relates to 3-methyl-1-butene copolymers, 3-methyl-1-butene copolymer particles, and methods for producing 3-methyl-1-butene polymer particles.

[0002] 3-methyl-1-butene polymers are widely known as high-melting-point polyolefins that can have high melting points (around 305°C) and are often used in various molding materials that require heat resistance. Due to their high melting points, 3-methyl-1-butene polymers require high processing temperatures, so techniques such as copolymerization to lower the melting point of the polymer have been employed to broaden the processing temperature range. However, this leads to the problem of decreased mechanical properties, and development of 3-methyl-1-butene polymers that can balance heat resistance, processability, and mechanical properties has been underway (for example, Patent Documents 1-3).

[0003] In recent years, the development of 3-methyl-1-butene polymers as dielectric modifiers for various electrical materials, nucleating agents for various polymers, powder coating materials, and materials for powder molding, such as materials for forming molded bodies produced by the SLS method of 3D printers, has been explored by micronizing 3-methyl-1-butene polymers. For example, Patent Document 4 discloses 3-methyl-1-butene polymer particles with a particle size of 30 μm or more at 50% of the cumulative volume and a narrow particle size distribution, as well as a method for producing the same.

[0004] Japanese Patent Publication No. 61-103910, Japanese Patent Publication No. 61-007349, Japanese Patent Publication No. 2024-057981, Japanese Patent Publication No. 2024-057983

[0005] However, the 3-methyl-1-butene polymers described in the above-mentioned Patent Documents 1 to 3 have a limited range of comonomers that can be used (α-olefins with 2 to 12 carbon atoms). Therefore, from the viewpoint of expanding the range of applications for 3-methyl-1-butene polymers, there has been a desire for the development of new 3-methyl-1-butene copolymers with superior physical properties.

[0006] Furthermore, when using 3-methyl-1-butene polymer particles as various additives or materials, it is generally considered preferable that the powder particle size is small and the particle size distribution is narrow, in terms of product uniformity and physical properties. However, polyolefin powders are light and prone to static electricity, which can cause powder aggregation, making it difficult to efficiently produce ultrafine particles with a small average particle diameter and a narrow particle size distribution. Patent Document 4 discloses 3-methyl-1-butene polymer particles with a cumulative volume of 50% and a particle size of 30 to 200 μm, but there are cases where particles with an even smaller average particle diameter are required.

[0007] The inventions in this disclosure have been made in view of the above, and the problem that the first aspect of this disclosure aims to solve is to provide a 3-methyl-1-butene copolymer that has excellent heat resistance and excellent toughness and dielectric properties. Furthermore, the problem that the second aspect of this disclosure aims to solve is to provide 3-methyl-1-butene polymer particles that have an even smaller particle size than conventional small-particle 3-methyl-1-butene polymer particles.

[0008] As a result of diligent study to solve the problems described herein, the inventors have found that the problems can be solved according to the first or second aspect of this disclosure, respectively, and have completed the inventions described herein. Examples of the configurations of the first and second aspects of this disclosure are described below.

[0009] Examples of the composition of the first aspect of this disclosure are as described in [1] to [9] below. [1] A 3-methyl-1-butene copolymer comprising a constituent unit derived from 3-methyl-1-butene and a constituent unit derived from an α-olefin (excluding 3-methyl-1-butene), having at least one melting point Tm (°C) measured by differential scanning calorimetry, and satisfying the following formula (1). Tm １ ≧-1.8α+300...(1) (In formula (1), Tm １α represents the melting point when there is one melting point Tm (°C), or the lowest melting point (°C) among multiple melting points when there are two or more melting points Tm (°C), and α represents the content percentage (mol%) of the constituent units derived from the α-olefin calculated from the FT-IR calibration curve. [2] The 3-methyl-1-butene copolymer according to [1], wherein the α-olefin is an α-olefin having 12 or more carbon atoms.

[0010] [3] The 3-methyl-1-butene copolymer according to [1] or [2], wherein the ratio of the storage modulus E'(23°C) at 23°C to the storage modulus E'(260°C) at 260°C (E'(23°C) / E'(260°C)) is 800 or less. [4] The 3-methyl-1-butene copolymer according to any one of [1] to [3], wherein the content of constituent units derived from 3-methyl-1-butene is 60 to 99.5 mol%, and the content of constituent units derived from α-olefin is 0.5 to 40 mol% (provided that the sum of the content of constituent units derived from 3-methyl-1-butene and the content of constituent units derived from α-olefin having 12 or more carbon atoms is 100 mol%). [5] The Tm １ A 3-methyl-1-butene copolymer according to any one of [1] to [4], wherein the temperature (°C) is 250°C or higher.

[0011] [6] The 3-methyl-1-butene copolymer according to any one of [1] to [5], wherein at least one of the Tm (°C) is 250 to 320°C. [7] The 3-methyl-1-butene copolymer according to any one of [1] to [6], wherein the number of folds in the flexural strength test in accordance with JIS P 8115:2001 is 10 or more. [8] The 3-methyl-1-butene copolymer according to any one of [2] to [7], wherein the α-olefin having 12 or more carbon atoms is at least one selected from the group consisting of 1-hexadecene and 1-octadecene. [9] The 3-methyl-1-butene copolymer according to any one of [1] to [8], wherein the tensile elongation at break X (%) and tensile yield stress Y (MPa), measured in accordance with JIS K 7161-1:2014, satisfy the following formula (2): Y ≤ (-X / 16) + 42.5 …(2)

[0012] Examples of the configuration of a second aspect of the present disclosure are as described in

[10] to

[15] below.

[10] 3-methyl-1-butene polymer particles having a particle size Dv50 of 50% of the cumulative volume of less than 30 μm.

[11] 3-methyl-1-butene polymer particles according to

[10] , wherein the melting point Tm measured by differential scanning calorimetry is greater than 290°C.

[12] 3-methyl-1-butene polymer particles according to

[10] or

[11] , wherein the 3-methyl-1-butene polymer constituting the 3-methyl-1-butene polymer particles is a 3-methyl-1-butene homopolymer.

[0013]

[13] A method for producing 3-methyl-1-butene polymer particles according to any one of

[10] to

[12] , comprising the steps of: synthesizing a solid transition metal catalyst component (C) by contacting a magnesium compound (A) with a transition metal compound (B); synthesizing a solid olefin polymerization catalyst (E) by contacting the solid transition metal catalyst component (C) with an organoaluminum compound (D); and polymerizing 3-methyl-1-butene in the presence of the solid olefin polymerization catalyst (E).

[14] The method for producing 3-methyl-1-butene polymer particles according to

[13] , wherein the particle size Dv'50 at 50% of the cumulative volume of the solid transition metal catalyst component (C) is less than 2.5 μm.

[15] The method for producing 3-methyl-1-butene polymer particles according to

[13] or

[14] , wherein the amount of polymer produced per 1 g of the solid transition metal catalyst component (C) is 2,000 g or less.

[0014] The 3-methyl-1-butene copolymer according to the first aspect of this disclosure exhibits excellent heat resistance, as well as excellent toughness such as fold resistance and dielectric properties. The 3-methyl-1-butene polymer particles according to the second aspect of this disclosure have an even smaller particle size than conventional small-particle 3-methyl-1-butene polymer particles.

[0015] The following describes in detail matters related to the embodiments. In this specification, numerical ranges indicated using "~" include the numbers indicated before and after "~" as the lower and upper limits, respectively.

[0016] The following describes in detail a 3-methyl-1-butene copolymer (hereinafter also referred to as "the copolymer") according to one embodiment of the First Disclosure. Note that the embodiments of the Disclosure are merely examples, and the Disclosure is not limited to these embodiments. Furthermore, various modifications or improvements can be made to the embodiments of the Disclosure, and such modified or improved forms may also be included in the Disclosure.

[0017] ≪3-Methyl-1-Butene Copolymer≫ This copolymer contains constituent units derived from 3-methyl-1-butene and constituent units derived from α-olefins (excluding 3-methyl-1-butene), has at least one melting point Tm (°C) measured by differential scanning calorimetry (DSC), and satisfies the following formula (1). Tm １ ≧-1.8α+300...(1) (In formula (1), Tm １ α represents the melting point when there is one melting point Tm (°C), or the lowest melting point (°C) among multiple melting points when there are two or more melting points Tm (°C), and α represents the content percentage (mol%) of the constituent units derived from the α-olefin calculated from the FT-IR calibration curve (hereinafter also referred to as "comonomer content").

[0018] Generally, in copolymers, the melting point decreases in proportion to the comonomer content, but the degree of this decrease is thought to be greater when the comonomer composition distribution is narrow and smaller when it is wide. １ The fact that the melting point is greater than or equal to the right-hand side of formula (1) means that it has a relatively broad comonomer composition distribution. Copolymers satisfying formula (1) maintain heat resistance without a drastic decrease in melting point, and because they have a relatively broad comonomer composition distribution, their crystallinity is reduced and their processability is excellent.

[0019] Examples of α-olefins constituting this copolymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexene, vinylnorbornane, and the like. The α-olefin is preferably an α-olefin having 12 or more carbon atoms, more preferably an α-olefin having 12 to 20 carbon atoms, with 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene being preferred. The α-olefin may be linear or branched.

[0020] The α-olefin may be a single type or two or more types. From the viewpoint of the heat resistance and toughness of the resulting copolymer, it is preferable to include at least one selected from the group consisting of 1-hexadecene and 1-octadecene, preferably both 1-hexadecene and 1-octadecene, and even more preferably both 1-hexadecene and 1-octadecene. The more carbon atoms an α-olefin has, the less likely it is to be incorporated into the crystal structure, so the resulting copolymer tends to be amorphous, and its toughness can be increased. As a result, it is believed that flexibility, impact resistance, and bending resistance are imparted.

[0021] The content of structural units derived from 3-methyl-1-butene in this copolymer is preferably 60 to 99.5 mol%, more preferably 70 to 99 mol%, even more preferably 80 to 98.5% by mass, particularly preferably 90 to 98 mol%, and most preferably 93 to 97 mol%. The content of structural units derived from α-olefin is preferably 0.5 to 40 mol%, more preferably 1 to 30 mol%, even more preferably 1.5 to 20 mol%, particularly preferably 2 to 10 mol%, and most preferably 3 to 7 mol%. However, the sum of the content of structural units derived from 3-methyl-1-butene and the content of structural units derived from α-olefin is set to 100 mol%.

[0022] When the α-olefin contains both 1-hexadecene and 1-octadecene, the mass fraction of 1-hexadecene and 1-octadecene (1-hexadecene:1-octadecene) is not particularly limited, but is preferably 70:30 to 40:60, more preferably 65:35 to 50:50, and even more preferably 60:40 to 54:46.

[0023] The copolymer may contain other monomer-derived units, other than those derived from 3-methyl-1-butene and α-olefins (excluding 3-methyl-1-butene), to the extent that the effects of the present disclosure are not impaired. Examples of other monomers include aromatic vinyl compounds, conjugated dienes, functionalized vinyl compounds, and unconjugated polyenes.

