Polymer composition, molded article, fiber-reinforced composite material, and fiber product

Abstract

To provide a polymer composition that achieves high solvent stability while retaining the heat resistance of a 4-methyl-1-pentene homopolymer.SOLUTION: A polymer composition comprises a 4-methyl-1-pentene polymer (A) meeting requirements (i) to (iii) and a solvent (B). Requirement (i): the 4-methyl-1-pentene polymer consists only of structural units derived from 4-methyl-1-pentene; Requirement (ii): the meso dyad fraction measured by 13C-NMR is 98.0% or less; Requirement (iii): the melting point measured by differential scanning calorimetry is 200°C or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer composition, a molding, a fiber composite material and a fiber product. [Background technology]

[0002] 4-Methyl-1-pentene polymers and polymer compositions containing the polymers are widely used in various applications because of their excellent heat resistance, releasability, chemical resistance, and the like. As such a 4-methyl-1-pentene polymer, for example, Patent Document 1 discloses a 4-methyl-1-pentene polymer having specific physical properties, and also discloses a polymer composition containing the polymer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 150265 Summary of the Invention [Problem to be solved by the invention]

[0004] Moreover, homopolymers of 4-methyl-1-pentene have particularly high rigidity among 4-methyl-1-pentene polymers and are particularly excellent in heat resistance, and therefore are used in various applications. Thus, although the homopolymer of 4-methyl-1-pentene has high heat resistance, it has low stability when dissolved in a solvent (hereinafter also referred to as "solvent stability"), and in this respect there is room for improvement.

[0005] For example, in order to improve the solvent stability of a polymer composition containing a 4-methyl-1-pentene homopolymer, it is conceivable to replace the homopolymer with a 4-methyl-1-pentene copolymer containing a structural unit derived from a comonomer. However, it has been found that the use of such a copolymer reduces heat resistance and may result in the loss of the properties of the 4-methyl-1-pentene homopolymer.

[0006] The present invention has been made in view of the above, and an object thereof is to provide a polymer composition having high solvent stability while maintaining the heat resistance of a 4-methyl-1-pentene homopolymer.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved according to the following configuration examples, and have completed the present invention. The configuration example of the present invention is as follows.

[0008] [1] A polymer composition comprising a 4-methyl-1-pentene polymer (A) satisfying the following requirements (i) to (iii) and a solvent (B). Requirement (i): Consisting only of structural units derived from 4-methyl-1-pentene Requirement (ii): 13 The meso dyad fraction measured by C-NMR is 98.0% or less Requirement (iii): The melting point measured by a differential scanning calorimeter is 200 ° C or higher

[0009] [2] The polymer composition according to [1], wherein the solvent (B) contains methylcyclohexane.

[0010] [3] The polymer composition according to [1] or [2], wherein the polymer (A) further satisfies the following requirement (iv). Requirement (iv): The intrinsic viscosity [η] measured in decalin at 135 ° C is 0.10 to 0.23 dl / g

[0011] [4] The polymer composition according to any one of [1] to [3], wherein the content of the polymer (A) in the polymer composition is 1.0 to 10.0% by mass.

[0012] [5] For the polymer (A), 13 The meso dyad fraction measured by C-NMR is 96.0% or less, The polymer composition according to any one of [1] to [4], wherein the polymer (A) has a melting point of 205° C. or higher as measured by a differential scanning calorimeter.

[0013] [6] A molded article formed from the polymer composition according to any one of [1] to [5]. [7] The molded article according to [6], which is a film or a container.

[0014] [8] A fiber composite material comprising a layer formed from the polymer composition according to any one of [1] to [5] and a fiber substrate. [9] A textile product comprising the fiber composite material described in [8]. Effect of the Invention

[0015] According to the present invention, it is possible to provide a polymer composition having high solvent stability while maintaining the high heat resistance of a 4-methyl-1-pentene homopolymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] The various compounds that are raw materials for the following polymers and other components may be compounds derived from fossil raw materials or compounds derived from biomass. Also, compounds derived from fossil raw materials and compounds derived from biomass may be used as raw materials for the following polymers and other components. In addition, a numerical range described using "~" means that the numerical values ​​before and after "~" are included as the upper and lower limits, and when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any manner.