[0024] This copolymer has at least one melting point Tm (°C) measured by differential scanning calorimetry (DSC). The method for measuring the melting point Tm (°C) of this copolymer is as follows. Weigh about 5.0 mg of the powdery sample, pack it into a measurement aluminum pan, heat it from 30 °C to 330 °C at a heating rate of 10 °C / min, hold it at 330 °C for 5 minutes, then cool it to 0 °C at a cooling rate of 10 °C / min, hold it at 0 °C for 5 minutes, and then heat it again from 0 °C to 330 °C at a heating rate of 10 °C / min, and complete the measurement by the cooling operation. The melting peak that appears during the second heating is taken as the melting point Tm (°C). That is, when the melting peak that appears during the second heating is single, the copolymer has one melting point Tm (°C), and when the melting peaks that appear during the second heating are plural, it means that the copolymer has two or more melting points Tm (°C).

[0025] In the present disclosure, when the copolymer has two or more melting points Tm (°C), from the lowest melting point (°C) among the plural melting points to Tm １ , Tm ２ , ···, Tm ｎ (n is an integer of 2 or more). Also, Tm １ in the present disclosure also means the melting point Tm when the copolymer has one melting point Tm (°C).

[0026] The Tm １ (°C) of this copolymer is preferably 250 °C or higher, more preferably 270 °C or higher, and even more preferably 280 °C or higher. If Tm １ (°C) is at or above the above lower limit value, it can be said that it is a copolymer with excellent heat resistance. The upper limit value of Tm １ (°C) is not particularly limited, but is preferably 320 °C.

[0027] In one aspect of this copolymer, at least one of Tm (°C) is preferably 250 to 320 °C, more preferably 270 to 315 °C, even more preferably 280 to 310 °C, and particularly preferably 290 to 307 °C. That is, when the copolymer has one melting point Tm (°C), it is preferable that the melting point is within the above range. Also, when the copolymer has two or more melting points Tm (°C), the plural melting points Tm １ , Tm ２, ..., Tm ｎ It is preferable that at least one of the (°C) temperatures falls within the aforementioned range, and it is particularly preferable that all melting points fall within the aforementioned range. The melting point of the copolymer can be adjusted by the comonomer species and comonomer content, and copolymers in which at least one melting point falls within the aforementioned range tend to exhibit not only excellent heat resistance but also excellent flexibility and toughness.

[0028] The ratio of the storage modulus E'(23°C) of this copolymer to the storage modulus E'(260°C) at 260°C (E'(23°C) / E'(260°C)) is preferably 1000 or less, more preferably 900 or less, even more preferably 700 or less, particularly preferably 500 or less, and most preferably 200 or less. The lower limit of E'(23°C) / E'(260°C) is not particularly limited, but for example, it is 1. E'(23°C) / E'(260°C) is preferably between 1 and 1000. The fact that E'(23°C) / E'(260°C) is within the above range means that the copolymer exhibits excellent solid viscoelasticity even under high temperature (260°C) conditions (little change from the 23°C state), and can maintain its elasticity under high temperature conditions. In other words, it means that the copolymer has excellent heat resistance.

[0029] The storage modulus E' (at 23°C) is not particularly limited, but is 1.0 × 10⁻⁶. ９ ~2.5 x 10 ９ Pa is preferred. The storage modulus E' (260°C) is not particularly limited, but is 3.0 × 10⁻⁶. ６ ~4.0 x 10 ７ Pa is preferred. The storage modulus E' (23°C) and the storage modulus E' (260°C) can be measured by the method described in the examples below.

[0030] The melt flow rate (MFR) of this copolymer, measured under conditions of 310°C and a 2.16 kg load in accordance with JIS K 7210, is preferably 0.1 to 25 g / 10 min, more preferably 0.2 to 20 g / 10 min, and even more preferably 0.4 to 10 g / 10 min.

[0031] The number of folds in the flexural strength test of this copolymer, measured in accordance with JIS P 8115:2001, is preferably 10 times or more, more preferably 100 times or more, and even more preferably 500 times or more. The higher the number of folds, the better the toughness of the copolymer.

[0032] Preferably, the copolymer satisfies the following equation (2) when the tensile elongation at break X (%) and tensile yield strength Y (MPa), measured in accordance with JIS K 7161-1:2014: Y ≤ (-X / 16) + 42.5 …(2) By satisfying the above equation (2), the copolymer tends to have excellent flexibility and toughness. The above equation (2) is derived from the balance between toughness and strength of the molded article obtained from the copolymer. Specifically, using the numerical values ​​of the tensile elongation at break and tensile yield elongation of the molded article obtained from the copolymer, the horizontal axis is set to tensile elongation at break and the vertical axis to tensile yield strength, and the straight line and its slope are determined from the plots that are excellent in both tensile elongation at break and tensile yield elongation, and this is equation (2).

[0033] The lower limit of the tensile elongation X of this copolymer is preferably 5 to 200%, more preferably 10 to 100%, and even more preferably 15 to 50% or more. The tensile elongation X can be adjusted by the amount, time, and timing of the addition of hydrogen and comonomers in the polymerization reaction, as well as the addition method.

[0034] The tensile yield strength Y of this copolymer is preferably 10 to 35 MPa, more preferably 15 to 30 MPa. The yield strength Y can be adjusted by the amount, time, and timing of hydrogen and comonomer addition in the polymerization reaction, as well as the addition method. The tensile elongation at break X and the tensile yield strength Y can be specifically measured by the method described in the examples.

[0035] The monomers used as raw materials for this copolymer (3-methyl-1-butene, α-olefin (excluding 3-methyl-1-butene), etc.) may be derived solely from biomass, solely from fossil fuels, or both.

[0036] Biomass-derived raw materials are raw materials made from any (renewable) natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, which are of plant or animal origin, for example, as carbon. １４ 1 × 10¹¹ C isotopes －１２ ~1 x 10 －１４ Examples of raw materials include those containing a certain proportion and having a biomass carbon concentration (unit: pMC) of approximately 100 pMC, as measured in accordance with ASTM D6866. Biomass-derived raw materials (e.g., monomers such as ethylene and α-olefins) can be obtained, for example, by conventionally known methods.

[0037] This copolymer, if the manufacturing conditions such as polymerization catalyst, polymerization process, and polymerization temperature are equivalent, can be a copolymer containing biomass-derived raw materials. １４ 1 × 10¹¹ C isotopes －１２ ~1 x 10 －１４ Aside from the proportion of biomass-derived materials present, the molecular structure is equivalent to that of copolymers made from fossil fuel-derived raw materials. Therefore, it is considered that copolymers containing biomass-derived raw materials and copolymers made from fossil fuel-derived raw materials have no difference in performance.

[0038] <Method for producing this copolymer> This copolymer is not particularly limited and can be produced by known polymerization methods, for example, using catalysts described in Japanese Patent Publication No. 56-811, Japanese Patent Publication No. 61-103910, Japanese Patent Publication No. 3-72548, Japanese Patent Publication No. 3-163110, Japanese Patent Publication No. 9-48813, Japanese Patent Publication No. 11-35622, and Japanese Patent Publication No. 2003-105022.

[0039] Of these manufacturing methods, it is preferable to manufacture the product by polymerization using a catalyst containing a compound having a transition metal atom of Group IV of the periodic table. It is more preferable to carry out the process in the presence of known catalysts such as metallocene catalysts and Ziegler-Natta catalysts.

[0040] Examples of catalysts containing compounds having Group IV transition metal atoms of the periodic table include the solid titanium trichloride catalyst described in Japanese Patent Publication No. 54-107989, etc., and the catalyst described in Japanese Patent Publication No. 56-811, Japanese Patent Publication No. 57-63310, Japanese Patent Publication No. 58-83006, Japanese Patent Publication No. 3-706, Japanese Patent No. 3476793, Japanese Patent Publication No. 4-218508, Japanese Patent Publication No. 2003-105022, etc. Gnesium-supported titanium catalysts; metallocene catalysts described in International Publication No. 2014 / 050817, International Publication No. 01 / 53369, International Publication No. 01 / 27124, Japanese Patent Publication No. 3-193796, or Japanese Patent Publication No. 2-41303, etc.; carrier-supported metallocene catalysts described in Japanese Patent Publication No. 2009-144148, or Japanese Patent Publication No. 2022-37931; so-called post-metallocene catalysts having titanium atoms or hafnium atoms described in "Polyoleffins Journal, Vol. 4, No. 1, pp. 123-136 (2017)", "Macromolecules, Vol. 40, pp. 4130-4137 (2007)", etc. are preferably used.

[0041] The catalysts mentioned above may be manufactured by referring to the above-mentioned publicly available documents, or they may be commercially available products. Examples of commercially available solid titanium trichloride catalysts include "Solvay Catalyst CATA-1" manufactured by Tosoh Finechem Co., Ltd. Examples of commercially available magnesium-supported titanium catalysts include "THC Series" manufactured by Toho Titanium Co., Ltd. and "PolyMax Series" manufactured by Clariant. Examples of commercially available metallocene catalysts include "rac-Dimethylsilylbis(1-indenyl)zirconiamdiclorid" manufactured by Ström.

[0042] In the production of this copolymer, it is preferable to use a co-catalyst. The co-catalyst is preferably an organometallic compound catalyst component, specifically an organoaluminum compound or its hydrated polymer.

[0043] The copolymer can be produced using liquid-phase polymerization methods such as solution polymerization, suspension polymerization (slurry polymerization), and bulk polymerization, as well as gas-phase polymerization and other known polymerization methods, with suspension polymerization being preferred.

[0044] In the method for producing this copolymer, when carried out by liquid-phase polymerization, no solvent may be used, or an inert hydrocarbon may be used as the solvent.

[0045] In the method for producing this copolymer, the polymerization reaction can be carried out using batch, semi-continuous, or continuous methods. Furthermore, the polymerization reaction can be carried out in two or more stages by changing the reaction conditions.

[0046] In the method for producing this copolymer, additives may be added to the polymerization reaction system or after the polymerization reaction as needed, to the extent that the effects of the present disclosure are not impaired. Examples of additives to the polymerization reaction system include hydrogen; silane compounds such as methyl(cyclohexyl)dimethoxysilane and dicyclohexyldimethoxysilane; ester compounds such as ethyl benzoate; ether compounds such as 2,2-alkyl-substituted-1,3-dimethoxypropane; and amine compounds such as 2,2,6,6-tetramethylpiperidine. Additives may be used individually or in combination of two or more.

[0047] Examples of additives after the polymerization reaction include alkyl radical scavengers, antioxidants, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clearing agents, lubricants, fluorescent whitening agents, rust inhibitors, and lubrication agents, from the viewpoint of preventing degradation. Other components may be used individually or in combination of two or more. The content of other components is not particularly limited, but is usually 0 to 50 parts by mass, preferably 0 to 10 parts by mass, per 100 parts by mass of the copolymer.

[0048] The method for producing this copolymer may include a step to remove the catalyst component contained in the 3-methyl-1-butene copolymer after the polymerization reaction.

[0049] In the method for producing this copolymer, it is preferable to include a step of drying the obtained 3-methyl-1-butene copolymer. The drying method is not particularly limited and known methods can be used.

[0050] <Applications of this copolymer> This copolymer is a resin with excellent heat resistance, toughness such as bending resistance, and dielectric properties, and is used in various fields such as medical devices, heat-resistant wires, heat-resistant tableware, and release agents. In particular, molded articles containing this copolymer (e.g., films, sheets, injection molded articles) can be suitably used in high-temperature release films and sheets, heat dissipation films and sheets, molds for manufacturing electronic component encapsulants, LED molds, laminates for high-frequency circuits (substrates for high-frequency circuits), coatings for high-frequency cables, optical waveguide substrates, connectors and cables for high-frequency applications, etc.