[0017] <Polymer composition> The polymer composition according to the present invention (hereinafter also simply referred to as "composition (X)") contains a 4-methyl-1-pentene polymer (A) (hereinafter also simply referred to as "polymer (A)") satisfying the following requirements (i) to (iii), and a solvent. Requirement (i): Consists of only structural units derived from 4-methyl-1-pentene Requirement (ii): 13The meso-dyad fraction measured by C-NMR is 98.0% or less. Requirement (iii): The melting point measured by a differential scanning calorimeter is 200°C or higher.

[0018] The reason why such composition (X) exhibits the above-mentioned effects is not entirely clear, but is believed to be due to the following reasons. When the mesodiad fraction of the polymer (A) is 98.0% or less, even if the structural units constituting the polymer (A) are only structural units derived from 4-methyl-1-pentene, the stereoregularity of the polymer (A) is low, and it becomes difficult for the molecules of the polymer (A) to be regularly aligned. As a result, the polymer (A) is difficult to crystallize, and the distance between the molecules of the polymer (A) becomes long, weakening the intermolecular force, and the solvent stability can be improved while maintaining the high heat resistance of the 4-methyl-1-pentene homopolymer.

[0019] <4-methyl-1-pentene polymer (A)> The polymer (A) is a 4-methyl-1-pentene homopolymer that satisfies the following requirements (ii) to (iii). The polymer (A) used in the composition (X) may be one type or two or more types.

[0020] Requirement (ii): 13 The meso-dyad fraction measured by C-NMR is 98.0% or less. The meso dyad fraction is preferably 97.5% or less, more preferably 97.0% or less, even more preferably 96.5% or less, and particularly preferably 96.0% or less. The lower limit of the meso dyad fraction is not particularly limited, but is, for example, 90.0% or more, preferably 95.0% or more. By using the polymer (A) having a mesodiad fraction within the above range, a composition (X) having high solvent stability can be easily obtained.

[0021] The meso dyad fraction in this specification is specifically measured by the method described in the following Examples. The mesodyad fraction is sometimes called isodyad isotacticity or mesodyad isotacticity. The meso diad fraction can be adjusted, for example, by the type of olefin polymerization catalyst described below.

[0022] Requirement (iii): The melting point (Tm) measured by differential scanning calorimetry (DSC) is 200°C or higher. The melting point is preferably 205° C. or higher, more preferably 210° C. or higher, and even more preferably 215° C. or higher. There is no particular upper limit to the melting point, but it is, for example, 250° C. or lower. By using the polymer (A) having a melting point within the above range, a composition (X) having high heat resistance can be easily obtained. The melting point in this specification is specifically measured by the method described in the Examples below. The melting point can be adjusted, for example, by the type of olefin polymerization catalyst described below.

[0023] The polymer (A) is preferably a 4-methyl-1-pentene homopolymer that satisfies the following requirement (iv). Requirement (iv): The intrinsic viscosity [η] measured in decalin at 135°C is 0.10 to 0.23 dl / g. The intrinsic viscosity [η] is more preferably 0.15 to 0.20 dl / g. By using the polymer (A) having an intrinsic viscosity [η] within the above range, it is possible to easily achieve a balance between the heat resistance and the solvent stability of the composition (X). The intrinsic viscosity [η] in this specification is specifically measured by the method described in the following examples. The intrinsic viscosity [η] can be adjusted, for example, by adjusting the polymerization conditions.

[0024] The content of the polymer (A) in the composition (X) is preferably from 1.0 to 10.0 mass %, more preferably from 2.0 to 8.0 mass %, and further preferably from 3.0 to 7.0 mass %. When the content of the polymer (A) is within the above range, the heat resistance and solvent stability of the composition (X) can be easily balanced.

[0025] <Method of synthesizing polymer (A)> The polymer (A) can be obtained, for example, by polymerizing 4-methyl-1-pentene in the presence of an olefin polymerization catalyst described below. The polymerization can be carried out by any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. The polymerization conditions and the like can be those described in WO 2014 / 050817. Conditions for synthesizing the polymer (A) that satisfies the above requirements (ii) and (iii) include, in particular, adjusting the polymerization temperature to 40 to 150°C and adjusting the amount of hydrogen added in the system to 0.00001 to 100 NL per mole of 4-methyl-1-pentene.