[0051] Examples of films and sheets containing this copolymer include the following: Film applications including sheets and tapes include, for example, release films (release films) for flexible printed circuit boards, ACM substrates, rigid substrates, rigid-flexible substrates, advanced composite materials, carbon fiber composite curing, glass fiber composite curing, aramid fiber composite curing, nanocomposite curing, filler curing, semiconductor encapsulation, polarizing plates, diffusion sheets, prism sheets, reflective sheets, cushion films for release films, fuel cell release films, various rubber sheets, urethane curing, epoxy curing; solar cell encapsulation sheets, solar cell back sheets, plastic films for solar cells, battery separators, lithium-ion battery separators, electrolyte membranes for fuel cells, adhesive separators, light guide plates, optical discs, dicing tapes and back glides. Substrates, adhesives, and separators for semiconductor process films such as adhesive tapes, die bonding films, two-layer FCCL, and films for film capacitors; adhesive films; stress relief films; pellicle films; polarizing plate films; protective films for polarizing plates, LCD panels, optical components, lenses, electrical components, and appliances; protective films for mobile phones, personal computers, touch panels, windows, paint coatings, masking films, capacitor films, fuel cell capacitor films, reflective films, diffusion films, laminates (including glass), radiation-resistant films, gamma-ray-resistant films, porous films, and other protective films; heat dissipation films and sheets; molds for manufacturing electronic component encapsulants; LED molds; laminates for high-frequency circuits; sheathing materials for high-frequency cables; optical waveguide substrates; glass fiber composites; carbon fiber composites; glass interlayers; films for laminated glass; window films for building materials; bulletproof materials; films for bulletproof glass; heat shielding sheets; heat shielding films;Examples of release papers include those for synthetic leather, advanced composite materials, carbon fiber composites, glass fiber composites, aramid fiber composites, nanocomposites, and fillers; and heat-resistant and water-resistant photographic paper.

[0052] Furthermore, examples of packaging applications for films and sheets containing this copolymer include food packaging, meat packaging, processed fish packaging, vegetable packaging, fruit packaging, fermented food packaging, confectionery packaging, oxygen absorber packaging, retort food packaging, freshness preservation film, pharmaceutical packaging, cell culture bags, cell inspection film, bulb packaging, seed packaging, film for vegetable and mushroom cultivation, heat-resistant vacuum-formed containers, prepared food containers, prepared food lids, commercial wrap film, household wrap film, and baking cartons.

[0053] Other applications of films and sheets containing this copolymer include, for example, automotive interior and exterior materials such as seat back garnishes, side step mats, trunk linings, seat belt buckles, step mats, seat adjustment knobs, and seat adjuster covers; waterproof sheets; building material sheets; building material window films; ground improvement sheets; health products (e.g., anti-slip mats and sheets, fall prevention films, mats, and sheets); shock-absorbing materials such as shock-absorbing sheets and shock-absorbing films and sheets; gymnastics mats; adhesives such as protective film adhesive layers and hot-melt adhesives; motor support mats, medical films and sheets, cell culture films and sheets, clear sheets, and desk mats.

[0054] Examples of injection-molded articles containing this copolymer include the following: Examples of containers include tableware, condiment containers, retort containers, frozen food storage containers, retort pouches, microwave-safe containers, frozen food containers, frozen dessert cups, cups, baby bottles, beverage bottles and other food containers, retort containers, bottle containers, etc., as well as transfusion sets, medical bottles, medical containers, medical hollow bottles, medical bags, infusion bags, blood storage bags, infusion bottles, medicine containers, detergent containers, fabric softener containers, bleach containers, shampoo containers, conditioner containers, cosmetic containers, perfume containers, toner containers, powder containers, adhesive containers, gasoline tank containers, kerosene containers, etc.

[0055] Other applications of injection molded articles containing this copolymer include, for example, instrument panel surfaces, door trim surfaces, rear package trim surfaces, ceiling surfaces, rear pillar surfaces, seat back garnishes, console boxes, armrests, airbag case lids, shift knobs, assist grips, recliner covers, seat belt buckles, air spoilers, license plate housings, air duct covers, air intake pipes, air dam skirts, bonnet cushions, cup holders, handbrake grips, wire harness grommets, suspension cover boots, glass guides, inner beltline seals, roof guides, trunk lid seals, molded quarter window gaskets, etc. Examples include vent moldings, glass encapsulation, hood seals, secondary seals, bumper parts, body panels, side shields, automotive connectors, ignition coils, switches, lamp reflectors, relays, electrical control unit cases, sensor housings, solenoid valves, coil sealing components, home appliance parts (motor parts, housings, etc.), medical caps, drug stoppers, automotive boot materials, rack and pinion boots, power tool components, agricultural machinery components, internal roller coverings for office automation equipment, heat-resistant packing for office automation equipment, syringes, optical measuring cells, clothing cases, clear cases, PET bottle cap liners, stationery, office supplies, support components for precision instruments and office automation equipment, and scientific and chemical laboratory equipment (beakers, graduated cylinders).

[0056] The following describes in detail 3-methyl-1-butene polymer particles (hereinafter also referred to as "the polymer particles") according to one embodiment of the second disclosure.

[0057] ≪3-Methyl-1-Butene Polymer Particles≫ These polymer particles are characterized by having a particle size Dv50 at 50% of the cumulative volume of less than 30 μm. In this specification, the particle size at 50% of the cumulative volume refers to the particle size at which the cumulative volume is 50%, as measured in accordance with JIS Z 8827-1:2008. Polymer particles with a Dv50 of less than 30 μm can be said to have a sufficiently small particle size, and these polymer particles, which also have excellent heat resistance, are expected to be used in various additives and powder materials.

[0058] The Dv50 of the polymer particles is preferably 25 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, and particularly preferably 10 μm or less. The Dv50 of the polymer particles is not particularly limited, but is preferably 1.0 μm or more. When the Dv50 of the polymer particles is below the above upper limit, particle aggregation can be suppressed. When the polymer particles are used as an additive such as a modifier or crystal nucleating agent, a mixture uniformly mixed with other components can be obtained. When the polymer particles are used in powder coating applications, a coating film with a good appearance can be obtained. When the polymer particles are used in SLS applications for 3D printers, a molded body with a good appearance and desired dimensions can be obtained. The Dv50 of the polymer particles can be specifically measured by the method described in the examples.

[0059] The ratio of the particle size Dv50 at 50% of the cumulative volume of the polymer particles to the particle size Dn50 at 50% of the cumulative number of particles (Dv50 / Dn50) is preferably 2.00 or less, more preferably 1.8 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. The Dv50 / Dn50 of the polymer particles is not particularly limited, but is usually 1.0 or more. When the Dv50 / Dn50 of the polymer particles is within the above range, when used as an additive such as a modifier or crystal nucleating agent, a mixture uniformly dispersed with other components can be obtained. When the polymer particles are used in powder coating applications, a coating film with a good appearance can be obtained. When the polymer particles are used in SLS (Single Laser Sculpture) applications of 3D printers, molded articles with a good appearance and desired dimensions can be easily obtained.

[0060] In this specification, the particle size at 50% cumulative number refers to the particle size at which the cumulative number reaches 50%, as measured in accordance with JIS Z 8827-1:2008. Furthermore, the ratio of the particle size at 50% cumulative volume to the particle size at 50% cumulative number (particle size at 50% cumulative volume / particle size at 50% cumulative number) is an indicator of the particle size distribution, and a larger ratio indicates a wider particle size distribution. Specifically, the Dn50 of these polymer particles can be measured by the method described in the examples.

[0061] The melting point Tm (°C) of the polymer particles, as measured by differential scanning calorimetry (DSC), is preferably greater than 290°C, more preferably 295°C or higher, even more preferably 297°C or higher, and particularly preferably 300°C or higher. The melting point Tm is not particularly limited, but is preferably 350°C or lower. When the melting point Tm of the polymer particles is within the above range, it can be said that the polymer particles have sufficiently excellent heat resistance, and such polymer particles are useful, for example, as dielectric modifiers for high-frequency substrates that have excellent heat resistance (can be used at reflow temperatures). By using these polymer particles, coatings and molded articles (for example, coatings formed by powder coating, or molded articles manufactured by the SLS method of a 3D printer, etc.) can be easily obtained. The melting point Tm of the polymer particles can be adjusted, for example, by the content of constituent units derived from monomers in the 3-methyl-1-butene polymer described later.

[0062] The method for measuring the melting point Tm of this polymer particle is as follows: A powder sample is placed in an aluminum pan for measurement, and the temperature is raised from 30°C to 320°C at a heating rate of 10°C / min under a nitrogen flow rate (100 mL / min). After holding at 330°C for 5 minutes, the temperature is lowered to -70°C at a cooling rate of 10°C / min, and the measurement is completed by holding at -70°C for 5 minutes. The melting peak that appears during the heating is taken as the melting point Tm (°C). If multiple melting peaks appear, the lowest temperature is used as the melting point Tm of this polymer particle.

[0063] The polymer particles are particles containing a 3-methyl-1-butene polymer, and may also be particles composed solely of the 3-methyl-1-butene polymer. The content of the 3-methyl-1-butene polymer in the polymer particles is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and may be 100% by mass.

[0064] <3-Methyl-1-Butene Polymer> The 3-methyl-1-butene polymer constituting the polymer particles may be a 3-methyl-1-butene homopolymer, or a copolymer of 3-methyl-1-butene and an α-olefin having 2 to 20 carbon atoms (excluding 3-methyl-1-butene) (hereinafter also referred to as "3-methyl-1-butene / α-olefin copolymer"). The 3-methyl-1-butene / α-olefin copolymer may be a random copolymer, a block copolymer, or an alternating copolymer. From the viewpoint of readily having a particulate form and exhibiting suitable heat resistance in various applications such as electrical materials, coatings, and molded articles, the 3-methyl-1-butene polymer is preferably a 3-methyl-1-butene homopolymer. The method for producing the polymer is not limited as long as it does not impair the effects of this disclosure, and known polymerization methods can be employed. Specifically, it is preferable to employ the polymerization method described in <Method for Producing the Polymer Particles> below.

[0065] When the 3-methyl-1-butene polymer is a 3-methyl-1-butene / α-olefin copolymer, the content of constituent units derived from 3-methyl-1-butene is preferably 80 mol% or more and less than 100 mol%. The content of constituent units derived from 3-methyl-1-butene is more preferably 85 mol% or more, and even more preferably 90 mol% or more, from the viewpoint of the copolymer easily having a particulate form and exhibiting suitable heat resistance in various applications such as electrical materials, coatings, and molded articles obtained using these polymer particles. The content of constituent units derived from 3-methyl-1-butene is more preferably 99.9 mol% or less, and even more preferably 99.5 mol% or less, from the viewpoint of flexibility and impact resistance of coatings and molded articles obtained using these polymer particles. However, the sum of the content of constituent units derived from 3-methyl-1-butene and the content of constituent units derived from α-olefins having 2 to 20 carbon atoms excluding 3-methyl-1-butene is set to 100 mol%.

[0066] When the 3-methyl-1-butene polymer is a 3-methyl-1-butene / α-olefin copolymer, the content of constituent units derived from α-olefins having 2 to 20 carbon atoms, excluding 3-methyl-1-butene, is preferably greater than 0 mol% and less than or equal to 20 mol%. From the viewpoint of appropriately exhibiting heat resistance in various applications such as electrical materials, coatings, and molded articles obtained using the polymer particles, the content of constituent units derived from α-olefins is more preferably 0.1 mol% or more, and even more preferably 0.5 mol% or more. From the viewpoint of the copolymer easily having a particulate form and the flexibility and impact resistance of coatings and molded articles obtained using the polymer particles, the content of constituent units derived from α-olefins having 2 to 20 carbon atoms, excluding 3-methyl-1-butene, is set to 100 mol%.

[0067] Examples of α-olefins having 2 to 20 carbon atoms, excluding 3-methyl-1-butene, include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, vinylcyclohexene, and vinylnorbornane. The α-olefins may be linear or branched. The α-olefin may be a single type or two or more types. From the viewpoint of exhibiting suitable heat resistance in various applications such as electrical materials, coatings, and molded articles obtained using these polymer particles, the α-olefin having 2 to 20 carbon atoms is preferably an α-olefin having 4 to 18 carbon atoms, and more preferably an α-olefin having 6 to 18 carbon atoms.

[0068] The 3-methyl-1-butene polymer may contain other monomer-derived units, in addition to the constituent units derived from 3-methyl-1-butene and the constituent units derived from α-olefins having 2 to 20 carbon atoms other than 3-methyl-1-butene, to the extent that the effects of the present disclosure are not impaired. Examples of other monomers include aromatic vinyl compounds, conjugated dienes, functionalized vinyl compounds, and unconjugated polyenes.

[0069] The monomers used as raw materials for the 3-methyl-1-butene polymer (3-methyl-1-butene, α-olefins having 2 to 20 carbon atoms other than 3-methyl-1-butene, other monomers, etc.) may be biomass-derived raw materials only, fossil fuel-derived raw materials only, or both biomass-derived and fossil fuel-derived raw materials.

[0070] Biomass-derived raw materials are raw materials made from any (renewable) natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, which are of plant or animal origin, for example, as carbon. １４ 1 × 10¹¹ C isotopes －１２ ~1 x 10－１４ Examples of raw materials include those containing a certain proportion and having a biomass carbon concentration (unit: pMC) of approximately 100 pMC, as measured in accordance with ASTM D6866. Biomass-derived raw materials (e.g., monomers such as ethylene and α-olefins) can be obtained, for example, by conventionally known methods.

[0071] The 3-methyl-1-butene polymer can be a copolymer containing biomass-derived raw materials, provided that the manufacturing conditions such as polymerization catalyst, polymerization process, and polymerization temperature are equivalent. １４ 1 × 10¹¹ C isotopes －１２ ~1 x 10 －１４ Aside from the proportion of biomass-derived materials present, the molecular structure is equivalent to that of polymers made from fossil fuel-derived raw materials. Therefore, it is considered that polymers containing biomass-derived raw materials and polymers made from fossil fuel-derived raw materials have no difference in performance.

[0072] <Method for Producing the Polymer Particles> The polymer particles are not particularly limited and can be produced by known polymerization methods. Specifically, they are preferably produced by a method comprising the following steps (1) to (3). Step (1): A step of synthesizing a solid transition metal catalyst component (C) by contacting a magnesium compound (A) with a transition metal compound (B). Step (2): A step of synthesizing a solid olefin polymerization catalyst (E) by contacting the solid transition metal catalyst component (C) obtained in step (1) with an organoaluminum compound (D). Step (3): A step of polymerizing 3-methyl-1-butene in the presence of the solid olefin polymerization catalyst (E) obtained in step (2).

[0073] [Step (1)] Step (1) is a step of synthesizing a solid transition metal catalyst component (C) by contacting a magnesium compound (A) with a transition metal compound (B).

[0074] Examples of methods for contacting a magnesium compound (A) with a transition metal compound (B) include the following methods (1-1) to (1-4): (1-1) Directly reacting the magnesium compound (A) with the transition metal compound (B). (1-2) Co-grinding and contacting the magnesium compound (A) and the transition metal compound (B) in the presence or absence of an electron donor or grinding aid. (1-3) After contacting the magnesium compound (A) with an electron donor in advance, contacting it with a reaction aid such as an organoaluminum compound or a halogen-containing silicon compound, or reacting it with the transition metal compound (B) without contact. (1-4) Further reacting the product obtained in (1-1) to (1-3) with one or more selected from an electron donor, an organoaluminum compound, and a transition metal compound (B). Of these methods, methods (1-3) and (1-4) are preferred. The compounds obtained by the methods described in (1-1) to (1-4) above are preferably thoroughly washed with hydrocarbons, halogenated hydrocarbons, etc.

[0075] Examples of magnesium compounds (A) include magnesium dihalides such as magnesium oxide, magnesium hydroxide, hydrotalcite, magnesium carboxylates, alkoxymagnesium, alyloxymagnesium, alkoxymagnesium halide, alyloxymagnesium halide, and anhydrous magnesium chloride; organomagnesium compounds; and organomagnesium compounds treated with electron donors, halosilanes, alkoxysilanes, silanols, or aluminum compounds.

[0076] As the transition metal compound (B), titanium compounds or vanadium compounds are preferred, and titanium compounds are more preferred. Examples of titanium compounds include TiCl4, TiBr4, TiI4, Ti(OCH3)Cl3, Ti(OC2H5)Cl3, Ti(OC6H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC3H7)2Cl2, Ti(OC2H5)3Cl, Ti(OC6H5)3Cl, Ti(OC2H5)4, Ti(OC3H7)4, Ti(OC4H9)4, Ti(OC6H 13 ) 4, Ti(OC6H 11 ) 4, Ti (OC8H17 )4, Ti[OCH2(C2H5)CHC4H9]4, Ti(OC9H 19 )4, Ti[OC6H3(CH3)2]4, Ti(OCH3)2(OC4H9)2, Ti(OC3H7)3(OC4H9), Ti(OC2H5)2(OC4H9)2, Ti(OC2H4Cl)4 and Ti(OR) such as Ti(OC2H4OCH3)4 n X 4-n Examples of titanium compounds are those represented as (where R is a hydrocarbon group, X is a halogen atom, and 0 ≤ n ≤ 4).

[0077] The titanium compound may be low-valence, and the crystal system is not limited. Specific examples of low-valence titanium compounds include TiCl3·T-type (obtained by reduction of titanium tetrachloride with titanium metal), TiCl3·A-type (obtained by reduction with aluminum metal), TiCl3·H-type (obtained by reduction with hydrogen), (C2H5)3Al, (C2H5)2AlCl, and (C2H5). 1.5 AlCl 1.5 Examples include titanium trihalides such as TiCl3 reduced with organoaluminum compounds, alkoxytitanium(III) compounds such as Ti(OCH3)3, Ti(OC2H5)3, Ti(OnC4H9)3, Ti(OCH3)Cl2・2CH3OH, and Ti(OCH3)2Cl・CH3OH, and TiCl2 obtained by hydrogen reduction of TiCl3. Transition metal compounds that are solid at room temperature, such as titanium trichloride (TiCl3) and titanium dichloride (TiCl2), may be used after liquefaction treatment.

[0078] The amount of transition metal compound (B) added should be such that the solid transition metal catalyst component (C) has the magnesium atom / transition metal atom (atomic ratio) described later, for example, 10 to 500 g, preferably 30 to 300 g, and more preferably 50 to 200 g per 1 g of magnesium compound (A).

[0079] Examples of electron donors used in the preparation of the solid transition metal catalyst component (C) include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, and esters, ethers, acid amides, acid anhydrides, and alkoxysilanes of organic or inorganic acids such as carboxylic acids; and nitrogen-containing electron donors such as ammonia, amines, nitriles, and isocyanates.

[0080] Specifically, as oxygen-containing electron donors and nitrogen-containing electron donors, C1-C18 alcohols such as methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, and isopropylbenzyl alcohol; alkyl groups such as phenol, cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol, and naphthol. Phenols having 6 to 25 carbon atoms that may be used; ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, and naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate ethyl dichloroethyl, methyl methacrylate, ethyl crotate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate Organic acid esters with 2 to 30 carbon atoms, such as ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, monobutyl phthalate, dibutyl nadicate, γ-butyrolactone, δ-valerolactone, coumarin, phthalides, and ethylene carbonate; alkoxysilanes such as ethyl silicate, butyl silicate, and vinyltriethoxysilane; acid halides with 2 to 15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluyl chloride, anisate chloride, and dichloride phthalate;Examples include ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amino ether, tetrahydrofuran, anisole, and diphenyl ether; acid amides such as acetic acid amide, benzoic acid amide, and toluyl acid amide; acid anhydrides such as benzoic anhydride and phthalic anhydride; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, trynzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, and 2,2,6,6-tetramethylpiperidine; and nitriles such as acetonitrile, benzonitrile, and tolunitrile. These electron donors may be used individually or in combination of two or more.

[0081] For the preparation of the solid transition metal catalyst component (C), the organoaluminum compound (D) described later can be used. Examples of halogen-containing silicon compounds used for the preparation of the solid transition metal catalyst component (C) include silicon tetrahalides, silicon alkoxyhalides, silicon alkylhalides, and halopolysiloxanes.

[0082] The solid transition metal catalyst component (C) produced by the above method contains magnesium atoms, transition metal atoms, and halogen atoms. Examples of the transition metal atoms include group 4 transition metal atoms of the periodic table, specifically titanium atoms, vanadium atoms, chromium atoms, and zirconium atoms, with titanium atoms being preferred. The magnesium atom / transition metal atom (atomic ratio) of the solid transition metal catalyst component (C) is usually 2 to 100, more preferably 4 to 70.

[0083] Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with chlorine atoms being preferred. The halogen atom / transition metal atom (atomic ratio) of the solid transition metal catalyst component (C) is usually 4 to 100, and particularly preferably 6 to 40.

[0084] In step (1), if necessary, an organic medium may be used to improve contact efficiency. Examples of organic mediums include inert hydrocarbons, preferably saturated aliphatic hydrocarbons.

[0085] The solid transition metal catalyst component (C) may contain atoms of other elements (including metal atoms), functional groups, and electron donors, in addition to magnesium atoms, transition metal atoms, and halogen atoms, to the extent that it does not impair the effects of the present disclosure. The specific surface area of ​​the solid transition metal catalyst component (C) is typically 3 m². ２ / g or more, preferably 40m ２ / g or more, more preferably 100 to 800 m ２ It is / g.

[0086] From the viewpoint of easily obtaining polymer particles having a particle size Dv50 at 50% of the cumulative volume within the aforementioned range, the particle size (Dv'50) at 50% of the cumulative volume of the solid transition metal catalyst component (C) is preferably less than 2.5 μm, more preferably 2.0 μm or less, even more preferably 1.5 μm or less, and particularly preferably 1.0 μm or less. Dv'50 is not particularly limited, but is preferably 0.1 μm or more. Dv'50 can be measured in the same way as Dv50 of the polymer particles.

[0087] From the viewpoint of easily obtaining polymer particles having the ratio (Dv50 / Dn50) of particle size Dv50 at 50% of the cumulative volume within the aforementioned range to particle size Dn50 at 50% of the cumulative number, the ratio (Dv'50 / Dn'50) of particle size Dv'50 at 50% of the cumulative volume of the solid transition metal catalyst component (C) to particle size Dn'50 at 50% of the cumulative number is preferably 2.00 or less, more preferably 1.8 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. Dv'50 / Dn'50 is not particularly limited, but is usually 1.0 or more. Dn'50 can be measured in the same way as Dn50 of the polymer particles.