[0026] [Olefin polymerization catalyst] The olefin polymerization catalyst includes A bridged metallocene compound (a), At least one compound (b) selected from an organometallic compound (b-1), an organoaluminum oxy compound (b-2), and a compound (b-3) which reacts with the compound (a) to form an ion pair; A catalyst comprising: The olefin polymerization catalyst preferably further contains a support (c), and may further contain an organic compound component (d) as necessary.

[0027] Bridged metallocene compounds (a) The compound (a) is preferably a compound represented by the following formula [a1]. Specific examples of compound (a) include the compounds described in WO 2014 / 050817, WO 2017 / 150265, and the like.

[0028] [ka]

[0029] In formula [a1], M is a transition metal atom of Group 4 of the periodic table, for example, a titanium atom, a zirconium atom, or a hafnium atom; Q is selected from the group consisting of halogen atoms, hydrocarbon groups, neutral conjugated or non-conjugated dienes having 10 or less carbon atoms, anionic ligands, and neutral ligands capable of coordinating with lone pairs of electrons, in any combination, whether the same or different; j is an integer from 1 to 4; R A and R B are mononuclear or polynuclear hydrocarbon residues which may be the same or different and can form a sandwich structure together with M, Y is a carbon atom or a silicon atom; R C and R D may be the same or different and are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom and a halogen-containing hydrocarbon group, and may be bonded to each other to form a ring.

[0030] A compound (b), a carrier (c) and an organic compound component (d) The carrier (c) may be, for example, an inorganic or organic compound, and may be a granular or fine particle solid. The compound (a) is preferably used in a form supported on the carrier (c). The organic compound component (d) is used as necessary for the purpose of improving the polymerization performance and the physical properties of the resulting polymer (A), etc. Examples of the organic compound component (d) include alcohols, phenolic compounds, carboxylic acids, phosphorus compounds, amides, polyethers, and sulfonates.

[0031] Examples of the compound (b), carrier (c) and organic compound component (d) include the compounds, carriers and organic compound components described in WO 2014 / 050817, JP 2015-183141 A and WO 2014 / 123212. As the carrier (c), carriers described in WO 2010 / 055652, WO 2011 / 142400, WO 2013 / 146337, and JP 2015-74645 A can also be used.

[0032] <Solvent (B)> The solvent (B) contained in the composition (X) is not particularly limited as long as it can dissolve the polymer (A), and is not limited to methylcyclohexane, which is a suitable solvent described later, and a stable composition can be obtained when any of the solvents listed below is used. The solvent (B) may be used alone or in combination of two or more kinds. Examples of the solvent (B) include aliphatic hydrocarbons such as n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc., and aromatic hydrocarbons such as toluene, xylene, etc. Among these, it is preferable to use toluene, cyclohexane, methylcyclohexane, etc. as the solvent (B), and it is more preferable to use methylcyclohexane.

[0033] <Other ingredients> The composition (X) may be a composition consisting of only the polymer (A) and the solvent (B). However, depending on the application, the composition (X) may contain other components, such as polymers other than the polymer (A) and resin additives, within the scope of not impairing the effects of the present invention. These other components may each be used alone or in combination of two or more.

[0034] Examples of the other polymers include thermoplastic resins described in WO 2018 / 179619.

[0035] Examples of the resin additives include (transparent) nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents, weather stabilizers, heat stabilizers, antislip agents, foaming agents, crystallization aids, antifogging agents, antiaging agents, hydrochloric acid absorbers, impact improvers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, and processing aids. Specific examples of these include the resin additives described in International Publication No. 2018 / 179619.

[0036] When other components are used in the composition (X), the total content of the other components is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the polymer (A).

[0037] <Method for preparing composition (X)> The method for preparing the composition (X) is not particularly limited, and the composition can be prepared by a commonly used method. For example, the composition can be prepared by mixing the polymer (A), the solvent (B) and the other components as required, and stirring the mixture at a temperature below the boiling point of the solvent (B) for a predetermined period of time.

[0038] <Molded body> The molded article according to the present invention (hereinafter also referred to as the "present molded article") is formed from the composition (X) and can be obtained, for example, by molding the composition (X) according to the application of the molded article. As the molding method, various known molding methods can be applied and can be appropriately selected depending on the desired application. Examples of the molding method include various molding methods such as injection molding, extrusion molding, injection stretch blow molding, blow molding, cast molding, calendar molding, press molding, stamping molding, inflation molding, and roll molding. During the molding and / or the molded article obtained by the molding method may be stretched.

[0039] For example, when the present molded article is to be made into a film, the present composition is a composition having excellent solvent stability, and therefore the present composition can be suitably subjected to cast molding. Therefore, when the present molded article is to be made into a film, it is preferable to form the film by cast molding in order to more effectively exert the effects of the present invention. As a specific method of the cast molding, the composition (X) is applied to a support, and the solvent (B) in the composition (X) applied to the support is removed to form a film on the support. In this case, a laminate of the support and the film may be used for a desired purpose by selecting a desired adherend (substrate) as the support, or the film may be peeled off from the laminate of the support and the film and used alone for a desired purpose.

[0040] Examples of the adherend (substrate) include metal substrates such as aluminum, nickel, copper, iron, steel, and stainless steel; metal-containing substrates such as semiconductor circuit boards; resin substrates such as polyolefins (e.g., polyethylene, polypropylene), polystyrene, polyamide, polyimide, fluororesins (including polytetrafluoroethylene, polyvinylidene fluoride, and the like), and polycarbonates; inorganic substrates such as metal oxides, carbon materials, and glass; and paper substrates. The shape of the adherend (substrate) is not particularly limited.

[0041] The present molded product has the physical properties of a 4-methyl-1-pentene polymer, and is particularly excellent in heat resistance, and is therefore suitable for use in applications requiring heat resistance, in that the effects of the present invention can be more effectively exhibited. Specific examples of uses for the molded articles include automobile parts, home appliance material parts, electrical and electronic parts, building materials, civil engineering materials, agricultural materials, daily necessities, various films, various containers (including bottles), foams suitable for general industrial and recreational uses, yarns and textiles, medical and sanitary products, and other uses.

[0042] Specific applications of the various films include, for example, protective films for various display devices, semiconductor devices, printed circuit boards, capacitors, etc., gas permeable films, peeling films, release films, optical components (including optical films, optical compensation films, etc.), liquid crystal reflective films, polarizing films, sealing films, liquid crystal display films, EL display films, capacitor films, freshness-preserving films, packaging materials (including bags), tableware films, medical films (including platelet storage bags and cell storage bags), and sheets for culture media. In this specification, there is no particular distinction between films and sheets, and plate-like bodies are generally referred to as films.

[0043] <Fiber composite materials> The fiber composite material according to the present invention (hereinafter also referred to as "the present fiber composite material") includes a layer (hereinafter also referred to as "layer (Z)") formed from the composition (X) and a fiber substrate. The present fiber composite material is preferably a fiber composite material in which at least a part of the fiber substrate is coated with layer (Z). The fiber composite material may include one layer (Z) or may include two or more layers. When the fiber composite material includes multiple layers (Z), these multiple layers may be the same or different.

[0044] The thickness of the layer (Z) may be appropriately selected depending on the application of the fiber composite material, but is preferably 10 μm or less, more preferably 0.001 to 9.5 μm, even more preferably 0.01 to 9.0 μm, still more preferably 0.01 μm or more and less than 4 μm, and particularly preferably 0.1 to 3 μm. When the fibre composite material comprises several layers (Z), the thickness is the thickness of each layer (Z).

[0045] The fiber substrate is a fiber or a substrate containing a fiber. The textile substrate is typically a fabric, including woven, knitted, nonwoven, braided, lace, netting, and the like.

[0046] The fiber base material may be one that has been subjected to known treatments such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, flame retardancy, singeing, calendaring, binder fixing, and adhesive coating.

[0047] The fibers constituting the fiber substrate may be of any type, including synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, and mixed fibers containing two or more of these fibers. Examples of the synthetic fibers include polypropylene fibers, polyethylene fibers, polyvinyl alcohol fibers, polyester (e.g., PET, PBT, PNT) fibers, wholly aromatic polyester fibers, polyamide fibers (e.g., nylon fibers, wholly aromatic polyamide fibers), aromatic heterocyclic polymer fibers (e.g., polybenzimidazole, polybenzoxazole, polybenzothiazole) fibers, acrylic fibers, polyurethane fibers, polyvinyl chloride fibers, fluorine-based fibers, aramid-based fibers, sulfone-based fibers, and mixed fibers thereof. The semi-synthetic fibers include rayon fibers and acetate fibers. Examples of the natural fibers include cotton fibers, wool fibers, feather fibers, silk fibers, and hemp fibers. Examples of the inorganic fibers include glass fibers, silica fibers, alumina fibers, silica alumina fibers, and carbon fibers.