[0088] The particle size of the solid transition metal catalyst component (C) can be adjusted, for example, by controlling the precipitation conditions when a solid product is precipitated by contacting a liquid magnesium compound with a liquid titanium compound, according to the method for producing a solid titanium catalyst component disclosed in Japanese Patent Publication No. 56-811. Specifically, the solid titanium catalyst component is produced by mixing a hydrocarbon solution containing dissolved magnesium chloride and higher alcohols with titanium tetrachloride at a low temperature, then raising the temperature to about 50 to 100°C and precipitating the solid product under strong stirring conditions. The particle size of the solid transition metal catalyst component (C) can be controlled by adjusting these stirring conditions.

[0089] [Step (2)] Step (2) is a step in which a solid olefin polymerization catalyst (E) is synthesized by contacting the solid transition metal catalyst component (C) obtained in step (1) with an organoaluminum compound (D).

[0090] The organoaluminum compound (D) can be any compound having at least one aluminum-carbon bond in its molecule. Examples include organoaluminum compounds represented by the following general formulas (i) or (ii). 1 m Al(OR) 2 ) n H p X q …(i) (R 1 and R 2 (These are hydrocarbon groups such as alkyl groups, alkenyl groups, and aryl groups, usually having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different from each other. X is a halogen atom. m is the number of 0 < m ≤ 3, n is the number of 0 ≤ n < 3, p is the number of 0 ≤ p < 3, and q is the number of 0 ≤ q < 3, where m + n + p + q = 3.) 1 AlR 1 4 … (ii) (M 1 is Li, Na, or K, and R 1 (This is equivalent to the same sign in formula (i) above.)

[0091] The organoaluminum compound represented by formula (i) is R 1 m Al(OR) 2 ) 3-m(R 1 and R 2 The same sign in formula (i) above is equivalent. m is preferably 1.5 ≤ m < 3. ), R 1 m AlX 3-m (R 1 The same sign as in formula (i) above. X is a halogen atom. m is preferably 0 < m < 3. ), R 1 m AlH 3-m (R 1 The same sign in formula (i) above is equivalent. m is preferably 2 ≤ m < 3. ) and R 1 m Al(OR) 2 ) n X q (R 1 and R 2 The symbol is equivalent to the same sign in formula (i) above. X is a halogen atom. 0 < m ≤ 3, 0 ≤ n < 3, 0 ≤ q < 3, and m + n + q = 3. Examples include compounds represented by ).

[0092] Specific examples of aluminum compounds represented by general formula (i) include trialkylaluminum such as triethylaluminum, tributylaluminum, triisobutylaluminum, and trihexylaluminum; trialkeneylaluminum such as triisoprenylaluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; and compounds with an average composition of R 1 2.5 Al(OR) 2 ) 0.5Partially alkoxylated alkylaluminum represented by, dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride and diethylaluminum bromide, alkylaluminum seside sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride and ethylaluminum sesquibromide, alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide, etc. partially halogenated alkylaluminum, dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride, partially hydrogenated alkylaluminum such as ethylaluminum dihydride and propylaluminum dihydride, and partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxychloride, butylaluminum butoxychloride and ethylaluminum ethoxybromide, etc. are mentioned. Further, as a compound similar to the general formula (i), an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom, etc. are mentioned, and such an organoaluminum compound may be used. As such a compound, for example, (CH ２ H ５ ), ２ AlOAl(CH ２ H ５ ), ２ (CH ４ H ８ ), ２ AlOAl(CH ４ H ９ ), ２ (CH ２ H ５ ), ２ AlN(CH ２ H[[ID=]] ５ (CH ２ H ５ ), ２ etc. are mentioned.

[0093] As the organoaluminum compound represented by the formula (ii), a complex alkylated product of a Group 1 metal and aluminum is mentioned. Specifically, LiAl(C2H5)4 and LiAl(C7H15 Examples include 4. Among these, trialkylaluminum, alkylaluminum halide, and mixtures thereof are preferred.

[0094] The amount of organoaluminum compound (D) added should be such that, per gram of solid transition metal catalyst component (C), 0.1 to 2,000 g, preferably 10 to 1,000 g, of polymer is produced. This is typically 0.1 to 1,000 moles, preferably 0.5 to 500 moles, and more preferably 1 to 200 moles, per mole of transition metal atoms in the solid transition metal catalyst component (C).

[0095] In step (2), if necessary, an organic medium may be used to improve contact efficiency. Examples of organic mediums include inert hydrocarbons, preferably saturated aliphatic hydrocarbons.

[0096] [Step (3)] Step (3) is a step of polymerizing 3-methyl-1-butene in the presence of the olefin polymerization catalyst (E) obtained in step (2). This step may be carried out after step (2), or it may be carried out simultaneously with step (2) in the same reaction vessel.

[0097] Polymerization can be carried out using liquid-phase polymerization methods such as solution polymerization, suspension polymerization (slurry polymerization), and bulk polymerization, as well as gas-phase polymerization and other known polymerization methods, with suspension polymerization being preferred. Using suspension polymerization allows for the stable production of this polymer with good catalytic efficiency. The polymerization reaction can be carried out using batch, semi-continuous, or continuous methods. Furthermore, the polymerization reaction can be carried out in two or more stages by changing the reaction conditions.

[0098] When polymerization is carried out by liquid-phase polymerization, the polymerization solvent may not be used, and the olefin itself may be used as the polymerization medium, or an inert hydrocarbon may be used as the polymerization solvent. As the inert hydrocarbon, saturated aliphatic hydrocarbons are preferred.

[0099] The polymerization temperature is typically 10 to 200°C, preferably 30 to 120°C. If the polymerization temperature is within this range, the polymerization reaction can be accelerated while maintaining good catalytic activity, resulting in good productivity. The polymerization pressure is typically atmospheric pressure to 5 MPaG (gauge pressure), preferably 0.05 to 4 MPaG. If the polymerization pressure is within this range, high-pressure reactors and exhaust pumps are unnecessary, which is economically advantageous. The polymerization time is typically 0.1 to 10 hours, preferably 0.5 to 7 hours. If the polymerization time is within this range, the deterioration of polymer properties due to thermal degradation is suppressed, making it easier to produce polymer particles with good properties.

[0100] The polymerization reaction may be stopped by removing the monomers by distillation or filtration, or by adding any polymerization inhibitor as needed. Preferred polymerization inhibitors are compounds that react with a catalyst containing a Group IV transition metal atom of the periodic table. Examples of polymerization inhibitors include water, alcohols, primary amines, secondary amines, thiols, compounds having active protons such as prestethic acid, ethers, phosphines, tertiary amines, thioethers, carbon dioxide, and oxygen molecules. Polymerization inhibitors may be used individually or in combination of two or more.

[0101] In the method for producing these polymer particles, additives may be added to the polymerization reaction system or after the polymerization reaction, if necessary. Examples of additives to the polymerization reaction system include hydrogen; silane compounds such as methyl(cyclohexyl)dimethoxysilane and dicyclohexyldimethoxysilane; ester compounds such as ethyl benzoate; ether compounds such as 2,2-alkyl-substituted-1,3-dimethoxypropane; and amine compounds such as 2,2,6,6-tetramethylpiperidine. One additive may be used alone, or two or more may be used in combination.

[0102] Examples of additives after the polymerization reaction include alkyl radical scavengers, antioxidants, antacids, fillers, light stabilizers, antistatic agents, flame retardants, pigments, polymerization inhibitors, heavy metal deactivators, ultraviolet absorbers, nucleating agents, clearing agents, lubricants, fluorescent whitening agents, rust inhibitors, and lubrication agents, from the viewpoint of preventing degradation. Other components may be used individually or in combination of two or more. The content of other components is not particularly limited, but is usually 0 to 50 parts by mass, preferably 0 to 10 parts by mass, per 100 parts by mass of the polymer particles.

[0103] When hydrogen is added to the polymerization reaction system, the addition method can be a single addition, sequential addition, or continuous addition, but continuous addition is preferred from the viewpoint of obtaining polymer particles with a more homogeneous molecular weight. By adding hydrogen, the catalytic activity value is improved and the physical properties of the polymer particles, such as the melt viscosity, can also be adjusted. As the catalytic activity value improves, the particle size of the polymer particles increases, so it is also possible to adjust the particle size of the polymer particles by adding hydrogen. As for the amount of hydrogen to add, from the viewpoint of obtaining 3-methyl-1-butene polymer particles with a predetermined particle size, the total amount per 1 kg of monomer introduced into the polymerization reaction system is preferably 2.4 NL or less, more preferably 2.0 NL or less, and even more preferably 1.8 NL or less.

[0104] The amount of olefin polymerization catalyst (E) used in suspension polymerization is typically 0.01 to 10 mmol, preferably 0.1 to 10 mmol, per liter of polymerization solvent or polymerization medium, when converted to transition metal atoms. Furthermore, organoaluminum compounds (D) may be added during the polymerization reaction. In this case, the Al atom / transition metal atom (atomic ratio) in the polymerization system is typically 0.1 to 1000, and it is preferable to use a ratio such that it is 1 to 200.

[0105] Since these polymer particles are so-called ultrafine particles with a Dv50 of less than 30 μm, fouling due to aggregation may occur during polymerization. In such cases, the occurrence of fouling can be suppressed by increasing the stirring capacity of the polymerization reactor. Depending on the polymerization method, if the peripheral speed of the tip of the stirring blade is preferably 3.0 m / sec or higher, and more preferably 3.5 m / sec or higher, the adhesion of powder to the wall surface of the polymerization reactor can be effectively suppressed.

[0106] To easily obtain polymer particles with a Dv50 of less than 30 μm, it is preferable to control the amount of polymer produced relative to the solid transition metal catalyst component (C). The amount of polymer produced (catalytic activity) per gram of solid transition metal catalyst component (C) is preferably 2,000 g or less, more preferably 1,500 g, even more preferably 1,000 g, and particularly preferably 500 g. The lower limit of the polymer production amount is usually 0.1 g, preferably 10 g, and more preferably 20 g. If the upper limit of the polymer production amount exceeds the above range, the Dv50 of the obtained polymer particles may increase, and the particle size distribution may widen. The amount of polymer produced per gram of solid transition metal catalyst component (C) can be adjusted by controlling the polymerization temperature, polymerization pressure, polymerization time, etc.

[0107] In the method for producing these polymer particles, it is preferable to include a step after the polymerization reaction described above (after step (3)) to remove catalyst components contained in the polymer (for example, unreacted solid transition metal catalyst component (C), organoaluminum compound (D), and solid olefin polymerization catalyst (E)).

[0108] The method for removing the catalyst components is not particularly limited and known methods can be used. For example, one method is to add an alcohol such as isobutanol or 2-propanol to the crude 3-methyl-1-butene polymer obtained by the polymerization reaction described above, stir at a temperature of about 10 to 100°C, and then separate the polymer. Another method is to add an alcohol such as isobutanol or 2-propanol and a mineral acid such as hydrochloric acid or nitric acid to the crude 3-methyl-1-butene polymer obtained by the polymerization reaction described above, stir at a temperature of about 10 to 100°C, and then separate the polymer. The catalyst component removal operation may be carried out immediately after the polymerization reaction using the polymer slurry, or after removing unreacted monomers and reaction solvents from the polymer slurry by distillation or filtration, or after the removal operation of soluble polymer components described later.

[0109] The crude 3-methyl-1-butene polymer obtained by the polymerization reaction described above may contain polymer components soluble in heated polymerization solvents (e.g., inert hydrocarbons) (hereinafter referred to as "soluble components"). Although the details of the soluble components are not clear, possible soluble components include oligomer components of the 3-methyl-1-butene polymer, polymer components with low stereoregularity, and polymer components with a low content of constituent units derived from 3-methyl-1-butene. Therefore, if soluble components are contained in the crude 3-methyl-1-butene polymer, the method for producing the polymer particles may include a step to remove the soluble components, or it may be used as is for various applications without removal.

[0110] The method for removing the above-mentioned soluble components is not particularly limited and any known method may be used. For example, the removal of soluble components can be performed by adding a hydrocarbon solvent such as heptane to the obtained crude 3-methyl-1-butene polymer, stirring at a temperature of about 50 to 100°C, and then filtering the solution. Furthermore, since the soluble components dissolve in unreacted monomers as well as the polymerization solvent, they can also be removed by stirring the polymer slurry obtained from the polymerization reaction at a temperature of about 50 to 100°C and then filtering the solution. These removal operations may be repeated. The removal of soluble components may be performed on the polymer slurry immediately after the polymerization reaction, or after removing unreacted monomers and reaction solvents from the polymer slurry by distillation or filtration.

[0111] In the method for producing these polymer particles, it is preferable to include a step of drying the obtained polymer. The drying method is not particularly limited and known methods can be used. Drying may be carried out, for example, by removing volatile components under conditions of atmospheric pressure to 1 mmHg and 20 to 200°C. During drying, the polymer particles may be left standing, flowed by applying air or an inert gas, or flowed by mechanical means such as a stirring rotary-blade dryer, a rotary dryer, a continuous shelf dryer, or a fluidized bed dryer.

[0112] <Applications of this Polymer Particle> This polymer particle has excellent heat resistance because the 3-methyl-1-butene polymer has a high melting point. For this reason, this polymer particle is used as a resin with excellent heat resistance in various fields where excellent heat resistance is required, such as electrical materials (e.g., high-frequency substrates), medical devices, heat-resistant wires, heat-resistant tableware, and release agents. This polymer particle may be used, for example, as a modifier (e.g., dielectric property modifier) ​​or resin crystal nucleating agent by adding it to other resins or solvents in powder form, or it may be used as a raw material for powder coating or as a laser-sinterable powder. Alternatively, it may be used as a raw material to be molded by known molding methods, such as injection molding, extrusion molding or compression molding, similar to general thermoplastic resins.

[0113] Specific applications include, for example, the following: In the industrial equipment sector, for example, linings (hoppers, silos, bunkers, chutes, etc. for coal, iron ore, cement, salt, grain, etc.); various parts for food, chemical, construction, and general machinery (guide rails, gaskets, packings, chain guides, chain rails, rollers, screws, gears, bearings, levers, pipes, pumps, etc.); various parts for automobiles, robots, sports and leisure (go-kart bumpers, ski linings, ice hockey protectors, snowmobile parts, bowling lanes, etc.); and battery separators such as lead-acid battery separators and wet LIB separators.

[0114] One application of this polymer in powder form, when added to other resins, is grease. This grease can be widely applied to various applications, such as power transmission devices including speed reducers, gears, chains, and motors; runway components and control system components such as anti-lock braking systems (ABS); steering components and drivetrain components such as transmissions; automotive reinforcement parts such as power window motors, power seat motors, and sunroof motors; hinge components for electronic information equipment and mobile phones; and various parts and relative-moving mechanical parts in industries such as food and pharmaceuticals, steel, construction, glass, cement, chemical, rubber, and resin industries including film tenters, environmental and power equipment, paper and printing industries, woodworking, and textile and apparel industries. It can also be applied to bearings such as rolling bearings, thrust bearings, hydrodynamic bearings, resin bearings, and linear motion devices in medical devices (casts, artificial joints, prosthetics, etc.), liners in cables and tubes, rubber and resin modifiers, sintered filters, and films (adhesive tapes).

[0115] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to the following examples. The first aspect of the present disclosure will be described below based on examples.

[0116] <Evaluation Method> <Comonomer Content> (Copolymers 1-10) The content of constituent units derived from α-olefins (comonomers) other than 3-methyl-1-butene in the copolymers obtained in Examples 1-1 to 1-10 was measured by transmission FT-IR measurement using a UV spectrophotometer manufactured by JASCO Corporation under the following conditions: • Measurement range: 5000-400 cm －１ ・Resolution 2cm －１ - Cumulative number of measurements: 16. The α-olefin content index is the CH of α-olefin. ２ Peak height (720 cm) originating from chain-like bending vibrations. －１ ) / CH stretching vibrations of butene copolymers and α-olefins and CH ２ Sum of peak heights originating from bending oscillations (4314 cm) －１ The amount was calculated using the following formula. When creating a calibration curve using the above measurement results, the absolute value of the amount of comonomer in the copolymer was calculated using the following relational formula, since the copolymer obtained in the example is insoluble in the solvent. (Amount of comonomer in copolymer) = (Amount of comonomer charged) - (Amount of comonomer in solvent-eluted components) - (Unreacted amount) The amount of comonomer in solvent-eluted components was measured using a nuclear magnetic resonance spectrometer (Bruker BioSpin AVANCE3 cryo-500) under the following conditions. Solvent: O-dichlorobenzene / benzene-d ６ (Volume ratio: 1 / 4) Mixed solvent / sample concentration: 60 mg / 0.6 mL Measurement temperature: 120°C Observed nuclei are １３ C (125 MHz) • Sequence: Single-pulse proton broadband decoupling • Pulse width: 5.0 μs (45° pulse) • Repetition time: 5.5 seconds • Number of integrations: 128 • Chemical shift reference: Benzene-d ６ The 128 ppm unreacted amount was measured using gas chromatography (Shimadzu Corporation GC-2010Plus) under the following conditions: • Capillary column: DB-1 • Column temperature: 80°C (0 min) → increased temperature at 10°C / min → 300°C (10 min) • Carrier gas: Helium • Inlet temperature: 280°C • Split ratio: 1:200 • Detector: FID, 300°C • Injection volume: 1.0 μL • Gas flow rate (column flow rate): 1.6 mL / min

[0117] (Copolymer 11) The comonomer content of the copolymer obtained in Comparative Example 1-1 was defined as the amount used when the copolymer was produced.

[0118] (Copolymer 12) The content of constituent units derived from 4-methyl-1-pentene and the content of ethylene or α-olefin (excluding 4-methyl-1-pentene) in the copolymer obtained in Comparative Example 2 were determined by the following apparatus and conditions: １３ The results were calculated from measurements taken by 13C-NMR. A JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer was used, with an orthodichlorobenzene / deuterated benzene (80 / 20 vol%) mixed solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120°C, and the observed nuclei were １３ The measurement was performed using C (125 MHz), a single-pulse proton decoupling sequence, a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, and an accumulation count of over 10,000 cycles, with 27.50 ppm as the reference value for chemical shift. １３ The content of constituent units derived from 4-methyl-1-pentene and those derived from ethylene or α-olefins (excluding 4-methyl-1-pentene) was quantified using 13C-NMR spectroscopy.

[0119] ≪Melting Point Tm≫ The melting points of the copolymers obtained in the examples and comparative examples were measured using a differential scanning calorimeter (DSC). Specifically, an exothermic and endothermic curve was obtained using a DSC measuring device manufactured by Hitachi High-Tech Science Co., Ltd., and the temperature at the position of the maximum melting peak during heating was defined as the melting point Tm. The measurement was performed as follows: Approximately 5.0 mg of the powder sample was weighed and placed in an aluminum measuring pan. The temperature was increased from 30°C to 330°C at a heating rate of 10°C / min, held at 330°C for 5 minutes, then cooled to 0°C at a cooling rate of 10°C / min, held at 0°C for 5 minutes, and then the temperature was increased again from 0°C to 330°C at a heating rate of 10°C / min, and the measurement was completed by cooling. The melting peak that appeared during the second heating was defined as the melting point Tm.

[0120] ≪Mel Flow Rate (MFR)≫ The MFR of the copolymers obtained in the examples and comparative examples was measured using an MFR measuring device manufactured by Toyo Seiki Seisakusho Co., Ltd., in accordance with the method compliant with JIS K 7210. Specifically, the test temperature was 310°C and the test load was 2.16 kgf (polymers 1-11) or the test temperature was 260°C and the test load was 5.0 kgf (polymer 12), and N was used inside the measurement furnace to suppress resin degradation. ２ The substitution was performed. Based on the aforementioned standards, the sample cutting time was defined by the MFR value, and the value converted to g / 10 mins was used as the MFR value.

[0121] <Storage Modulus E'> The storage modulus E' of the copolymers obtained in the examples and comparative examples was measured using a solid viscoelasticity measurement with an RSA-G2 manufactured by T.A. Instruments. Heating rate 4°C / min, frequency 1 Hz, N ２ In the measurements taken below from -50 to 350°C, the storage modulus E' (Pa) at room temperature (23°C) and the storage modulus E' (Pa) at 260°C, which is assumed to be the reflow heat resistance (practical heat resistance), were read. The fact that the modulus can be read at 260°C indicates that the copolymer can retain its elasticity even under high-temperature conditions, and a larger value of the modulus indicates superior heat resistance.

[0122] <<Toughness (Number of Folds Endurance)>> The number of folds in the folding strength test of the copolymers obtained from the examples and comparative examples was measured in accordance with JIS P 8115:2001 using a MIT type folding strength tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. The folding strength characteristics were evaluated by determining the number of folds (number of folds endurance) until the test piece broke, under test temperature of 23±2℃, folding angle of 270°, and folding speed of 175 times / min. A film with a length of 150 mm × width of 100 mm × thickness of 0.1 mm was used as the test piece.

[0123] ≪Tensile Properties (Tensile Elongation at Breaking X, Tensile Yield Stress Y, Tensile Modulus)≫ The tensile properties of the copolymers obtained in the examples and comparative examples were measured using an autograph with a dumbbell-shaped test specimen of type 5A according to JIS K 7161-2:2014. Specifically, the test was performed using an AG-X-plus-F manufactured by Shimadzu Corporation under the following conditions: test temperature 23°C, test speed 50 mm / min, grip distance 50 mm, gauge distance 20 mm. The tensile stress at breaking (MPa), tensile modulus (MPa), and tensile elongation at breaking (%) were measured by pulling the specimen to the point of fracture. Five measurements were taken for each value, and the average value was adopted.

[0124] ≪Dielectric Properties≫ The dielectric properties of the copolymers obtained in the examples and comparative examples were measured at 24 GHz using the TE mode in accordance with JIS R 1641:2007, IEC 62810 (2015), etc., with a YHP Synthesized Sweeper 8340B, a Network Analyzer 8510B, a copper cylindrical cavity resonator with an internal mirror finish, and a semi-rigid cable for signal transmission. A 50 mm square x 0.5 mm thick film was used as the test specimen, and measurements were performed at 23°C. Smaller values ​​for both the relative permittivity and dielectric loss tangent indicate better dielectric properties.

[0125] [Synthesis Example 1-1] Synthesis of Solid Titanium Catalyst Component A Solid titanium catalyst component A was synthesized by the same method as described in Example 1 of Japanese Patent Publication No. 56-811.