[0048] The basis weight of the fiber base material is preferably 10 to 500 g / m 2 , more preferably 30 to 400 g / m 2 , and more preferably 50 to 300 g / m 2 It is.

[0049] <Method of manufacturing fiber composite material> The fiber composite material is preferably produced by a method including a step of applying the composition (X) to a part or the entire surface of a fiber substrate and removing the solvent (B) to form a layer (Z). The fiber composite material can also be produced by a method including a step of immersing a fiber substrate in the composition (X), removing the fiber substrate from the composition (X), and then removing the solvent (B) to form a layer (Z). The conditions for removing the solvent (B) are not particularly limited, and the heating temperature, heating time, pressure, and the like may be appropriately selected depending on the type of the solvent (B) and the fiber base material.

[0050] <Textile products> The textile product according to the present invention contains the present fiber composite material. The textile product may consist of the present fiber composite material alone, or may contain, in addition to the present fiber composite material, conventionally known components that have been used in textile products.

[0051] Examples of the textile products include ropes, protective nets, fishing nets, fishing lines, insect nets, clothing (e.g., outdoor wear, life jackets, underwear, down, vests, windbreakers, surgical gowns, ski wear, golf wear, swimsuits and other sportswear, socks), masks, release fabrics, oil-absorbing fabrics, waterproof fabrics, supports, bandages, sleeping bag fabrics, tent fabrics, artificial turf, futon fillings, futon side fabrics, futon covers, blankets, blanket side fabrics, blanket covers, sheets, pillow fillings, pillow covers, stuffed animal fillings, paper diapers, sanitary products, sanitary products, sewing threads, filters (including bag filters, dust collection filters, hollow fiber filters, water purification filters, etc.), air cleaners, gas separation membranes, dental floss, brushes (including toothbrushes, etc.), wigs, belts, bags, shoes, shoe insoles, tablecloths, curtains, carpets, (automotive) mats, belt conveyor base fabrics, optical fibers, sound absorbing materials, and heat insulating materials. EXAMPLES

[0052] The present invention will be described in more detail below with reference to examples, although the present invention is not limited to these examples.

[0053] [Production Example 1] Production of 4-methyl-1-pentene polymer 1 At room temperature (25°C) and under a nitrogen stream, 400mL of 4-methyl-1-pentene and 0.23mL (0.40mmol in terms of aluminum atoms) of a hexane solution of modified methylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.) (1.74mmol / mL in terms of aluminum atoms) were charged into a SUS polymerization vessel equipped with a stirrer with an internal volume of 1L, and the temperature was raised to 45°C. Next, 0.21mL of a toluene solution containing 0.0005mmol of ethylene bisindenyl zirconium dichloride that had been prepared in advance was added. Then, 695NmL of hydrogen was charged to start polymerization. The temperature was kept at 45°C for 30 minutes from the start of the hydrogen charging. After 30 minutes had passed from the start of polymerization, the pressure was released, and then methanol was added to stop the polymerization. The reaction solution after the polymerization was stopped was poured into a mixed solution of methanol and acetone in a 1:2 (mass ratio) solution to which hydrochloric acid had been added, and the entire amount of polymer was precipitated, and recovered by filtration. The recovered polymer was then dried under reduced pressure at 80° C. for 8 hours to obtain 4-methyl-1-pentene (homo)polymer 1 (hereinafter also simply referred to as “polymer 1”). The yield was 74 g.

[0054] [Production Example 2] Production of 4-methyl-1-pentene polymer 2 In accordance with the polymerization method described in Example 3B of WO 2014 / 050817, the proportion of hydrogen used was changed so that the physical properties of the resulting polymer 2 would be the values ​​shown in Table 1, thereby obtaining 4-methyl-1-pentene (homo)polymer 2 (hereinafter also simply referred to as "polymer 2").