[0126] [Synthesis Example 1-2] Synthesis of Solid Titanium Catalyst Component B Solid titanium catalyst component B was synthesized by the same method as described in Example 4 of Japanese Patent Application Publication No. 2003-105022.

[0127] [Example 1-1] (Synthesis of Copolymer 1) 425 mL of decane, 160 g of 3-methyl-1-butene, and 5 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 0.6 mmol of the solid titanium catalyst component A obtained above was charged in terms of titanium atoms, and polymerization was started. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was sequentially supplied, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 1. The yield was 116 g. The obtained copolymer 1 was subjected to various evaluations according to the evaluation method described above. The results are shown in Table 1-1.

[0128] (Preparation of samples for dielectric property evaluation) The obtained copolymer was processed using equipment manufactured by Shinto Metal Industries Co., Ltd. After setting the following order between metal plates: aluminum sheet / polyimide film / spacer / polymer 1 / polyimide film / aluminum sheet, the mixture was preheated at 320°C for 3.0 minutes and de-bubbled for 0.5 minutes. The spacer size was 80 mm square x 0.5 mm thick, and the amount of copolymer used was 3.3 g. The polyimide film used was UPILEX manufactured by UBE Co., Ltd. After heating and pressurizing at 320°C and 5 MPa for 2.0 minutes, it was cooled at 20°C and 1.0 MPa for 4 minutes, cut to 50 mm square x 0.5 mm thick, and obtained resin film samples for dielectric property evaluation. The dielectric properties of the obtained samples were evaluated according to the evaluation method described above. The results are shown in Table 1-1.

[0129] (Preparation of samples for evaluating folding resistance) Except for changing the spacer size from 80 mm square x 0.5 mm thick to 150 mm long x 100 mm wide x 0.1 mm thick and changing the amount of copolymer used from 3.3 g to 1.5 g, the same processing method as described above (Preparation of samples for evaluating dielectric properties) was used to obtain resin film samples for evaluating folding resistance. The obtained samples were evaluated for folding resistance according to the evaluation method described above. The results are shown in Table 1-1.

[0130] (Preparation of samples for tensile property evaluation) 100 parts by mass of the obtained copolymer were dry blended with 0.15 parts by mass of a phenolic antioxidant and 0.40 parts by mass of a sulfuric antioxidant, and then melt-kneaded at 50 rpm and 310°C under a nitrogen atmosphere using a kneader (DSM small injection molding machine (manufactured by Leo Lab Co., Ltd.)). 1. After melt-kneading for 1.5 minutes, a sample for tensile property evaluation (a 1BA type dumbbell test piece as described in Annex A of JIS 7161-2) was molded using an injection molding machine attached to the above-mentioned kneader (DSM small injection molding machine (Leo Lab Co., Ltd.)). In the first stage, the material was injected into the mold at an injection pressure of 0.9 MPa, in the second stage at an injection pressure of 1.2 MPa with a mold holding time of 15 seconds and a mold temperature of 80°C, and in the third stage at an injection pressure of 1.2 MPa with a mold holding time of 35 seconds and a mold temperature of 80°C. The tensile properties of the obtained sample were evaluated according to the evaluation method described above. The results are shown in Table 1-1.

[0131] [Example 1-2] (Synthesis of Copolymer 2) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 3.0 mmol of the solid titanium catalyst component B obtained above (in terms of titanium atoms) was charged in, and polymerization was started. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 2. The yield was 125 g. Various samples were prepared from the obtained copolymer 2 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation), (Preparation of samples for folding endurance evaluation), and (Preparation of samples for tensile property evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-1.

[0132] [Examples 1-3] (Synthesis of Copolymer 3) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 3.0 mmol of the solid titanium catalyst component B obtained above (in terms of titanium atoms) was charged in, and polymerization was started. A total of 29 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 3. The yield was 171 g. Various samples were prepared from the obtained copolymer 3 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-1.

[0133] [Examples 1-4] (Synthesis of Copolymer 4) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerization reactor with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 30°C, 3.75 mmol of the solid titanium catalyst component B obtained above (in terms of titanium atoms) was charged in, and polymerization was started. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 4. The yield was 142 g. Various samples were prepared from the obtained copolymer 4 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-1.

[0134] [Examples 1-5] (Synthesis of Copolymer 5) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triisobutylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerization reactor with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 3.75 mmol of the solid titanium catalyst component B obtained above (in terms of titanium atoms) was charged in, and polymerization was started. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 5. The yield was 155 g. Various samples were prepared from the obtained copolymer 5 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-1.

[0135] [Examples 1-6] (Synthesis of Copolymer 6) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 3.75 mmol of the solid titanium catalyst component B obtained above (in terms of titanium atoms) was charged in, and polymerization was started. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 6. The yield was 164 g. Various samples were prepared from the obtained copolymer 6 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation), (Preparation of samples for folding endurance evaluation), and (Preparation of samples for tensile property evaluation), and various evaluations were performed according to the evaluation methods described above. The results are shown in Table 1-1.

[0136] [Examples 1-7] (Synthesis of Copolymer 7) 425 mL of decane, 160 g of 3-methyl-1-butene, and 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 3.75 mmol of solid titanium catalyst component B (in terms of titanium atoms) was charged in order to start polymerization. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 4 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 7. The yield was 171 g. Various samples were prepared from the obtained copolymer 7 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-2.

[0137] [Examples 1-8] (Synthesis of Copolymer 8) 425 mL of decane, 160 g of 3-methyl-1-butene, and 6.6 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 2.0 mmol of solid titanium catalyst component B (in terms of titanium atoms) was charged in order to start polymerization. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 6 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 8. The yield was 165 g. Various samples were prepared from the obtained copolymer 8 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-2.

[0138] [Examples 1-9] (Synthesis of Copolymer 9) 425 mL of decane, 160 g of 3-methyl-1-butene, and 6.6 mmol of a decane solution of triisobutylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerization reactor with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 2.0 mmol of solid titanium catalyst component B (in terms of titanium atoms) was charged in order to start polymerization. A total of 22 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 6 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 9. The yield was 162 g. Various samples were prepared from the obtained copolymer 9 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-2.

[0139] [Examples 1-10] (Synthesis of Copolymer 10) 425 mL of decane, 160 g of 3-methyl-1-butene, and 6.9 mmol of a decane solution of triisobutylaluminum (1.0 mol / L in terms of aluminum atoms) were charged into a SUS polymerization reactor with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 2.1 mmol of solid titanium catalyst component B (in terms of titanium atoms) was charged in order to start polymerization. A total of 28.2 g of a mixture of C16 α-olefin and C18 α-olefin (trade name: Linearene 168, manufactured by Idemitsu Kosan Co., Ltd.) was supplied sequentially, and after 6.5 hours, methanol was charged as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 copolymer 10. The yield was 127 g. Various samples were prepared from the obtained copolymer 10 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation), (Preparation of samples for folding endurance evaluation), and (Preparation of samples for tensile property evaluation), and various evaluations were performed according to the evaluation methods described above. The results are shown in Table 1-2.

[0140] [Comparative Example 1-1] (Synthesis of Copolymer 11) 10 mmol of triethylaluminum decane solution (1.0 mol / L in terms of aluminum atoms), 30 g of 4-methyl-1-pentene, and 260 g of 3-methyl-1-butene were charged into a SUS polymerization reactor with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 0.68 mmol of solid titanium catalyst component B (in terms of titanium atoms) was charged in and polymerization was started. After holding at 40°C for 4 hours, methanol was charged in as a polymerization stopper. After cooling to below 10°C and depressurizing, the polymerization solution containing the 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 copolymer 11. The yield was 96 g. Various samples were prepared from the obtained copolymer 11 using the same methods as in Example 1-1 (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation), and various evaluations were performed according to the evaluation method described above. The results are shown in Table 1-2. In MFR measurement, the copolymer 11 was too fluid to be measured, so measurement was not possible.

[0141] [Comparative Example 1-2] (Synthesis of Copolymer 12) In the method described in Comparative Example 7 of International Publication No. 2006 / 054613, 4-methyl-1-pentene / 1-decene copolymer 12 was obtained by changing the amount of monomer charged so that the content of constituent units derived from 4-methyl-1-pentene and 1-decene in the obtained copolymer was as shown in Table 1-2. Various samples of the obtained copolymer 12 were prepared in the same manner as in Example 1-1, except that the preheating temperature and heating temperature during processing were changed from 320°C to 260°C in (Preparation of samples for dielectric property evaluation) and (Preparation of samples for folding resistance evaluation) of Example 1-1, and various evaluations were performed according to the evaluation method described above. In addition, in the measurement of storage modulus, the copolymer 12 was in a molten state at 260°C, so the modulus at 260°C could not be measured. The results are shown in Table 1-2.

[0142]

[0143]

[0144] A second aspect of this disclosure will be described below based on an example.

[0145] <Evaluation Method> <Melting Point Tm> The melting point of the polymer particles obtained in the examples was measured using a differential scanning calorimeter (DSC). Specifically, an exothermic / endothermic curve was obtained using a DSC measuring device manufactured by Hitachi High-Tech Science Co., Ltd., and the temperature at the position of the maximum melting peak during heating was defined as the melting point Tm. The measurement was performed as follows: The powder sample was packed into an aluminum measuring pan, and the temperature was increased from 30°C to 320°C at a heating rate of 10°C / min under a nitrogen flow rate (100 mL / min), held at 330°C for 5 minutes, and then cooled to -70°C at a cooling rate of 10°C / min, held at -70°C for 5 minutes to complete the measurement. The melting peak that appeared during heating was defined as the melting point Tm (°C).

[0146] <<Particle size at 50% cumulative volume (Dv50, Dv'50), and particle size at 50% cumulative number (Dn50, Dn'50)>> The particle size at 50% cumulative volume and 50% cumulative number of the solid transition metal catalyst component (C) and polymer particles obtained in the examples were measured in accordance with JIS Z 8827-1:2008. Using a scanning electron microscope (TM4000, Hitachi High-Tech Corporation), images were taken at three arbitrary locations in a sample of several grams, and the resulting SEM images were analyzed using image analysis particle size distribution measurement software (MacView, Mountec Co., Ltd.).

[0147] ≪Dielectric Properties≫ The dielectric properties of the copolymers obtained in the examples and comparative examples were measured at 24 GHz using the TE mode in accordance with JIS R 1641:2007, IEC 62810 (2015), etc., with a YHP Synthesized Sweeper 8340B, a Network Analyzer 8510B, a copper cylindrical cavity resonator with an internal mirror finish, and a semi-rigid cable for signal transmission. A 50 mm square x 0.5 mm thick film was used as the test specimen, and measurements were performed at 23°C. Smaller values ​​for both the relative permittivity and dielectric loss tangent indicate better dielectric properties.

[0148] ≪Surface Characteristics (Arithmetic Mean Roughness Ra, Maximum Peak Height Rp)≫ The surface roughness of the polymers obtained in the Examples and Comparative Examples was measured using a shape measuring laser microscope VK-X100 (manufactured by KEYENCE Corporation). The average roughness of the irregularities in the captured image was defined as the arithmetic mean roughness, and the highest peak among the convex parts was defined as the maximum peak height. For both parameters, a lower value indicates a smoother and better surface of the molded product.