[0055] [Production Example 3] Production of 4-methyl-1-pentene polymer 3 500 mL of 4-methyl-1-pentene and 220 mL of heptane were charged at 23°C into a 1.5 L stainless steel autoclave equipped with an agitator, which had been thoroughly purged with nitrogen. 30 mL of 1-decene and 0.3 mL of a 1.0 mmol / mL toluene solution of triisobutylaluminum (TIBAL) were then charged into the autoclave, and stirring was started. Next, 140 mL of hydrogen was charged into the autoclave, and the internal temperature of the autoclave was raised to 60°C. Next, 2 mL of a toluene solution containing 0.039 mmol of liquid methylaluminoxane in terms of aluminum atom, which had been prepared in advance, and further containing 0.00013 mmol of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride obtained in Preparation Example 1 below, was pressed into the autoclave with nitrogen to initiate polymerization. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60°C. After 10 minutes had elapsed from the start of polymerization, 5 mL of methanol was pressed into the autoclave with nitrogen to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. The reaction solution after the polymerization was terminated was poured into acetone with stirring, and the polymer was precipitated and collected by filtration. Thereafter, the recovered polymer was dried at 130° C. under reduced pressure for 10 hours to obtain 4-methyl-1-pentene (co)polymer 3 (hereinafter also simply referred to as “polymer 3”).

[0056] [Preparation Example 1] Preparation of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride Based on the method described in Preliminary Experiment 5 of WO 2014 / 123212, (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride was synthesized.

[0057] <Composition> The content of the structural unit (i) and the content of the structural unit (ii) in each of the polymers synthesized in the above Production Examples were measured using the following apparatus and conditions. 13 A C-NMR spectrum was obtained. 13 The chemical shifts were calculated from the C-NMR spectrum. The reference value for the chemical shifts was 27.50 ppm. The results are shown in Table 1. Here, the structural unit (i) is a structural unit derived from 4-methyl-1-pentene, and the structural unit (ii) is a structural unit derived from a copolymerizable monomer with 4-methyl-1-pentene.

[0058] Equipment: JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer Solvent: o-dichlorobenzene / heavy benzene (80% by volume / 20% by volume) mixed solvent Sample concentration: 55mg / 0.6mL Measurement temperature: 120℃ Observation kernel: 13 C(125MHz) Sequence: Single pulse proton decoupling Pulse width: 4.7μsec (45° pulse) Repeat time: 5.5 seconds Number of times: 10,000 or more

[0059] <Intrinsic viscosity [η]> The intrinsic viscosity [η] of each of the polymers synthesized in the above Production Examples was measured at 135° C. using decalin as a solvent. Specifically, about 20 mg of each polymer synthesized in the above Production Examples was weighed out, dissolved in 15 mL of decalin, and the specific viscosity η sp The decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity η was measured in the same manner. sp This dilution procedure was repeated two more times, and the η sp The value of / C was calculated as the intrinsic viscosity (see the following formula). The results are shown in Table 1. [η]=lim(η sp / C) (C→0)

[0060] <Meso-dyad fraction> The meso diad fraction of each polymer synthesized in the above production example was defined as the ratio at which the directions of the isobutyl branches were the same when any two head-to-tail linked 4-methyl-1-pentene unit chains in the polymer chain were represented in a planar zigzag structure, 13 and was determined from the C-NMR spectrum by the following formula. The results are shown in Table 1. Meso diad fraction (%) = [m / (m + r)] × 100 (In the formula, m and r represent the absorption intensities (integrated values) derived from the main chain methylene of the 4-methyl-1-pentene units linked head-to-tail, which will be described later.)