[0149] [Example 2-1] (Synthesis of Solid Transition Metal Catalyst Component (C-1)) 4.76 g of anhydrous magnesium chloride, 23.2 mL of 2-ethylhexyl alcohol, and 25 mL of decane were heated at 120°C for 2 hours to form a homogeneous solution as magnesium compound (A), and then 0.9 mL of ethyl benzoate was added. After cooling this homogeneous solution to -20°C, transition metal compound (B) was added dropwise with stirring over 1 hour to 200 mL of titanium tetrachloride. After the dropwise addition was complete, the mixture was heated to 90°C over 1.5 hours, 1.8 mL of ethyl benzoate was added, and the mixture was held at 90°C with stirring for 2 hours, after which the solid component was collected by filtration. Next, this solid component was added again to 200 mL of titanium tetrachloride, heated at 90°C for 2 hours, and then the solid component was collected by filtration. The mixture was thoroughly washed with purified hexane until the free titanium compound was no longer detected in the washings to obtain solid transition metal catalyst component (C-1). The particle size Dv'50 at 50% of the cumulative volume and the particle size Dn'50 at 50% of the cumulative number of particles of the obtained solid transition metal catalyst component (C-1) were measured according to the measurement method described above. The results are shown in Table 2.

[0150] (Synthesis of Polymer Particle 1) 290 g of 3-methyl-1-butene, 10 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) as an organoaluminum compound (D), and 160 N mL of hydrogen were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 1.0 mmol of solid transition metal catalyst component (C-1) in terms of titanium atoms was charged in and polymerization was started. After holding at 40°C for 1 hour, methanol was charged in as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 particle 1. The yield of polymer particle 1 was 265 g, and the amount of polymer produced per 1 g of solid transition metal catalyst component (C-1) (catalytic activity) was 194 g / g-cat. Furthermore, the particle size Dv50 at 50% of the cumulative volume and the particle size Dn50 at 50% of the cumulative number of polymer particles 1 were measured according to the measurement method described above. The results are shown in Table 2.

[0151] [Example 2-2] (Synthesis of Polymer Particles 2) 290 g of 3-methyl-1-butene, 10 mmol of decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) as organoaluminum compound (D), 5 mmol of dicyclohexyldimethoxysilane, and 160 N mL of hydrogen were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 1.0 mmol of solid transition metal catalyst component (C-1) in terms of titanium atoms was charged in and polymerization was started. After holding at 40°C for 4 hours, methanol was charged in as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 particles 2. The yield of polymer particles 2 was 76 g, and the amount of polymer produced per 1 g of solid transition metal catalyst component (C-1) (catalytic activity) was 55.5 g / g-cat. In addition, the particle size Dv50 at 50% of the cumulative volume and the particle size Dn50 at 50% of the cumulative number of polymer particles 2 were measured according to the measurement method described above. The results are shown in Table 2.

[0152] [Example 2-3] (Synthesis of Polymer Particles 3) 290 g of 3-methyl-1-butene, 20 mmol of a decane solution of triethylaluminum (1.0 mol / L in terms of aluminum atoms) as an organoaluminum compound (D), and 10 mmol of dicyclohexyldimethoxysilane were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 2.0 mmol of solid transition metal catalyst component (C-1) in terms of titanium atoms was charged in and polymerization was started. After holding at 40°C for 4 hours, methanol was charged in as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 particles 3. The yield of polymer particles 3 was 85 g, and the amount of polymer produced per 1 g of solid transition metal catalyst component (C-1) (catalytic activity) was 31.1 g / g-cat. In addition, the particle size Dv50 at 50% of the cumulative volume and the particle size Dn50 at 50% of the cumulative number of polymer particles 3 were measured according to the measurement method described above. The results are shown in Table 2.

[0153] [Comparative Examples 2-1 to 2-4] Comparative Examples 2-1 to 2-4 are 3-methyl-1-butene polymer particles (X1) to (X4) described in Examples 1 to 4 of Japanese Patent Application Publication No. 2024-57983 (comparative polymers 1 to 4 in Table 2, respectively). Table 2 shows the Dv50, Dv50 / Dn50 and Tm of comparative polymers 1 to 4, and the Dv'50, Dv'50 / Dn'50 and catalytic activity of the catalyst component used in the polymerization of comparative polymers 1 to 4. Note that the Dv'50, Dv'50 / Dn'50, catalytic activity, Dv50, Dv50 / Dn50 and Tm in Comparative Examples 2-1 to 2-4 are values ​​measured or calculated according to the method described in paragraphs

[0073] to

[0075] of Japanese Patent Application Publication No. 2024-57983.

[0154] [Comparative Example 2-5] (Synthesis of Solid Titanium Catalyst Component B) Solid titanium catalyst component B was synthesized in the same manner as described in Example 4 of Japanese Patent Application Publication No. 2003-105022. (Synthesis of Comparative Polymer 5) 290 g of 3-methyl-1-butene, 10 mmol of a decane solution of triethylaluminum as an organoaluminum compound (1.0 mol / L in terms of aluminum atoms), and 160 N mL of hydrogen were charged into a SUS polymerizer with a 1 L internal volume stirrer purged with nitrogen. After raising the temperature of the autoclave to 40°C, 1.0 mmol of solid transition metal catalyst component B (in terms of titanium atoms) was charged in and polymerization was started. After holding at 40°C for 4 hours, methanol was charged in as a polymerization stopper. After cooling to below 10°C and depressurizing, 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 comparative polymer 5. The yield of comparative polymer 5 was 90 g, and the amount of polymer produced per 1 g of solid transition metal catalyst component B (catalytic activity) was 75 g / g-cat. Furthermore, the particle size Dv50 at 50% of the cumulative volume and the particle size Dn50 at 50% of the cumulative number of particles of the obtained comparative polymer 5 were measured according to the measurement method described above. The results are shown in Table 2.

[0155]

[0156] [Example 3-1] 50% by mass of the obtained polymer particles 2 and 50% by mass of PPS (polyphenylene sulfide) were dry-blended. 0.15 parts by mass of a phenolic antioxidant and 0.40 parts by mass of a sulfuric antioxidant were added to 100 parts by mass of the dry-blended mixture, and the mixture was melt-kneaded for 1.5 minutes at 50 rpm and 300°C under a nitrogen atmosphere using a kneader (DSM small injection molding machine (Leo Lab Co., Ltd.)) to obtain a resin strand.

[0157] (Preparation of samples for surface property evaluation) The obtained resin strands were processed using equipment manufactured by Kansai Roll Co., Ltd. After setting the aluminum sheet / polyimide film / resin strand / polyimide film / aluminum sheet in that order between metal plates, a vacuum was applied at 300°C for 9.0 minutes, followed by preheating for 1.0 minute, and de-bubbling 20 times. The polyimide film used was UPILEX manufactured by UBE Co., Ltd. After that, the sample was heated and pressurized at 300°C and 10 MPa for 2.0 minutes, then cooled at 20°C and 10 MPa for 4 minutes to obtain an evaluation sample in which the resin strands had been formed into a sheet. The dielectric properties of polymer particle 2 were evaluated according to the method described above. In addition, the surface properties of the obtained evaluation sample were evaluated according to the method described above. The results are shown in Table 3.

[0158] [Comparative Example 3-1] The dielectric properties of the polymer particles were evaluated in the same manner as in Example 3-1, except that the obtained comparative polymer particles 5 were used. Evaluation samples were prepared and their surface properties were evaluated. The results are shown in Table 3.

[0159] [Reference Example 3-1] The dielectric properties of PPS were evaluated in the same manner as in Example 3-1, except that 100% by mass of PPS was used. Evaluation samples were prepared and their surface properties were evaluated. The results are shown in Table 3.

[0160]

[0161] Since Example 3-1 used particles with a smaller particle size than Comparative Example 3-1, the surface properties (arithmetic mean roughness Ra and maximum peak height Rp) were better.

Claims

1. A 3-methyl-1-butene copolymer comprising a constituent unit derived from 3-methyl-1-butene and a constituent unit derived from α-olefin (excluding 3-methyl-1-butene), having at least one melting point Tm (°C) measured by differential scanning calorimetry, and satisfying the following formula (1): Tm １ ≧-1.8α+300...(1) (In formula (1), Tm １ (where Tm(°C) is the melting point when there is one melting point Tm(°C), or the lowest melting point (°C) among multiple melting points when there are two or more melting points Tm(°C), and α represents the content percentage (mol%) of the constituent units derived from the α-olefin calculated from the FT-IR calibration curve.) 2. The 3-methyl-1-butene copolymer according to claim 1, wherein the α-olefin is an α-olefin having 12 or more carbon atoms.

3. The 3-methyl-1-butene copolymer according to claim 1, wherein the ratio of the storage modulus E'(23°C) at 23°C to the storage modulus E'(260°C) at 260°C (E'(23°C) / E'(260°C)) is 800 or less.

4. The 3-methyl-1-butene copolymer according to claim 1, wherein the content of the constituent units derived from 3-methyl-1-butene is 60 to 99.5 mol%, and the content of the constituent units derived from α-olefin is 0.5 to 40 mol% (provided that the sum of the content of the constituent units derived from 3-methyl-1-butene and the content of the constituent units derived from α-olefin having 12 or more carbon atoms is 100 mol%).

5. The aforementioned Tm １ The 3-methyl-1-butene copolymer according to claim 1, wherein the temperature (°C) is 250°C or higher.

6. The 3-methyl-1-butene copolymer according to claim 1, wherein at least one of the Tm (°C) is 250 to 320°C.

7. The 3-methyl-1-butene copolymer according to claim 1, wherein the number of folds in the fold strength test in accordance with JIS P 8115:2001 is 10 or more.

8. The 3-methyl-1-butene copolymer according to claim 2, wherein the α-olefin having 12 or more carbon atoms is at least one selected from the group consisting of 1-hexadecene and 1-octadecene.

9. The 3-methyl-1-butene copolymer according to claim 1, wherein the tensile elongation at break X (%) and tensile yield stress Y (MPa), measured in accordance with JIS K 7161-1:2014, satisfy the following formula (2): Y ≤ (-X / 16) + 42.5 …(2) 10. 3-methyl-1-butene polymer particles having a particle size Dv50 of less than 30 μm at a cumulative volume of 50%.

11. 3-methyl-1-butene polymer particles according to claim 10, wherein the melting point Tm measured by differential scanning calorimetry is greater than 290°C.

12. The 3-methyl-1-butene polymer particle according to claim 10, wherein the 3-methyl-1-butene polymer constituting the 3-methyl-1-butene polymer particle is a 3-methyl-1-butene homopolymer.

13. A method for producing 3-methyl-1-butene polymer particles according to any one of claims 10 to 12, comprising the steps of: synthesizing a solid transition metal catalyst component (C) by contacting a magnesium compound (A) with a transition metal compound (B); synthesizing a solid olefin polymerization catalyst (E) by contacting the solid transition metal catalyst component (C) with an organoaluminum compound (D); and polymerizing 3-methyl-1-butene in the presence of the solid olefin polymerization catalyst (E).

14. A method for producing 3-methyl-1-butene polymer particles according to claim 13, wherein the particle size Dv'50 of 50% of the cumulative volume of the solid transition metal catalyst component (C) is less than 2.5 μm.

15. A method for producing 3-methyl-1-butene polymer particles according to claim 13, wherein the amount of polymer produced per 1 g of the solid transition metal catalyst component (C) is 2,000 g or less.

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