[0061] 13 The C-NMR spectrum was measured under the following apparatus and conditions. Note that 128 ppm of benzene-d6 was used as the reference value for chemical shift. Apparatus: ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. Solvent: o-dichlorobenzene / benzene-d6 (volume ratio 4 / 1) mixed solvent Sample concentration: 60 mg / 0.6 mL Measurement temperature: 120 °C Observed nucleus: 13 C (125 MHz) Sequence: Single pulse proton broadband decoupling Pulse width: 5.0 μs (45° pulse) Repetition time: 5.5 s

[0062] In the obtained 13 C-NMR spectrum peak region, the region of 41.5 to 43.3 ppm was divided by the minimum point of the peak profile, and the high magnetic field side was classified as the first region and the low magnetic field side was classified as the second region. In the first region, the main chain methylene in the two-chain of 4-methyl-1-pentene units indicated by (m) resonates, and the integrated value when the measured polymer was regarded as a 4-methyl-1-pentene homopolymer was defined as "m". In the second region, the main chain methylene in the two-chain of 4-methyl-1-pentene units indicated by (r) resonates, and the integrated value was defined as "r". The detection limit was defined as less than 0.01%.

[0063] <Melting point (Tm)> For each of the polymers synthesized in the above Production Examples, the exothermic and endothermic curves were obtained using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the peak position during the temperature rise was taken as the melting point (Tm). The measurement was performed as follows. About 5 mg of the polymer was packed in an aluminum pan for measurement, and the temperature was raised from 20°C to 280°C at a heating rate of 10°C / min. After holding at 280°C for 5 minutes, the temperature was lowered to 20°C at a cooling rate of 10°C / min and held at 20°C for 5 minutes. Next, the temperature was raised again from 20°C to 280°C at a heating rate of 10°C / min, and the temperature was lowered again to 50°C at a cooling rate of 50°C / min. The melting point (Tm) was determined based on the melting peak that appeared during the second heating. When there were multiple melting peaks, the higher peak temperature was taken as the melting point (Tm). The results are shown in Table 1.

[0064] <Example 1> [Preparation of Composition] Methylcyclohexane (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to 1.0 g of polymer 1 so that the solid concentration was 5 mass%, and the mixture was stirred at 90°C, 3 hours, and 600 rpm to prepare a composition containing polymer 1.

[0065] [Evaluation of Solvent Stability] The prepared compositions were stored at room temperature (25° C.) for 3 hours after the completion of preparation, and then visually observed under visible light and evaluated according to the following evaluation criteria. The results are shown in Table 1. (Evaluation Criteria) ○: Haze value measured by the following method is less than 5%. ×: Haze value measured by the method described below is 5% or more.

[0066] [Haze measurement] Using the prepared composition, the proportion of transmitted light that deviated from the incident light by 2.5° or more due to forward scattering among the transmitted light that passed through the composition filled in a glass cell was measured in accordance with JIS K 7136:2000 using a turbidity meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.

[0067] <Comparative Example 1> A composition was prepared and evaluated in the same manner as in Example 1, except that Polymer 2 was used instead of Polymer 1. The evaluation results of the obtained composition are shown in Table 1.

[0068] <Comparative Example 2> A composition was prepared and evaluated in the same manner as in Example 1, except that Polymer 3 was used instead of Polymer 1. The evaluation results of the obtained composition are shown in Table 1.

[0069] [Table 1]

Claims

1. A polymer composition comprising a 4-methyl-1-pentene polymer (A) that satisfies the following requirements (i) to (iii), and a solvent (B). Requirement (i): Consists only of structural units derived from 4-methyl-1-pentene Requirement (ii): 13 The mesodiad fraction measured by C-NMR is 98.0% or less. Requirement (iii): The melting point measured by a differential scanning calorimeter is 200° C. or higher.

2. The polymer composition of claim 1 , wherein the solvent (B) comprises methylcyclohexane.

3. The polymer composition according to claim 1 or 2, wherein the polymer (A) further satisfies the following requirement (iv): Requirement (iv): The intrinsic viscosity [η] measured in decalin at 135° C. is 0.10 to 0.23 dl / g.

4. The polymer composition according to claim 1 or 2, wherein the content of the polymer (A) in the polymer composition is 1.0 to 10.0 mass %.

5. The polymer (A), 13 The mesodiad fraction measured by C-NMR is 96.0% or less, 3. The polymer composition according to claim 1, wherein the polymer (A) has a melting point of 205° C. or higher as measured by a differential scanning calorimeter.

6. A molded article formed from the polymer composition according to claim 1 or 2.

7. The molded article according to claim 6, which is a film or a container.

8. A fiber composite material comprising a layer formed from the polymer composition according to claim 1 or 2 and a fiber substrate.

9. A textile product comprising the fibre composite material according to claim 8.

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